제출문 환경부장관귀하 본보고서를 나노기술기반폐글리세롤및폐락틱산 / 숙신산활용 고부가가치바이오화합물제조촉매기술및공정개발 과제의 최종보고서로제출합니다 년 10 월 주관연구기관 : 서울대학교산학협력단주관연구기관장 : 성노현 ( 주관 ) 연구책임자 : 이종협 ( 주

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1 보안과제 [ ], 일반과제 [ ] 최종보고서 환경융합신기술개발사업 나노기술기반폐글리세롤및폐락틱산 / 숙신산활용고부가가치바이오화합물제조촉매기술및공정개발 Process Development for Production of high-valued bio-chemicals From Waste Biomass 서울대학교 / 이종협 환경부한국환경산업기술원 - 1 -

2 제출문 환경부장관귀하 본보고서를 나노기술기반폐글리세롤및폐락틱산 / 숙신산활용 고부가가치바이오화합물제조촉매기술및공정개발 과제의 최종보고서로제출합니다 년 10 월 주관연구기관 : 서울대학교산학협력단주관연구기관장 : 성노현 ( 주관 ) 연구책임자 : 이종협 ( 주관 ) 참여연구원 : 강경보, 강종원, 김왕규, 김지현, 김태용, 김현아, 박대성, 박홍석, 백광현, 백자연, 서영종, 송현돈, 유성주, 유재경, 유종철, 윤다님, 윤양식, 이수영, 이재연, 이종권, 전진오, 조정모, 채한승, 최영헌 - 2 -

3 요약서 사업명환경융합신기술개발사업과제번호 환경융합신기술폐바이오매스환경자원순환단위사업명대분류중분류에너지화개발사업융합기술개발융합기술개발 과제명 최종성과기술 연구책임자 연구기관명및소속부서명 나노기술기반폐글리세롤및폐락틱산 / 숙신산활용고부가가치바이오화합물제조촉매기술및공정개발 폐글리세롤및폐락틱산 / 숙신산유래고부가가치화합물생산을위한제조공정해당단계총 : 25 명참여내부 : 25 명연구원수외부 : 0 명 이종협 총연구기간참여연구원수 총 : 63 명내부 : 63 명외부 : 0 명 기술단계 참여기업 1 단계원천 2 단계응용 롯데케미칼 총연구기간 ~ 총연구비 정부 :1,951,000 천원기업 :1,191,000 천원계 : 3,142,000 천원 연락처 이메일 jyi@snu.ac.kr 총연구기간 09.06~ 연구기관서울대학교산학협력단국공립연구기관유형 위탁기관명 개발목적 및필요성 연구개발 결과 위탁책임자 지속적인에너지수요의증가와국제유가의불안정성으로인해석유를대 체할차세대신재생에너지원개발이활발하게이루어지고있는가운데바이 오매스유래의에너지원이유리함. 바이오에너지원중에서도버려지는폐자원을에너지화하여활용하는것이 매우중요하며바이오연료공정의경제성과효용도를높이기위해바이오리 파이너리공정에서발생하는폐자원이나바이오디젤생산시발생하는많은 양의폐글리세롤을고부가가치화학제품으로생산하는공정이필수적임. 본과제에서는폐자원에서발생하는글리세롤과폐락틱산및폐숙신산으 로부터고부가가치바이오화합물및 C3/C4 바이오단량체제조기술과공정 을개발함을목적으로함. 글리세롤로부터 1,2-프로판디올, 1,3-프로판디올, 폴리우레탄및아크릴산 직접생산기술개발 - 고온 / 고압반응기설계및제조 - 구리담지촉매에의한 1,2- 프로판디올생산과조촉매의첨가로 90% 이상의 수율달성 - 글리세롤로부터 1,3- 프로판디올생산을위한귀금속 (Pt) 담지촉매의경우 최고성능확인 (55.6% 수율 ) - PCL (polycaprolactone) 을사용하여기존에쉽게깨지는성질을보완하여 유연한폴리우레탄을합성함

4 - 3차원의열린중형기공구조를갖는산촉매물질을제조하여기존의상용산촉매 (HZSM-5, MCM-41) 와비교하여우수한활성과높은안정성을나타냄 - 일정한구조를유지하면서산특성을조절할수있는특징을가져응용가능성이높음 - 산촉매와산화촉매의이중층촉매시스템을통해글리세롤로부터아크릴산을생산함. 특히, 이번연구에서새로개발된촉매와몰리브데늄-바나듐의혼합산화물촉매를이용하여 40% 이상의아크릴산수율을얻음. - 정제하지않은글리세롤을반응물을사용하여테스트를진행하였음. - 이원기능촉매개발을통하여한촉매하에서아크릴산직접생산가능. - 벤치규모에서의아크릴산생산을위해산촉매와산화촉매를성형함. 스케일업후에도 40 % 이상의아크릴산수율달성. - 산촉매와산화촉매의이중층반응시스템에서반응속도론적연구를기반으로하여반응속도파라미터를계산함. 이를통해글리세롤로부터아크릴산을생산하는공정의설계, 모사및유용성평가. 폐락틱산 / 폐숙신산전환연구 - 고온, 고압분위기에일어나는폐락틱산의수소화분해반응을위해회분식반응기를설계 - 금속스크리닝을통하여루테늄담지촉매의높은활성및프로필렌글리콜의선택도확인 - 반응장치설계및반응실험조건확립 - 팔라듐 (Pd) 담지촉매에서의반응온도와압력에따른감마부티로락톤의수율변화를확인. 알루미나제어로젤에담지된촉매가상용알루미나에담지된촉매에비해우수한활성을보임. - 팔라듐 (Pd)-알루미나복합체촉매를제조후폐숙신산의수소화반응에응용함. - 레늄 (Re) 과구리 (Cu) 가포함된탄소복합체촉매를이용하여벤치규모의실증화를달성함. 레늄이포함된촉매가재이용성과안정성에서더우수함을보임. 연구결과로 SCI 논문 18 건, 특허 9 편등록및 13 편출원의성과를달성함

5 <3 차원기공을갖는새로운모양의산촉매 > 공정 제품 사진및도면 < 글리세롤산화탈수반응공정모식도 > < 벤치규모반응기의모습 > - 5 -

< 레늄과구리가포함된탄소복합체촉매 > 성능사양및 기술개발수준 활용계획 - 기존 1,2-프로판디올및 1,3-프로판디올의생물학적생산공정을대체할수있는새로운촉매공정을제시하고높은전환율과선택도를보임. - 새로운모양을갖는산촉매개발을통하여바이오매스유래및석유화학의분자크기가큰물질의전환에서기존산업에서사용되고있는 HZSM-5보다더높은활성을보임.

6 < 레늄과구리가포함된탄소복합체촉매 > 성능사양및 기술개발수준 활용계획 - 기존 1,2-프로판디올및 1,3-프로판디올의생물학적생산공정을대체할수있는새로운촉매공정을제시하고높은전환율과선택도를보임. - 새로운모양을갖는산촉매개발을통하여바이오매스유래및석유화학의분자크기가큰물질의전환에서기존산업에서사용되고있는 HZSM-5보다더높은활성을보임. - 촉매의비활성화에대한저항성이강한열린기공구조의산촉매와이원기능촉매를이중층시스템에적용하여 1000시간동안의글리세롤전환율유지 (>99%) 를달성하였고이는세계최고수준의안정성임. - 반응속도론적연구를통하여스케일업의초석을마련하고, 공정모사를통하여경제성을확인하여추후실증화에대한기초자료로사용가능. - 폐락틱산 / 숙신산전환반응에서수소압을낮추면서도높은안정성과성능을갖는촉매개발하였함. 본연구를통하여많은특허출원및등록과논문출판으로우수성을증명함. 폐글리세롤로부터고분자소재의제조기술상용화를위하여다양한촉매를제조하고공정의개발. 관련기술의지적재산권을확보하여기술선점의우위를확보하고더나아가촉매소재의상용화를통해고부가가치창출기대. 락틱산및숙신산으로부터 C3, C4 단량체를제조하는공정의상용화를기대하며바이오플라스틱과같은새로운산업용제품과석유화학대체화학제품등의산업화기술확보

7 주요성과 색인어 ( 각 5 개이상 ) 특허 출원 ( 국내 ) 13 건등록 ( 국내 ) 9 건출원 ( 국외 ) 출원 ( 국외 ) 논문 SCI급 18 건 일반 인증 신기술인증 신기술검증 매출 국내매출 해외수출 기타성과 환경부차세대핵심기술사업최우수등급 ( 한글 ) 폐글리세롤, 폐락틱산, 폐숙신산, 촉매반응, 바이오화합물 ( 영문 ) Waste glycerol, Waste Lactic acid, Waste succinic acid, Catalysis, Bio-chemicals - 7 -

8 요약문 연구개발결과의보안등급 보안등급분류 보안과제 일반과제 결정사유 보안과제인경우필히전문위원과협의한후결정사유에대해전문위원이내용작성 본문의내용을요약하여작성 ( 최종평가시평가활용자료이므로반드시작성 ) 평가의착안점및기준 협약용연구개발계획서내용을참고하여작성 구분 세부내용 평가의착안점및기준 글리세롤전환을위한반응시스템설치및촉매계스크리닝 반응온도 300 o C, 반응압력 250 기압이하 글리세롤로부터폴리올합성기술수립폴리올합성유무 1차 C3, C4 바이오단량체제조를위한년도반응온도 400 o C 이하 / 반응압력 200기압이하반응기설계및초기조건선정 C3, C4 바이오단량체제조를위한금속및산화물촉매선별및반응실험 폐락틱산 70% 이상 / 폐숙신산전환율 65 % 이상 2 차년도 3 차년도 글리세롤전환을위한불균일상촉매개발및촉매계선정 폴리우레탄계열바이오폴리머제조 C3, C4 바이오단량체제조를위한생성물별선택적촉매계개발및담체성분선정글리세롤전환을위한나노구조의촉매제조및특성변화연구 C4 바이오단량체생산을위한나노구조의촉매제조및특성변화연구 촉매의재이용및안정성연구 연속식불균일촉매공정및분리정제공정연구 글리세롤전환율 60% 이상, 아크롤레인선택도 60 % 이상글리세롤전환율 60% 이상, 1,2-PDO 선택도 60% 이상글리세롤전환율 40% 이상, 1,3-PDO 선택도 40% 이상 폴리우레탄합성유무 PG/PDO/MA/AA 수율 65% 이상, BDO/GBL/THF/NMP 수율 60% 이상에탄올 / 부탄올수율 40% 이상 글리세롤전환율 80% 이상아크릴산선택도 15% 이상폐숙신산전환율 80% 이상 BDO/GBL/THF 수율 65% 이상촉매수명 > 10 h 촉매재이용효율 > 70% 공정반응기설계및초기조건선정 - 8 -

9 4 차년도 5 차년도 최종평가 글리세롤전환을위한촉매의각생성물별수율향상촉매반응현상및안정성연구 C4 바이오단량체생산을위한촉매의각생성물별수율향상촉매반응현상및안정성연구 촉매의재이용및분리공정기술확립 글리세롤전환을위한최적의촉매제안 C4바이오단량체생산을위한최적의촉매제안글리세롤전환및 C4 바이오단량체제조를위한벤치규모실증화 글리세롤전환용최적의나노촉매 C4 바이오단량체생성물별최적나노촉매시스템개발 촉매의재이용및분리공정기술확립 글리세롤전환및 C4 바이오단량체제조공정벤치규모실증화 글리세롤전환율 90% 이상아크릴산선택도 25% 이상 폐숙신산전환율 85% 이상 BDO/GBL/THF 수율 70% 이상 촉매수명 > 1000h 촉매재이용효율 > 80% 글리세롤전환율 90% 이상아크릴산선택도 40% 이상. 폐숙신산전환율 90% 이상 BDO/GBL/THF 수율 75% 이상 벤치규모 10kg/day 글리세롤전환율 90% 이상아크릴산선택도 40% 이상폐숙신산전환율 90% 이상 BDO/GBL/THF 수율 75% 이상촉매수명 > 1,000h 촉매재이용효율 > 80% 벤치규모 10kg/day Ⅰ. 연구과제명 주관과제명 : 나노기술기반폐글리세롤및폐락틱산 / 숙신산활용고부가가치바이오화합물제조촉매기술및공정개발 ( 세부1) 과제명 :NT기반촉매공정에의한폐바이오매스의저탄소형고급연료화전환기술개발 ( 세부2) 과제명 : 폐식용유로부터초임계 촉매융합공정을이용한차세대바이오디젤생산기술개발 - 9 -

10 Ⅱ. 연구개발의목적및필요성 지속적인에너지수요의증가와국제유가의불안정성으로인해석유를대체할차세대신재생에너지원개발이활발하게이루어지고있는가운데바이오매스유래의에너지원이유리함. 바이오에너지원중에서도버려지는폐자원을에너지화하여활용하는것이매우중요하며바이오연료공정의경제성과효용도를높이기위해바이오리파이너리공정에서발생하는폐자원이나바이오디젤생산시발생하는많은양의폐글리세롤을고부가가치화학제품으로생산하는공정이필수적임. 본과제에서는폐자원에서발생하는글리세롤과폐락틱산및폐숙신산으로부터고부가가치바이오화합물및 C3/C4 바이오단량체제조기술과공정을개발함을목적으로함. Ⅲ. 연구개발의내용및범위 폐글리세롤로부터고부가가치제품제조용촉매개발 - 금속촉매를이용한글리세롤로부터 1,2-PDO 및 1,3-PDO의직접생산기술개발 - 글리세롤로부터폴리올합성기술수립및폴리우레탄제조기술개발 - 글리세롤탈수반응을위한나노구조촉매제조및특성변화에따른영향분석 - 이중층촉매시스템에서의글리세롤의산화탈수반응에의한아크릴산생산기술개발 - 이원기능촉매개발을통한글리세롤로부터아크릴산으로의직접전환기술개발 폐락틱산및폐숙신산유래 C3 및 C4 바이오단량체제조기술개발 - 폐락틱산전환공정시스템설계및반응조건선정 - 폐락틱산의탈수반응에의한프로필렌글리콜의제조촉매개발 - 폐숙신산으로부터 C4 바이오단량체생산을위한반응장치설계및반응실험조건확립 - 폐숙신산유래의 C4 바이오단량체목표생성물에따른선택적촉매물질

11 선정및제조 벤치규모의실증화및반응공정모사 - 글리세롤로부터아크릴산생산반응시스템의스케일업 - 스케일업에의해얻어진생성물의분석및사용된촉매의성능평가 - 반응속도론적연구를바탕으로한공정모사및유용성평가 - 회분식반응시스템에서의숙신산전환반응의벤치규모실증화 Ⅳ. 연구개발결과 금속촉매를이용한글리세롤로부터 1,2-PDO 및 1,3-PDO의직접생산기술개발 - 고온 / 고압반응기설계및제조 - 금속 (Cu) 담지촉매에의한 1,2-PDO 생산과조촉매성분의영향분석. 글리세롤로부터 1,3-PDO 생산을위한귀금속 (Pt) 담지촉매의경우 2wt% 담지하였을때수율이 55.6% 로가장높았다. 글리세롤로부터폴리올합성기술수립및폴리우레탄제조기술개발 - 폴리올을이용한폴리우레탄의합성은 MDI (Methylene diphenyl diisocyanate diisocyanate) 나 HDI (Hexamethylene diisocyanate) 를이용. Polylactide를함유해쉽게깨지는성질을보완하기위해 PCL (polycaprolactone) 을사용하여유연한폴리우레탄을합성함. 글리세롤탈수반응을위한나노구조촉매제조및특성변화에따른영향분석 - 3차원의열린중형기공구조를갖는산촉매물질을제조하여기존의상용산촉매 (HZSM-5, MCM-41) 와비교하여우수한활성과높은안정성을나타냄 - 일정한구조를유지하면서산특성을조절할수있는특징을가져응용가능성이높음 이중층촉매시스템에서의글리세롤의산화탈수반응에의한아크릴산생산

12 기술개발 - 산촉매와산화촉매의이중층촉매시스템을통해글리세롤로부터아크릴산을생산함. 특히, 이번연구에서새로개발된촉매와몰리브데늄-바나듐의혼합산화물촉매를이용하여 40% 이상의아크릴산수율을얻음. - 정제되지않은글리세롤을반응물로사용하여약 20% 의아크릴산수율을얻음 이원기능촉매개발을통한글리세롤로부터아크릴산으로의직접전환기술개발 - 몰리브데늄-바나듐-텅스텐을기반으로한이원기능촉매를제조하여중간생성물인아크롤레인을단일반응기에서아크릴산까지전환시키는데성공함. 폐락틱산전환공정시스템설계 - 고온, 고압분위기에일어나는폐락틱산의수소화분해반응을위해회분식 반응기를설계 폐락틱산의탈수반응에의한프로필렌글리콜의제조촉매개발 - 은 (Ag), 코발트 (Co), 크롬 (Cr), 구리 (Cu), 니켈 (Ni), 백금 (Pt), 루테늄 (Ru) 을실리카에담지하여촉매제조. 루테늄을담지한촉매에서가장높은활성을확인. - 루테늄을담지한담체의종류에따른반응성의차이를확인. 폐숙신산유래의 C4 바이오단량체생산을위한반응장치설계및반응실험조건확립 C~300 C의반응온도에서 100bar의반응압력을견딜수있는회분식반응시스템의설계 폐숙신산유래의 C4 바이오단량체목표생성물에따른선택적촉매물질선정및제조 - 팔라듐 (Pd) 담지촉매에서의반응온도와압력에따른감마부티로락톤의수율변화를확인. 알루미나제어로젤에담지된촉매가상용알루미나에담지된촉매에비해우수한활성을보임

13 - 팔라듐 (Pd)- 알루미나복합체촉매를제조후폐숙신산의수소화반응에응용 함. 글리세롤로부터아크릴산생산반응시스템의스케일업과반응결과및촉매성능분석 - 벤치규모에서의아크릴산생산을위해산촉매와산화촉매를성형함. 스케일업이후의반응결과를바탕으로촉매의성능을분석함. 반응속도론적연구를바탕으로한공정모사및유용성평가 - 산촉매와산화촉매의이중층반응시스템에서반응속도론적연구를기반으로하여반응속도파라미터를계산함. 이를통해글리세롤로부터아크릴산을생산하는공정의설계및모사. 회분식반응시스템에서의숙신산전환반응의벤치규모실증화 - 레늄 (Re) 과구리 (Cu) 가포함된탄소복합체촉매를이용하여벤치규모의실증화를달성함. 레늄이포함된촉매가재이용성과안정성에서더우수함을보임. 연구결과로 SCI 논문 18 건, 특허 9 편등록및 13 편출원의성과를달성함. Ⅴ. 연구개발결과의활용계획 폐글리세롤로부터고분자소재의제조기술상용화를위하여다양한촉매를제조하고공정의개발. 관련기술의지적재산권을확보하여기술선점의우위를확보하고더나아가촉매소재의상용화를통해고부가가치창출기대. 락틱산및숙신산으로부터 C3, C4 단량체를제조하는공정의상용화를기대하며바이오플라스틱과같은새로운산업용제품과석유화학대체화학제품등의산업화기술확보

14 SUMMARY ( 영문요약문 ) Ⅰ. Title Total Project Name : Process Development for Production of high-valued bio-chemicals From Waste Biomass Unit Research Project 1 : Development of NT-based Catalytic Process for Production of Advanced Biofuel from Waste Biomass Unit Research Project 2 : Next generation biodiesel production from waste cooking oil using supercritical fluid catalyst fusion technology Ⅱ. The Objective & Necessity of the Research Under the circumstance of depletion of fossil fuels and growing environmental issues, biomass-derived energy resources are highly promising alternative sources due to renewability and potential sustainability. Transformation of the waste glycerol, lactic acid, and succinic acid into higher value added chemicals can contribute to reduce the cost of biomass-derived renewable energy resources and substitute petrochemical based process progressively. Therefore the development of catalytic process to convert crude glycerol, lactic acid, and succinic acid are necessary in terms of utilization of wasting raw materials. This project is supposed to developed catalytic process for effective conversion of glycerol and lactic/succinic acid into commercially value-added chemical or C3/C4 platform chemicals

15 Ⅲ. Contents and Scope Development of new catalysts to convert glycerol into high value chemicals - Development of metal supported catalysts to produce 1,2-PDO and 1,3-PDO from glycerol - Synthesis of polyurethane exploiting polyols derived from glycerol - Preparation of nano-structured acid catalysts for glycerol dehydration and elucidation on effects of catalytic properties on the reaction - Production of acrylic acid from glycerol on the two bed catalytic system - Direct conversion of glycerol into acrylic acid over bifunctional catalyst Development of catalysts and chemical process to convert lactic acid and succinic acid into C3/C4 chemicals - Design of reaction system and optimization of reaction condition - Development of efficient catalysts to produce propylene glycol via dehydration of lactic acid - Design of batch reactor system for conversion of succinic acid reactions - Screening and preparation of catalytic materials for conversion of succinic acid into any desired products. Scale up and process simulation of the forementioned reactions - Scale up of the reaction system producing acrylic acid from glycerol - Evaluation of product distribution and catalytic performance at a bench-scaled reactor - Process simulation of acrylic acid production from glycerol based on kinetic studies - Scale up of succinic acid conversion process This project is supposed to developed catalytic process for effective conversion of glycerol and lactic/succinic acid into commercially

16 value-added chemical or C3/C4 platform chemicals. Ⅳ. Results Development of metal supported catalysts to produce 1,2-PDO and 1,3-PDO from glycerol - Design of reactor for high T, P conditions - Glycerol was converted into 1,2-PDO over Cu-supported catalysts and effects of promoters such as Cr were studied. Over Pt-supported catalysts the highest yield (55.6%) for 1,3-PDO was achieved. Synthesis of polyurethane exploiting polyols derived from glycerol - MDI (Methylene diphenyl diisocyanate diisocyanate) and HDI (Hexamethylene diisocyanate) were used to synthesize polyurethane from polyols derived from glycerol. The more flexible polyurethane were synthesized by using PCL (polycaprolactone) to cover its fragile property. Preparation of nano-structured acid catalysts(das, DASP) for glycerol dehydration and elucidation on effects of catalytic properties on the reaction - Development of 3D mesoporous acid catalysts. Compared to typical acid catalysts such as HZSM-5 and MCM-41, the developed catalysts showed high catalytic performance and stability. - Due to the uniform structure and tuneable acidic properties, the developed catalysts are expected to applicable to various reactions. Production of acrylic acid from glycerol on the two bed catalytic system - Acrylic acid were produced from glycerol over the catalyst bed consisting of acid catalyst and oxidative catalyst. Over DASP and Mo-V oxide catalysts, glycerol afforded acrylic acid in more than 40% yield. Direct conversion of glycerol into acrylic acid over bifunctional catalyst - Preparation of Mo-V-W based catalysts to convert glycerol into acrylic acid directly. The bifunctional catalyst make it possible to simplify the reactor system. Design of reaction system and optimization of reaction condition

17 - Batch reactor system was used for hydrogenolysis of lactic acid under high T, P conditions Development of efficient catalysts to produce propylene glycol via dehydration of lactic acid - Metal supported catalysts were prepared and test to convert lactic acid into propylene glycero. Among various metal, Ru was the most active material for the reaction. - The effects of support materials were studied. Design of batch reactor system for conversion of succinic acid reactions - Installation of batch reactor system for high T, P conditions Screening and preparation of catalytic materials for conversion of succinic acid into any desired products. - Over Pd supported catalysts, effects of reaction condition(t, P) on yields for γ-butyrolactone were studied. Pd catalysts using alumina Xerogel showed more enhanced catalytic activity than typical alumina support. - Pd-Alumina composite catalysts were prepared and applied to hydrogenation of succinic acid. Scale up of the reaction system producing acrylic acid from glycerol - Extrusion of acid catalysts and coating of oxidative catalysts were preceded and the reactor system was scaled up. Based on the results of bench-scaled reaction tests, catalytic performance was evaluated. Evaluation of product distribution and catalytic performance at a bench-scaled reactor Process simulation of acrylic acid production from glycerol based on kinetic studies - Based on kinetic studies, kinetic parameters for the reactions to produce acrylic acid from glycerol were estimated. The process producing acrylic acid from glycerol was designed and the kinetic parameters were applied to reflect catalytic performance in the simulating software. Scale up of succinic acid conversion process - Re- and Cu-Carbon composite catalysts were used in the bench-scaled reaction tests. The former catalysts showed better catalytic performance

18 in terms of reneration and stability. Ⅴ. Business Application Based the Outcomes The technology allows more effective catalytic process for various chemicals derived from glycerol, lactic acid and succinic acid and provides fundamental for the commercialization of new chemical process or catalysts. Based on fundamental technology, the commercialization of catalysts or process for higher value chemicals can be possible by occupying intellectual property rights of technologies mentioned above in advance. The catalytic processes developed from this project are highly expected to replace the petrochemical process and create new market for C3 and C4 chemicals

19 제 1 장서론 30 제 1 절연구개발과제의개요 연구개발의목적및필요성 연구개발대상기술의차별성 38 제 2 절연구개발의국내외현황 41 제 3 절연구개발의내용및범위 연구개발의최종목표 연도별연구개발목표및평가방법 연도별추진체계 60 제 2 장연구개발수행내용및결과 64 제 1 절연구개발결과및토의 폐글리세롤의고부가가치화합물로의전환 64 가. 글리세롤로부터 1,2- 프로판디올생산반응 64 나. 글리세롤로부터 1,3- 프로판디올생산반응 85 다. 글리세롤로부터아크롤레인생산반응 96 라. 폴리올을이용한폴리우레탄합성물질제조 101 마. 글리세롤로부터아크릴산생산반응 폐락틱산및숙신산의고부가가치화합물로의전환 243 가. 폐락틱산의전환반응 243 나. 폐숙신산의전환반응 261 제 2 절연구개발결과요약 314 제 3 장목표달성도및관련분야기여도 316 제 1 절연도별연구개발목표의달성도 316 제 2 절관련분야의기술발전기여도 ( 환경적성과포함 ) 317 제 4 장연구개발결과의활용계획등 320 제 1 절연구개발결과의활용계획 320 제 2 절연구개발과정에서수집한해외과학기술정보 325 제 3 절연구개발결과의보안등급

20 제 4 절 NTIS 에등록한연구시설 장비현황 326 제 5 장참고문헌

21 [ 그림 1] 글리세롤로부터 1,2-PDO 전환반응의메커니즘 65 [ 그림 2] 고온고압반응기의설치모습 66 [ 그림 3] 다양한담체에서 Cu 를촉매로한 TEM image 분석결과 : (a)alumina, (b)silica, (c)titania, (d)carbon 69 [ 그림 4] 다양한담체에서 Cu 를촉매로한 XRD 분석결과 70 [ 그림 5] 각담체에서의반응성결과및 Fe 를조촉매로한촉매에서의반응성결과 71 [ 그림 6] Alumina 와 mesorporous alumina 를담체로촉매 (Cu, Cu/Fe) XRD 분석결과 72 [ 그림 7] Cu/M-alu, Cu/Fe/M-alu 의 TEM 이미지 73 [ 그림 8] 다중기공성알루미나담체의 BET 분석결과 73 [ 그림 9] TPR 분석결과 (Cu 2 O, CuO) 74 [ 그림 10] 상용 alumina 와중형기공의 alumina 를담체로한 Cu 촉매의반응성결과 75 [ 그림 11] BET 분석결과 (Activated carbon, Large pore carbon) 76 [ 그림 12] Activated carbon 과 Large Pore Carbon 의 TEM image 77 [ 그림 13] 큰기공구조를가진 carbon 담체에서의반응결과 [ 그림 14] 소성후 NiCu 촉매의 XRD 결과 79 [ 그림 15] 환원처리후 XRD 결과 ( 녹색 : Ni, 파란색 : Cu) 79 [ 그림 16] 글리세롤을프로필렌글리콜로전환시키는수소화분해반응의결과 [ 그림 17] ZnCuCr 촉매의환원후 XRD 결과 (a) CuCr 2 O 4, (b) ZnCuCr-1, (c) ZnCuCr-5 (d) ZnCuCr-10, (e) ZnCuCr-25, (f) ZnCuCr-33, (g) ZnCr 2 O 4, Cu ( ), reduced CuCr 2 O 4 ( ), ZnCr 2 O 4 ( ), ZnO(О). 82 [ 그림 18] ZnCuCr 촉매의 H 2 -TPR 결과 : (a) CuCr 2 O 4, (b) ZnCuCr-1, (c) ZnCuCr-5 (d) ZnCuCr-10, (e) ZnCuCr-25, (f) ZnCuCr-33, (g) ZnCr 2 O [ 그림 19] ZnCuCr 를사용하여글리세롤전환반응수행결과. 반응온도 : 220, 반응시간 : 12h, 수소압력 : 80bar. 84 [ 그림 20] 수소화반응을통해서글리세롤을저가폴리올또는알코올로전환시키는반응의반응경로 85 [ 그림 21] 가 ) 수소화반응기, 나 ) Gas Chromatography(GC), 다 ) High Performance Liquid Chromatography(HPLC), 라 ) 수소화반응용기 100, 30, 10cc, 마 ) GC 용 columns(hp-innowax, HP-FFAP). 86 [ 그림 22] 글리세롤수소화반응후예상되는물질에대한 GC 분석결과 87 [ 그림 23] Pt/supported ZrO 2 촉매위에수소흡착메커니즘 88 [ 그림 24] Zirconia, sulfated zirconia 및 Pt-sulfated zirconia 의 XRD 분석결과. (T: tetragonal of ZrO 2, M: monoclinic ZrO 2 ) 89 [ 그림 25] Zirconia, sulfated zirconia 및 Pt-sulfated zirconia 의 H 2 -TPR 결과 90 [ 그림 26] Zirconia, sulfated zirconia 및 Pt-sulfated zirconia 의 NH 3 -TPD 결과 91 [ 그림 27] Zirconia, sulfated zirconia 및 Pt-sulfated zirconia 의 NH 3 흡착 In-situ FTIR 결과 91 [ 그림 28] Zirconia, sulfated zirconia, Pt/supported zirconia 를사용하여글리세롤의 1,3-PDO 로의전환반응적용결과 93 [ 그림 29] Pt-sulfated zirconia 촉매의재이용성테스트 95 [ 그림 30] 글리세롤로부터아크롤레인생산을위한반응시스템 97 [ 그림 31] 글리세롤탈수반응온도스크리닝결과 98 [ 그림 32] 반응물주입속도스크리닝결과

22 [ 그림 33] 반응시간 time-on-stream 결과 99 [ 그림 34] 다양한실리카담체에담지한헤테로폴리산촉매 99 [ 그림 35] 다양한실리카담체에담지한헤테로폴리산촉매의반응결과 ( 글리세롤전환율 ) 100 [ 그림 36] 다양한실리카담체에담지한헤테로폴리산촉매의반응결과 ( 아크롤레인선택도 ) 101 [ 그림 37] 폴리올로부터폴리우레탄및폴리에스터합성개략도 101 [ 그림 38] 생분해성을가지는폴리우레탄 102 [ 그림 39] 생분해성고분자합성모식도 103 [ 그림 40] Polylactide 의구조적특성 ( 1 H-NMR) 103 [ 그림 41] Polylactide 의분자량분포 (GPC) 104 [ 그림 42] 용매증류장치를이용한용매정제 104 [ 그림 43] Polylactide 를포함하는블록공중합체 PLA-b-PS 105 [ 그림 44] Polylactide 를포함하는블록공중합체 P3HT-b-PLA 105 [ 그림 45] 생분해성을가지는 polylactide 를포함하는폴리우레탄 106 [ 그림 46] 폴리우레탄합성장치 106 [ 그림 47] Polyol 로부터생분해성을가지는 Polyurethane 합성개략도 107 [ 그림 48] 생분해성 polyurethane 의분자량및분자량분포도 108 [ 그림 49] FT-IR 와 DSC 를이용한생분해성 polyurethane 의구조및열적성질확인 109 [ 그림 50] ZDiisocyanate 에따른 polyurethane 의 flexibility 측정 109 [ 그림 51] DAS 촉매의개략도 111 [ 그림 52] DAS 와 DASP 촉매의제조법 111 [ 그림 53] 첫번째수열처리시간을조절한 DAS 의 SEM 사진. a) 1 시간, b) 2 시간, c) 3 시간, d) 4시간 112 [ 그림 54] ph 조절없이제조한 DAS의 SEM 사진 113 [ 그림 55] 다양한적정 ph에서제조된 DAS의 SEM 사진 (Si/Al=40) a) ph 7, b) ph 6, c) ph 5, d) ph [ 그림 56] 다양한적정 ph에서제조된 DAS의 SEM 사진 (Si/Al=15) a) ph 7, b) ph 6, c) ph 5, d) ph [ 그림 57] 다양한비율의 Si/Al을갖는 DAS와 DASP 촉매의 SEM 사진 DAS: Si/Al = a) 15, b) 25, c) 40, d) 50, and e) 60, DASP: Si/Al = f) 25, g) 40, and h) [ 그림 58] 다양한비율의 Si/Al을갖는 DAS와 DASP 촉매의 TEM 사진 DAS: Si/Al = a) 15, b) 25, c) 40, d) 50, and e) 60, DASP: Si/Al = f) 25, g) 40, and h) [ 그림 59] DAS-60의 a) HAADF-STEM 사진, STEM-EDS mapping 결과 b) Si, and c) Al 117 [ 그림 60] 다양한비율의 Si/Al을갖는 DAS 촉매의흡착등온선, Si/Al = a) 15, b) 25, c) 40, d) 50, and e) [ 그림 61] DAS 촉매의기공크기분산도곡선, Si/Al = a) 15, b) 25, c) 40, d) 50, and e) [ 그림 62] 다양한비율의 Si/Al을갖는 DASP 촉매의흡착등온선 Si/Al = a) 15, b) 25, c) 40, and d) [ 그림 63] DASP 촉매의기공크기분산도곡선 Si/Al = a) 15, b) 25, c) 40, and d) [ 그림 64] DAS 촉매의 XRD 패턴 Si/Al = a) 15, b) 25, c) 40, d) 50, and e)

23 [ 그림 65] DASP 촉매의 XRD 패턴 Si/Al = a) 15, b) 25, c) 40, and d) [ 그림 66] 다양한비율의 Si/Al 을갖는 DAS 촉매의 27 Al MAS NMR 스펙트럼. Si/Al = a) 15, b) 25, c) 40, d) 50, and e) [ 그림 67] 다양한비율의 Si/Al 을갖는 DASP 촉매의 27 Al MAS NMR 스펙트럼. Si/Al = a) 15, b) 25, c) 40, and d) [ 그림 68] DAS 및 DASP 의예상구조 124 [ 그림 69] 다양한비율의 Si/Al 을갖는 DAS 촉매의 In-situ NH 3 FT-IR 결과 Si/Al = a) 15, b) 25, c) 40, d) 50, and e) [ 그림 70] 다양한비율의 Si/Al 을갖는 DAS 와 DASP 촉매의 In-situ NH 3 FT-IR 결과 126 [ 그림 71] 다양한비율의 Si/Al 을갖는 DAS 촉매의 NH 3 -TPD 분석결과 Si/Al = a) 15, b) 25, c) 40, d) 50, and e) [ 그림 72] 다양한비율의 Si/Al 을갖는 DAS 와 DASP 촉매의 NH 3 -TPD 분석결과 128 [ 그림 73] DAS-40 과 MCM-41 촉매의수열안정성테스트후 TEM 사진 129 [ 그림 74] 산촉매하에서 1,3,5-TIPB 의크래킹반응경로 130 [ 그림 75] DAS 와상용촉매를이용한 1,3,5-TIPB 크래킹반응장기테스트 132 [ 그림 76] 촉매의비활성화분석을위한피팅식 132 [ 그림 77] 수크로오스의수화반응 133 [ 그림 78] DAS 와상용촉매를이용한수크로오스의수화반응결과 134 [ 그림 79] 글리세롤을아크릴산으로전환하는반응의경로 135 [ 그림 80] 산촉매물질의 a) SEM 과 b) TEM 사진 ; 1) DAS(40), 2) DASP(40), 3) Al-MCM-41 and 4) HZSM [ 그림 81] 각촉매 (DAS, DASP, MCM-41, HZSM-5) 의흡착등온선 137 [ 그림 82] 촉매들의기공크기분산도곡선 a) DAS(40), b) DASP(40), c) MCM-41, d) HZSM [ 그림 83] XRD 패턴 (DAS(40), DASP(40), MCM-41, ZSM-5) 138 [ 그림 84] 각촉매의 NH 3 -TPD 분석결과 140 [ 그림 85] 각촉매의 In-situ NH 3 FT-IR 결과 141 [ 그림 86] 각촉매에서의글리세롤전환율, 촉매의양 : A) 0.1g, B) 0.05g 143 [ 그림 87] 촉매표면의산점밀도에따른 TOF(0) 변화 144 [ 그림 88] D 각촉매에서의아크롤레인선택도, 촉매의양 : A) 0.1g, B) 0.05g 145 [ 그림 89] 생성된아크롤레인 / 아세톨비와브뢴스테드산점 / 루이스산점비의상관관계, 촉매의양 : A) 0.1g, B) 0.05g 146 [ 그림 90] 사용한촉매의 TGA 분석결과 148 [ 그림 91] 촉매의기공크기에따른코크의생성량 148 [ 그림 92] 반응전후촉매들의기공크기분산도곡선 a) DAS(40), b) DASP(40), c) MCM-41, d) HZSM [ 그림 93] DAS-40 와 MoV ( 함침 ) 촉매의장기안정성테스트 (3 차년도연구목표달성 ) 150 [ 그림 94] 산촉매와산화촉매 (MoV oxide) 이중층에서의글리세롤산화탈수반응결과 151 [ 그림 95] 혹독한조건에서의 250 시간동안의장기실험 151 [ 그림 96] DASP-40 과 MoV oxide 를이용한장기반응실험결과 152 [ 그림 97] 산촉매에서의글리세롤전환반응경로 153 [ 그림 98] HZSM-5 의반응실험결과및피팅곡선 a) 250, b) 275, c) [ 그림 99] HZSM-5 를이용한각단계에서의 Arrhenius plot

24 [ 그림 100] DASP-40 의반응실험결과및피팅곡선 a) 250, b) 275, c) [ 그림 101] DASP-40 를이용한각단계에서의 Arrhenius plot 158 [ 그림 102] 시간에따른실험결과와각모델식의피팅곡선, a) DASP-40, b) HZSM-5162 [ 그림 103] 시간에따른실험결과와피팅곡선 163 [ 그림 104] 시간에따른생성물의선택도 (HZSM-5) 164 [ 그림 105] 시간에따른생성물의선택도 (DASP-40) 165 [ 그림 106] 반응시간에따른촉매 (HZSM-5, DASP-40) 의기공크기분산도곡선 167 [ 그림 107] 반응시간에따른촉매 (HZSM-5, DASP-40) 의 NH 3 -TPD 분석결과 168 [ 그림 108] 반응시간에따른촉매 (HZSM-5, DASP-40) 의 TPO 분석결과 170 [ 그림 109] 반응시간에따른촉매 (HZSM-5, DASP-40) 의 13 C NMR 분석결과 171 [ 그림 110] 산화촉매 (MoV oxide) 에서의아크롤레인전환반응경로 171 [ 그림 111] MoV oxide 촉매에서의반응실험결과와피팅곡선 173 [ 그림 112] 글리세롤산화탈수반응공정모식도 175 [ 그림 113] 공정의스케일에따른비용및수익변화 176 [ 그림 114] 공정의스케일에따른 a) 각각의비용및 b) 차지하는비중 176 [ 그림 115] 공정스케일에따른예상투자액회수기간 ( 위 ) 및원료 ( 정제된글리세롤 ) 의가격증가에 따른예상투자액회수기간 177 [ 그림 116] 벤치규모반응기의모습 (a) 반응물주입기, (b) 반응기, (c) 온도및 MFC 컨트롤러, (d) 냉각기, (e) 전기로 180 [ 그림 117] 성형된촉매의전후모습. (a) HZSM-5, (b) MoV 181 [ 그림 118] GHSV 변화에따른 HZSM-5 촉매의활성정도 185 [ 그림 119] GHSV 변화에따른 MoV 촉매의활성정도 186 [ 그림 120] 산소비율에따른생산물의수율및글리세롤의전환율 187 [ 그림 121] 글리세롤 / 산소 =1 일때의생성물의수율및글레세롤의전환율 188 [ 그림 122] 산소비율에따른아크릴산수율의변화양상 188 [ 그림 123] 산소비율에따른아크롤레인수율의변화양상 189 [ 그림 124] 산소비율에따른아세트산수율의변화양상 189 [ 그림 125] 글리세롤의탈수및산화반응경로 190 [ 그림 126] 반응온도별글리세롤전환반응의생산물별수율및글리세롤의전환율 191 [ 그림 127] 250 에서시간에대한반응생성물들의수율및글리세롤전환율변화 192 [ 그림 128] 50 에서시간에대한반응생성물들의수율및글리세롤전환율변화 193 [ 그림 129] 반응온도에따른아크롤레인수율의변화양상 194 [ 그림 130] 반응온도에따른아세트산수율의변화양상 194 [ 그림 131] 반응온도에따른아크릴산수율의변화양상 195 [ 그림 132] HZSM-5 의반응전후형태 196 [ 그림 133] MoV 촉매의열중량분석결과 196 [ 그림 134] HZSM-5 촉매의열중량분석결과 197 [ 그림 135] 장시간벤치규모반응결과생성물의수율및글리세롤의전환율 198 [ 그림 136] 참여기업 ( 롯데케미칼 ) 에있는병렬반응기 a) 주입부, b) 전기로및반응기, c) 반응물주입기, d) 주입부확대사진 198 [ 그림 137] 소성전후의몰리브덴 - 바나듐 - 텅스텐성형촉매의모습 200 [ 그림 138] 촉매의성형및소성순서에따른반응결과 200 [ 그림 139] 이중층반응시스템에서의선택적산화촉매스크리닝결과

25 [ 그림 140] MoV-NbP 촉매의제조방법 204 [ 그림 141] Mo-V-W 촉매의제조방법 205 [ 그림 142] MoV-NbP 촉매들의아크릴산수율 206 [ 그림 143] MoV-NbP 촉매들의아크롤레인수율 206 [ 그림 144] MoV-Nbp 촉매들의이산화탄소및이산화탄소수율 207 [ 그림 145] 다양한 ph 를갖는용액에서제조한 Mo-V-W 촉매의 SEM 사진 208 [ 그림 146] 전구체용액의다양한 ph 조건에서합성된 Mo-V-W 촉매의 XRD 패턴 209 [ 그림 147] 글다양한 ph 조건에서제조된 Mo-V-W 촉매들의글리세롤산화탈수반응결과 210 [ 그림 148] 다양한온도에서열처리를거친 Mo-V-W 촉매의 XRD 패턴 212 [ 그림 149] 다양한온도에서열처리를거친 Mo-V-W 촉매의반응결과 212 [ 그림 150] 이성분계와삼성분계촉매들의 XRD 패턴 213 [ 그림 151] 이성분계와삼성분계촉매들의반응결과비교 214 [ 그림 152] 수열합성법을통한 Mo-V-O 촉매생성원리 215 [ 그림 153] Mo-V 용액과 Mo-V-W 4:1:5 용액의 UV/Vis 분광기분석결과 215 [ 그림 154] 다양한 Mo:V:W 비율을갖는 Mo-V-W 촉매의 XRD 패턴 216 [ 그림 155] Mo-V-W 촉매들의 XRD 패턴 217 [ 그림 156] Mo-V-W 촉매들의 TEM 사진 218 [ 그림 157] Mo-V-W 촉매들의 HR-TEM 사진 218 [ 그림 158] MoVW 촉매의 W L3-edge 에서의 XANES 피크 219 [ 그림 159] MoVW 촉매들의 FT-IR 과 Raman 분석 220 [ 그림 160] Mo 을치환한 W 원자로인한 charge density 변화계산결과 a) Mo 원자치환, b) MoVW 4:1:5 221 [ 그림 161] Mo-V-W 촉매들의 NH 3 -TPD 분석결과 223 [ 그림 162] Mo-V-W 촉매들의 TPR 분석결과 224 [ 그림 163] Mo-V-W 촉매들의글리세롤의산화탈수반응결과 225 [ 그림 164] Mo-V-W 촉매들의글리세롤의산화탈수반응결과 225 [ 그림 165] WO 3 과 MoV 을물리적으로혼합한촉매와 MoVW 4:1:5 촉매와의활성비교 226 [ 그림 166] Mo-V-W 4:1:5 촉매의장기안정성테스트 227 [ 그림 167] 이온교환수지의형태. (a) IRN-97H, (b) IRA-410, (c) IRN [ 그림 168] (a) 등온반응이가능한히팅맨틀, (b) 이온수지를여과시키기위한진공여과기 231 [ 그림 169] 산도조절을거친폐글리세롤 233 [ 그림 170] (a) 페글리세롤, (b) IRN-150, (c) IRN-97H, (d) IRA-410 이온수지와반응후의글리세롤 ; (1): 1 시간, (2): 2 시간, (3): 3 시간 235 [ 그림 171] 순수글리세롤, 폐글리세롤, 정제글리세롤의반응실험결과 239 [ 그림 172] 나트륨이온농도변화에따른아크릴산수율변화 240 [ 그림 173] 폐글리세롤전환반응의수율및전환율 ; HZSM-5 : MoV = 3 : [ 그림 174] 폐글리세롤전환반응의수율및전환율 ; HZSM-5 : MoV = 2.5 : [ 그림 175] 락틱산의반응경로 243 [ 그림 176] 고온고압반응기제원 244 [ 그림 177] 반응속도결정단계 245 [ 그림 178] 랭뮤어 - 힌셀우드매커니즘

26 [ 그림 179] 촉매제조과정 ( 탄소를담지체로한백금 - 금촉매 ) 246 [ 그림 180] 백금 - 금담지촉매의 XRD 그래프 247 [ 그림 181] 촉매별 TEM 사진 (a)p1 (b)p2 (c)p3 (d)p4 248 [ 그림 182] 촉매별전환율및선택도 249 [ 그림 183] 다양한금속을담지한촉매의 XRD 그래프 250 [ 그림 184] 다양한금속을담지한촉매의 XRD 그래프 252 [ 그림 185] 촉매별 TEM 사진 (a)ag/sio 2 (B)Co/SiO 2 (c)cu/sio 2 (d)ni/sio 2 (e)pt/sio 2 (f)ru/sio [ 그림 186] 금속촉매별전환율비교 254 [ 그림 187] Ru/SiO 2 촉매에서시간에따른전환율, 선택도및수율 255 [ 그림 188] Ru/SiO 2 촉매에서압력에따른전환율, 선택도및수율 256 [ 그림 189] Ru/SiO 2 촉매에서온도에따른전환율, 선택도및수율 257 [ 그림 190] (a) XRD 그래프, (b) 투과전자현미경 258 [ 그림 191] 카본담체별반응물의전환율 259 [ 그림 192] Ru/ketjen black 촉매에서시간에따른전환율, 선택도및수율 259 [ 그림 193] Ru/ketjen black 촉매에서온도와압력에따른전환율, 선택도및수율 260 [ 그림 194] 숙신산의수소화반응경로및활성촉매 261 [ 그림 195] 감마부티로락톤제조반응경로 262 [ 그림 196] 폐숙신산의회분식수소화전환반응기설계 264 [ 그림 197] 반응압력별숙신산의수소화반응활성 265 [ 그림 198] 반응온도별숙신산의수소화반응활성 265 [ 그림 199] 반응시간별, 반응물대비촉매양별숙신산의수소화반응활성 266 [ 그림 200] 알루미나제어로젤담체의제조과정모식도 267 [ 그림 201] 알루미나제어로젤담체 (AX) 와알루미나제어로젤담체에담지된팔라듐담지촉매 (Pd/AX) 의질소흡착 - 탈착실험결과 268 [ 그림 202] 알루미나담체와팔라듐담지촉매의 XRD 그래프 269 [ 그림 203] 팔라듐담지촉매의 HR-TEM 이미지 270 [ 그림 204] 팔라듐담지촉매의온도별전환율및선택도 271 [ 그림 205] 팔라듐담지촉매의온도별수율 271 [ 그림 206] 반응부피별반응활성 272 [ 그림 207] 교반속도에따른반응활성 273 [ 그림 208] 숙신산으로부터감마부티로락톤제조반응메커니즘 274 [ 그림 209] 소성온도별제조된알루미나제어로젤담체에담지된팔라듐담지촉매의 X- 선회절스펙트럼분석결과 275 [ 그림 210] 소성온도별제조된알루미나제어로젤담체에담지된팔라듐담지촉매의질소흡착 - 탈착분석결과 277 [ 그림 211] 소성온도별제조된알루미나제어로젤담체에담지된팔라듐담지촉매의숙신산수소화반응활성과산특성의상관관계 279 [ 그림 212] 졸 - 겔법에의한팔라듐 - 알루미나복합체촉매의제조과정 280 [ 그림 213] 졸 - 겔법에의한팔라듐 - 알루미나복합체촉매의질소흡착 - 탈착분석곡선결과 281 [ 그림 214] 환원된팔라듐 - 알루미나복합체촉매 (Pd-A650, Pd-A750, Pd-A850) 의 X- 선회절스펙트럼

27 [ 그림 215] 팔라듐 - 알루미나복합체촉매와팔라듐 / 알루미나담지촉매와의폐숙신산수소화활성비교 283 [ 그림 216] 팔라듐 / 알루미나담지촉매의소성온도에따른팔라듐표면적과촉매활성비교 284 [ 그림 217] 계면활성 - 주형법을이용하여제조된기공성탄소담체및그비교군으로써구형탄소담체와주형법으로제조된기공성탄소담체의제조과정 285 [ 그림 218] 계면활성 - 주형법을이용하여제조된기공성탄소담체및그비교군으로써구형탄소담체와주형법으로제조된기공성탄소담체의전계방출주사전자현미경이미지 287 [ 그림 219] Ru/SC, Ru/TC, Ru/STC 촉매들의질소흡착 - 탈착분석곡선 288 [ 그림 220] Ru/SC, Ru/TC, Ru/STC 촉매들의 X- 선회절스펙트럼 289 [ 그림 221] Ru/SC, Ru/TC, Ru/STC 촉매들의고배율투과전자현미경 (HR-TEM) 이미지 289 [ 그림 222] 황산처리농도에따른중형기공탄소담체제조 292 [ 그림 223] 탄소담체 (MC) 의전계방출주사전자현미경 (FE-SEM) 이미지 293 [ 그림 224] 탄소담체 (MC) 의소각 X- 선회절스펙트럼 294 [ 그림 225] Re/MC 촉매들의질소흡착 - 탈착그래프 296 [ 그림 226] Re/MC 촉매들의 HR-TEM 이미지 297 [ 그림 227] Re/MC 촉매들의 TPR 그래프 298 [ 그림 228] Re/MC 촉매에서레늄금속의입자크기와숙신산수소화반응활성간의상관관계도 300 [ 그림 229] 메탄올을이용하여숙신산으로부터 1,4- 부탄디올을생산하는비고리수소화반응경로 303 [ 그림 230] 구리가포함된기공성탄소담체에담지된레늄담지촉매 305 [ 그림 231] 레늄과구리가포함된탄소복합체촉매의 BET 분석결과 309 [ 그림 232] 레늄과구리가포함된탄소복합체촉매의 HR-TEM 이미지 310 [ 그림 233] 중형기공성레늄 - 구리 - 탄소복합체촉매의 STEM-EDX 이미지 310 [ 그림 234] Re-Cu-MC 와 Re/Cu/MC 촉매에대한재이용성테스트결과

28 [ 표 1] 촉매무게변화에따른글리세롤로부터프로필렌글리콜을만드는전환반응의변화 ( 반응조건 ; 80% 글리세롤수용액, 수소분압 200psi, 24 시간 ) 67 [ 표 2] 반응온도변화에따른글리세롤로부터프로필렌글리콜을만드는전환반응의변화 ( 반응조건 ; 80% 글리세롤수용액, 수소분압 200psi, 24 시간 ) 67 [ 표 3] 수소분압변화에따른글리세롤로부터프로필렌글리콜을만드는전환반응의변화 ( 반응조건 ; 80% 글리세롤수용액, 수소분압 200psi, 24 시간 ) 67 [ 표 4] 초기물농도에따른글리세롤로부터프로필렌글리콜을만드는전환반응의변화 ( 반응조건 ; 80% 글리세롤수용액, 수소분압 200psi, 24 시간 ) 68 [ 표 5] ZnCuCr 촉매하에서 Cu 의비표면적및표시 92 [ 표 6] Pt 가담지된 ZrO2 담체의영향 93 [ 표 7] 반응성결과에미치는황산처리양 94 [ 표 8] Pt 의담지량에따른반응성결과 94 [ 표 9] 담지금속에따른반응성결과 94 [ 표 10] 아크롤레인생산을위한반응실험조건 96 [ 표 11] DAS 와 DASP 촉매들의표면적, 기공부피및기공크기 120 [ 표 12] DAS 와 DASP 촉매들의 EPMA 분석결과 121 [ 표 13] DAS 와 DASP 촉매의브뢴스테드 / 루이스산비율 126 [ 표 14] DAS 와 DASP 촉매들의산세기분포 128 [ 표 15] DAS-40 과 MCM-41 촉매의수열안정성테스트후비표면적 129 [ 표 16] 다양한비율의 Si/Al 을갖는 DAS 촉매와상용촉매들을사용한 1,3,5-TIPB 반응결과 ( 주입 16 분후 ) 131 [ 표 17] DAS, MCM-41 및 HZSM-5 촉매의비활성화속도 (1,3,5-TIPB 크래킹 ) 133 [ 표 18] DAS, DASP, MCM-41, HZSM-5 촉매의표면적, 기공부피및기공크기 138 [ 표 19] 각촉매의브뢴스테드 / 루이스산비율 141 [ 표 20] 반응속도상수및활성화에너지 159 [ 표 21] HZSM-5 와 DASP-40 촉매의비활성화속도 164 [ 표 22] 반응시간에따른촉매의표면적, 기공부피, 기공크기및탄소함유량 166 [ 표 23] 반응시간에따른촉매 (HZSM-5, DASP-40) 의산량변화 168 [ 표 24] 각반응경로에서의반응속도파라미터 174 [ 표 25] 특정규모 (40kt/year) 의공정가동시예상투자비용및이익 178 [ 표 26] 실험실규모의반응조건 182 [ 표 27] 벤치규모의반응조건 183 [ 표 28] HZSM-5 촉매의질량및그에따른 GHSV 변화 184 [ 표 29] MoV 촉매의질량및그에따른 GHSV 변화 184 [ 표 30] 서울대학교 bench-scale 반응기와롯데케미칼병렬반응기비교 199 [ 표 31] 다양한 ph 조건에서제조된 Mo-V-W 촉매들의 SEM-EDS 결과 210 [ 표 32] DFT 와 XRD 결과를바탕으로계산한 [100] 방향으로의격자상수값 221 [ 표 33] 반응전후 Mo-V-W 촉매들의 XPS 분석결과 222 [ 표 34] Mo-V-W 촉매의산량 222 [ 표 35] 폐글리세롤및글리세롤의성분과조성비 228 [ 표 36] 각이온교환수지의성분 229 [ 표 37] 글리세롤수용액의반응조건 231 [ 표 38] 각이온교환수지의반응시간별잔류나트륨이온농도

29 [ 표 39] 폐글리세롤및이온교환수지와 1 시간반응한글리세롤속염소이온농도 234 [ 표 40] 이온교솬수지의반응시간별전기전도도변화 235 [ 표 41] 이온교환수지의양에따른나트륨이온농도 237 [ 표 42] 이온교환실험횟수에따른나트륨이온농도 238 [ 표 43] 수용액에서전구체의비율과촉매에담지된비율 247 [ 표 44] 금속별촉매의전구체및소성환경 250 [ 표 45] 금속촉매별반응조건 251 [ 표 46] SiO2 에담지된금속촉매의종류에따른 BET 특성 254 [ 표 47] 카본담체종류에따른 BET 특성 258 [ 표 48] 알루미나에담지된팔라듐담지촉매들의물성 268 [ 표 49] 소성온도별제조된알루미나제어로젤담체에담지된팔라듐담지촉매의물리화학적특성 276 [ 표 50] 소성온도별제조된알루미나제어로젤담체에담지된팔라듐담지촉매을이용한폐숙신산수소화반응결과 278 [ 표 51] 팔라듐 - 알루미나복합체촉매의물리화학적특성 281 [ 표 52] 팔라듐 - 알루미나복합체촉매의폐숙신산수소화반응활성 282 [ 표 53] Ru/SC, Ru/TC, Ru/STC 촉매들의물리화학적특성 287 [ 표 54] Ru/SC, Ru/TC, Ru/STC 촉매들의폐숙신산수소화반응활성 290 [ 표 55] Re/MC 촉매들의물리화학적특성 295 [ 표 56] Re/MC 촉매들의수소흡착량과레늄입자크기 297 [ 표 57] Re/MC 촉매둘의폐숙신산수소화반응활성 299 [ 표 58] Re/MC-0.4 촉매의재생실험결과 301 [ 표 59] Re/MC-0.4 촉매의 12 시간반응실험결과 301 [ 표 60] Re/MC 촉매의폐숙신산수소화반응활성 302 [ 표 61] Re/MC-0.4 촉매의재생실험결과 303 [ 표 62] Re/Cu-MC 촉매의물리화학적특성 306 [ 표 63] Re/Cu-MC 촉매의반응활성 307 [ 표 64] 레늄과구리가포함된탄소복합체촉매의물리화학적특성 309 [ 표 65] 레늄과구리가포함된탄소복합체촉매의 CO 화학흡착분석결과 311 [ 표 66] 레늄과구리가포함된탄소복합체촉매를이용한숙신산의수소화반응 312 [ 표 67] 레늄과구리가포함된탄소복합체촉매를이용한벤치규모실증화

30 제 1 장서론 < 바이오매스로부터유용한화합물을생산하는바이오리파이너리공정 >

31 - 31 -

32 < 폐바이오매스유래에너지 - 환경산업육성필요성도식화 >

33 - 33 -

34 - 34 -

35 < 다양한글리세롤유도체 >

36 < 숙신산과숙신산에서유도된 C4 단량체의종류와활용분야 >

37 < 숙신산및유도체시장동향 >

38 - 38 -

39 - 39 -

40 < 본연구의차별성도식화 >

41 제 2 절연구개발의국내외현황

42 < 폐글리세롤유래아크로레인, 1,2- 프로판디올및 1,3- 프로판디올생성메카니즘 >

43 < 폐글리세롤유래화학제품및바이오폴리머생성메카니즘도식화 >

44 < 폐글리세롤유래아크롤레인 (acrolein), 아크릴산 (acrylic acid) 생성메카니즘 >

45 < 글리세롤유래아크롤레인 (acrolein) 생산용촉매의성능및효과 > < 아크롤레인유래아크릴산생산용촉매및구조 >

46 < 폐락틱산유래 C3 바이오단량체의생성메카니즘 >

47 < 폐숙신산유래 C4 바이오단량체의생성매카니즘 >

48 < 숙신산에서유도된 C4 화합물제조연구사례 > 목표생성물반응조건촉매종류출처 THF bar 8 hr Ru-Co/Carbonate Catalysis Communications 3: 269 1,4-BDO bar 50 hr Ru, Pd, Re/Activated Carbon Topics in Catalysis 53 : 1270 GBL 1,4-BDO bar 72 hr Ru(acac) 3 Journal of Organometallic Chemistry 695 : 1314 목표생성물반응조건촉매종류출처 1,4-BDO bar 24 hr Pd, Ru, Pt, Rh/Carbon Chemical Communications 2009, 5305 GBL bar 4 hr Pd /Al 2O 3 Catalysis Letters 141, 332 GBL bar 4 hr 240 Pd-Al 2O 3 Catalysis Letters 138, 28 Journal of Industrial and GBL 60 bar Ru/Carbon Engineering Chemistry THF 8 hr bar 8 hr Re/Carbon 18(1), 462 Applied Catalysis A : General ,

49 < 숙신산유도체의해외시장현황 (2003~2008 년 )>

50 - 50 -

51 - 51 -

< 글리세롤의연도별수출입통계 ( 관세청자료 )> 아크릴산수출입량 ( 톤 ) 60000

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52 < 글리세롤의연도별수출입통계 ( 관세청자료 )> 아크릴산수출입량 ( 톤 ) 연도 아클리산수출량아크릴산수입량합계 < 아크릴산의연도별수출입통계 ( 관세청자료 )>

53 < 숙신산유도체의국내시장현황 (2003~2008 년 )>

54 제 3 절연구개발의내용및범위

55 < 본연구과제목표및세부과제의목표 > < 본연구과제의 1 단계목표및최종목표진행도 >

56 < 본연구과제의 2단계내용및최종목표진행도 > γ

57 - 57 -

58 - 58 -

59 - 59 -

60 < 통합연구과제의각과제간연계성 > < 통합연구과제의과제간목표및추진체계도 >

61 < 통합과제연구팀간의연계연구 >

62 <1 단계연차별추진체계 >

63 <2 단계연차별추진체계 > 참여기업 ( 롯데케미칼 ) 총괄기관공동 ( 서울대학교, 롯데케미칼 ( 주 ))

64 제 2 장연구개발수행내용및결과

65 그림 1 글리세롤로부터 1,2-PDO 전환반응의메커니즘

66 그림 2 고온고압반응기의설치모습

67 표 1 촉매무게변화에따른글리세롤로부터프로필렌글리콜을만드는전환반응 의변화 ( 반응조건 ; 80% 글리세롤수용액, 수소분압 200psi, 24 시간 ) wt.% of catalyst Conversion (%) Yield (%) Selectivity (%) 표 2 반응온도변화에따른글리세롤로부터프로필렌글리콜을만드는전환반응의 변화 ( 반응조건 ; 80% 글리세롤수용액, 수소분압 200psi, 24 시간 ) Temperature ( ) Conversion (%) Yield (%) Selectivity (%) 표 3 수소분압변화에따른글리세롤로부터프로필렌글리콜을만드는전환반응의변화 ( 반응 조건 ; 80% 글리세롤수용액, 수소분압 200psi, 24 시간 ) Pressure (psi) Conversion (%) Yield (%) Selectivity (%)

68 표 4 초기물농도에따른글리세롤로부터프로필렌글리콜을만드는전환반응의변화 ( 반응 조건 ; 80% 글리세롤수용액, 수소분압 200psi, 24 시간 ) Water (wt.%) Conversion (%) Yield (%) Selectivity (%)

69 그림 3 다양한담체에서 Cu 를촉매로한 TEM image 분석 결과 : (a)alumina, (b)silica, (c)titania, (d)carbon

70 그림 4 다양한담체에서 Cu 를촉매로한 XRD 분석결과

71 그림 5 각담체에서의반응성결과및 Fe 를조촉매로한촉 매에서의반응성결과

72 그림 6 Alumina 와 mesorporous alumina 를담체로 촉매 (Cu, Cu/Fe) XRD 분석결과

73 그림 7 Cu/M-alu, Cu/Fe/M-alu 의 TEM 이미지 그림 8 다중기공성알루미나담체의 BET 분석결과

74 그림 9 TPR 분석결과 (Cu 2 O, CuO)

75 그림 10 상용 alumina 와중형기공의 alumina 를 담체로한 Cu 촉매의반응성결과

76 그림 11 BET 분석결과 (Activated carbon, Large pore carbon)

77 그림 12 Activated carbon 과 Large Pore Carbon 의 TEM image 그림 13 큰기공구조를가진 carbon 담체에서의반응결과

78 - 78 -

79 그림 14 소성후 NiCu 촉매의 XRD 결과 그림 15 환원처리후 XRD 결과 ( 녹색 : Ni, 파란색 : Cu)

80 그림 16 글리세롤을프로필렌글리콜로전환시키는수소화분해반응의결과

81 표 5 ZnCuCr 촉매하에서 Cu 의비표면적및표시 Catalysts Zn wt% loading Cu surface area (m 2 /g) Designation CuCr 2 O CuCr 2 O 4 1% Zn + CuCr 2 O ZnCuCr-1 5% Zn + CuCr 2 O ZnCuCr-5 10% + CuCr 2 O ZnCuCr-10 25% + CuCr 2 O ZnCuCr-25 33% + CuCr 2 O ZnCuCr-33 ZnCr 2 O 4 - ZnCr 2 O

82 그림 17 ZnCuCr 촉매의환원후 XRD 결과 (a) CuCr 2 O 4, (b) ZnCuCr-1, (c) ZnCuCr-5 (d) ZnCuCr-10, (e) ZnCuCr-25, (f) ZnCuCr-33, (g) ZnCr 2 O 4, Cu ( ), reduced CuCr 2 O 4 ( ), ZnCr 2 O 4 ( ), ZnO(О). r 2 O 4 r 2 O

83 그림 18 ZnCuCr 촉매의 H 2 -TPR 결과 : (a) CuCr 2 O 4, (b) ZnCuCr-1, (c) ZnCuCr-5 (d) ZnCuCr-10, (e) ZnCuCr-25, (f) ZnCuCr-33, (g) ZnCr 2 O

84 그림 19 ZnCuCr 를사용하여글리세롤전환반응수행결과. 반응온도 : 220, 반 응시간 : 12h, 수소압력 : 80bar. r 2 O

85 그림 20 수소화반응을통해서글리세롤을저가폴리올또는알코올로전환시 키는반응의반응경로

86 그림 21 가 ) 수소화반응기, 나 ) Gas Chromatography(GC), 다 ) High Performance Liquid Chromatography(HPLC), 라 ) 수소화반응용기 100, 30, 10cc, 마 ) GC 용 columns(hp-innowax, HP-FFAP)

87 그림 22 글리세롤수소화반응후예상되는물질에대한 GC 분석결과

88 그림 23 Pt/supported ZrO 2 촉매위에수소흡착메커니즘

89 그림 24 Zirconia, sulfated zirconia 및 Pt-sulfated zirconia 의 XRD 분석결과. (T: tetragonal of ZrO, M: monoclinic ZrO )

90 그림 25 Zirconia, sulfated zirconia 및 Pt-sulfated zirconia 의 H 2 -TPR 결과

91 그림 26 Zirconia, sulfated zirconia 및 Pt-sulfated zirconia 의 NH 3 -TPD 결과 그림 27 Zirconia, sulfated zirconia 및 Pt-sulfated zirconia 의 NH 3 흡착 In-situ FTIR 결과

92 - 92 -

93 그림 28 Zirconia, sulfated zirconia, Pt/supported zirconia 를사 용하여글리세롤의 1,3-PDO 로의전환반응적용결과 표 6 Pt가담지된 ZrO 2 담체의영향 수율 (%) 글리세롤 촉매 1,3-PDO 1,2-PDO 1-PrOH 전환율 (%) Pt/SZ Pt/WZ Pt/STA/Z Pt/PTA/Z SZ

94 표 7 반응성결과에미치는황산처리양 1N 의황산수용액첨가량 수율 (%) 1,3-PDO 1,2-PDO 1-PrOH 글리세롤 전환율 (%) 7.3ml ml ml 표 8 Pt 의담지량에따른반응성결과 Pt 담지량 (%) 수율 (%) 1,3-PDO 1,2-PDO 1-PrOH 글리세롤 전환율 (%) 표 9 담지금속에따른반응성결과 수율 (%) 글리세롤 1,3-PD 1,2-PD 1-PrOH Ethylene 전환율 (%) 촉매 O O Glycol Ru/SZ Ni/SZ Cu/SZ Ni/Cu/SZ Fe/SZ Mn/SZ Al/SZ

95 그림 29 Pt-sulfated zirconia 촉매의재이용성테스트

96 표 10 아크롤레인생산을위한반응실험조건 반응물농도 ( 글리세롤 / 물 ) 10wt.% 전처리온도 300 반응물주입속도 0.035ml/min 라인온도 270 주입가스 N 2, He, O 2 반응온도 260~320 주입가스주입속도 30ml/min GC 분석온도 40~

97 그림 30 글리세롤로부터아크롤레인생산을위한반응 시스템

98 그림 31 글리세롤탈수반응온도스크리닝결과 그림 32 반응물주입속도스크리닝결과

99 그림 33 반응시간 time-on-stream 결과 그림 34 다양한실리카담체에담지한헤테로폴리산촉매

100 그림 35 다양한실리카담체에담지한헤테로폴리산촉매의반 응결과 ( 글리세롤전환율 )

101 그림 36 다양한실리카담체에담지한헤테로폴리산촉매의반 응결과 ( 아크롤레인선택도 ) 그림 37 폴리올로부터폴리우레탄및폴리에스터합성 개략도

102 그림 38 생분해성을가지는폴리우레탄

103 그림 39 생분해성고분자합성모식도 그림 40 Polylactide 의구조적특성 ( 1 H-NMR)

104 그림 41 Polylactide 의분자량분포 (GPC) 그림 42 용매증류장치를이용 한용매정제

105 그림 43 Polylactide 를포함하는블록공중합체 PLA-b-PS 그림 44 Polylactide 를포함하는블록공중합체 P3HT-b-PLA

106 그림 45 생분해성을가지는 polylactide 를포함하는폴리우레탄 그림 46 폴리우레탄합성장치

107 그림 47 Polyol 로부터생분해성을가지는 Polyurethane 합성개략도

108 그림 48 생분해성 polyurethane 의분자량및분자량분포도

109 그림 49 FT-IR 와 DSC 를이용한생분해성 polyurethane 의구조및 열적성질확인 그림 50 Diisocyanate 에따른 polyurethane 의 flexibility 측정

110

111 그림 51 DAS 촉매의개략도 그림 52 DAS 와 DASP 촉매의제조법

112 그림 53 첫번째수열처리시간을조절한 DAS 의 SEM 사진. a) 1 시간, b) 2 시간, c) 3 시간, d) 4 시간

113 그림 54 ph 조절없이제조한 DAS 의 SEM 사진

114 그림 55 다양한적정 ph 에서제조된 DAS 의 SEM 사진 (Si/Al=40) a) ph 7, b) ph 6, c) ph 5, d) ph 4 그림 56 다양한적정 ph 에서제조된 DAS 의 SEM 사진 (Si/Al=15) a) ph 7, b) ph 6, c) ph 5, d) ph

115

116 그림 57 다양한비율의 Si/Al 을갖는 DAS 와 DASP 촉매의 SEM 사진 DAS: Si/Al = a) 15, b) 25, c) 40, d) 50, and e) 60, DASP: Si/Al = f) 25, g) 40, and h)

117 그림 58 다양한비율의 Si/Al 을갖는 DAS 와 DASP 촉매의 TEM 사진 DAS: Si/Al = a) 15, b) 25, c) 40, d) 50, and e) 60, DASP: Si/Al = f) 25, g) 40, and h) 60 그림 59 DAS-60 의 a) HAADF-STEM 사진, STEM-EDS mapping 결과 b) Si, and c) Al

118 그림 60 다양한비율의 Si/Al 을갖는 DAS 촉매의흡착등온선, Si/Al = a) 15, b) 25, c) 40, d) 50, and e) 60 그림 61 DAS 촉매의기공크기분산도곡선 Si/Al = a) 15, b) 25, c) 40, d) 50, and e)

119 그림 62 다양한비율의 Si/Al 을갖는 DASP 촉매의흡착등온선 Si/Al = a) 15, b) 25, c) 40, and d) 60 그림 63 DASP 촉매의기공크기분산도곡선 Si/Al = a) 15, b) 25, c) 40, and d)

120 표 11 DAS와 DASP 촉매들의표면적, 기공부피및기공크기 촉매 전체비표면적 (m 2 g -1 ) 소형기공비표면적 (m 2 g -1 ) 소형기공부피 (cm 3 g -1 ) 전체기공부피 (cm 3 g -1 ) 평균기공크기 (nm) DAS DAS DAS DAS DAS DASP-1 5 DASP-2 5 DASP-4 0 DASP

121 표 12 DAS와 DASP 촉매들의 EPMA 분석결과 촉매 Si/Al 몰비 Si/Al 몰비 Al/P 몰비 ( 전구체 ) ( 촉매 ) ( 촉매 ) DAS DAS DAS DAS DAS DASP DASP DASP DASP

122 그림 64 DAS 촉매의 XRD 패턴 Si/Al = a) 15, b) 25, c) 40, d) 50, and e) 60 그림 65 DASP 촉매의 XRD 패턴 Si/Al = a) 15, b) 25, c) 40, and d)

123 그림 66 다양한비율의 Si/Al 을갖는 DAS 촉매의 27 Al MAS NMR 스펙트럼. Si/Al = a) 15, b) 25, c) 40, d) 50, and e)

124 그림 67 다양한비율의 Si/Al 을갖는 DASP 촉매의 27 Al MAS NMR 스펙트럼. Si/Al = a) 15, b) 25, c) 40, and d) 60 그림 68 DAS 및 DASP 의예상구조

125 그림 69 다양한비율의 Si/Al 을갖는 DAS 촉매의 In-situ NH 3 FT-IR 결과 Si/Al = a) 15, b) 25, c) 40, d) 50, and e)

126 그림 70 다양한비율의 Si/Al 을갖는 DAS 와 DASP 촉매의 In-situ NH 3 FT-IR 결과 표 13 DAS 와 DASP 촉매의브뢴스테드 / 루이스산비율 촉매 브뢴스테드 / 루이스산 비율 촉매 브뢴스테드 / 루이스산 비율 DAS DASP DAS DASP DAS DASP DAS DASP

127 그림 71 다양한비율의 Si/Al 을갖는 DAS 촉매의 NH 3 -TPD 분석결과 Si/Al = a) 15, b) 25, c) 40, d) 50, and e)

128 그림 72 다양한비율의 Si/Al 을갖는 DAS 와 DASP 촉매의 NH 3 -TPD 분석결과 표 14 DAS와 DASP 촉매들의산세기분포 산세기분포 촉매 약산 중간산 강산 피크온도 ( ) 비율 (%) 피크온도 ( ) 비율 (%) 피크온도 ( ) 비율 (%) DAS DAS DAS DAS DAS DASP DASP DASP DASP

129 그림 73 DAS-40 과 MCM-41 촉매의수열안정성테스트후 TEM 사진 표 15 DAS-40 과 MCM-41 촉매의수열안정성테스트후비표면적 Surface area (m 2 g -1 ) DAS-40 MCM-41 No treatment Water in autoclave (180, 24h) Water in autoclave (180, 48h) Steam (600, 2h)

130 그림 74. 산촉매하에서 1,3,5-TIPB 의크래킹반응경로

131 표 16 다양한비율의 Si/Al 을갖는 DAS 촉매와상용촉매들을사용한 1,3,5-TIPB 반응결과 ( 주입 16 분후 ) 촉매 1,3,5-TIPB 전환율 생성물분포 (%) 벤젠큐멘 DIPB DAS DAS DAS DAS DAS MCM HZSM

132 그림 75 DAS 와상용촉매를이용한 1,3,5-TIPB 크래킹반응장기테스트 그림 76 촉매의비활성화분석을위한피팅식

133 표 17 DAS, MCM-41 및 HZSM-5 촉매의비활성화속도 (1,3,5-TIPB 크래킹 ) DAS-40 MCM-41 Deactivation rate (h -1 ) 그림 77 수크로오스의수화반응

134 그림 78 DAS 와상용촉매를이용한수크로오스의수화반응결과 (2) 열린중형기공구조의산촉매의글리세롤탈수반응으로의응용및산촉 매특성에따른영향

135 그림 79. 글리세롤을아크릴산으로전환하는반응의경로

136 그림 80 산촉매물질의 a) SEM 과 b) TEM 사진 ; 1) DAS(40), 2) DASP(40), 3) Al-MCM-41 and 4) HZSM

137 그림 81 각촉매 (DAS, DASP, MCM-41, HZSM-5) 의흡착등온선 그림 82 촉매들의기공크기분산도곡선 a) DAS(40), b) DASP(40), c) MCM-41, d) HZSM

138 표 18 DAS, DASP, MCM-41, HZSM-5 촉매의표면적, 기공부피및기 공크기 평균소형기공의소형기공전체기공비표면적기공크기비표면적부피부피 [m 2 /g] [nm] [m 2 /g] [cm 3 /g] [cm 3 /g] DASP(4 0) DAS(40) MCM HZSM 그림 83 XRD 패턴 (DAS(40), DASP(40), MCM-41, ZSM-5)

139

140 그림 84 각촉매의 NH 3 -TPD 분석결과

141 그림 85 각촉매의 In-situ NH 3 FT-IR 결과 표 19 각촉매의브뢴스테드 / 루이스산비율 브뢴스테드 / 루이스산비율 DAS(40) 1.53 DASP(40) 2.87 AlMCM HZSM

142

143 그림 86 각촉매에서의글리세롤전환율 촉매의양 : A) 0.1g, B) 0.05g

144 그림 87 촉매표면의산점밀도에따른 TOF(0) 변화

145 그림 88 각촉매에서의아크롤레인선택도 촉매의양 : A) 0.1g, B) 0.05g

146 그림 89 생성된아크롤레인 / 아세톨비와브뢴스테드 산점 / 루이스산점비의상관관계 촉매의양 : A) 0.1g, B) 0.05g

147

148 그림 90 사용한촉매의 TGA 분석결과 그림 91 촉매의기공크기에따른코크의생성량

149 그림 92 반응전후촉매들의기공크기분산도곡선 a) DAS(40), b) DASP(40), c) MCM-41, d) HZSM

150 그림 93 DAS-40 와 MoV ( 함침 ) 촉매의장기안정성테스트 (3 차년도연구목표달성 )

151 그림 94 산촉매와산화촉매 (MoV oxide) 이중층에서의글리세롤산화탈수반응 결과 그림 95 혹독한조건에서의 250 시간동안의장기실험

152 그림 96 DASP-40 과 MoV oxide 를이용한장기반응실험결과 (3) 글리세롤의산화탈수반응에의한아크릴산생성의반응속도론적연구 및경제성분석을위한공정모사

153 그림 97 산촉매에서의글리세롤전환반응경로

154 τ

155 그림 98 HZSM-5 의반응실험결과및피팅 곡선 a) 250, b) 275, c)

156 그림 99 HZSM-5 를이용한각단계에서의 Arrhenius plot

157 그림 100 DASP-40 의반응실험결과및피팅곡선 a) 250, b) 275, c)

158 그림 101 DASP-40 를이용한각단계에서의 Arrhenius plot

159 표 20 반응속도상수및활성화에너지 Reaction rate constant (mol/g cat h) HZSM-5 Reaction T (K) Activation energy (kj/mol) k k k k DASP-40 k k k k

160 ln exp ln ln ln ln

161 ln ln ln

162 그림 102 시간에따른실험결과와각모델식의피팅곡선 a) DASP-40, b) HZSM

163 그림 103 시간에따른실험결과와피팅곡선

164 W/F(gcatalysth/ mol) 표 21 HZSM-5 와 DASP-40 촉매의비활성화속도 HZSM-5 k d (h -1 ) W/F(gcatalysth/ mol) DASP-40 k d (h -1 ) 그림 104 시간에따른생성물의선택도 (HZSM-5)

165 그림 105 시간에따른생성물의선택도 (DASP-40)

166 표 22 반응시간에따른촉매의표면적, 기공부피, 기공크기및탄소 함유량 SBET Dave Smicro Vmicro Time(h) (m 2 g -1 ) (nm) (m 2 g -1 ) (cm 2 g -1 ) HZSM-5 Vtotal (cm 3 g -1 ) Carbon contents (%) DASP

167 그림 106 반응시간에따른촉매 (HZSM-5, DASP-40) 의기공크기 분산도곡선

168 그림 107 반응시간에따른촉매 (HZSM-5, DASP-40) 의 NH 3 -TPD 분석결과 표 23 반응시간에따른촉매 (HZSM-5, DASP-40) 의산량변화 Amount of Amount of Time (h) acid sites Time (h) acid sites (mmol g -1 ) (mmol g -1) HZSM-5 DASP (75.0%) (16.2%) (75.9%) (50.5%) (90.8%) (49.2%) (94.2%) (41.1%)

169

170 그림 108 반응시간에따른촉매 (HZSM-5, DASP-40) 의 TPO 분석결과

171 그림 109 반응시간에따른촉매 (HZSM-5, DASP-40) 의 13 C NMR 분석결과 그림 110 산화촉매 (MoV oxide) 에서의아크롤레인전환반응경로

172

173 그림 111 MoV oxide 촉매에서의반응실험결과와 피팅곡선

174 Reaction rate constant (mol/g catalysts ) 표 24 각반응경로에서의반응속도파라미터 R1 R2 R3 R4 R5 R6 k E a (kj/mol)

175 그림 112 글리세롤산화탈수반응공정모식도

176 그림 113 공정의스케일에따른비용및수익 변화 그림 114 공정의스케일에따른 a) 각각의비용 및 b) 차지하는비중

177 그림 115 공정스케일에따른예상투자액회수기간 ( 위 ) 및원료 ( 정제된 글리세롤 ) 의가격증가에따른예상투자액회수기간

178 표 25 특정규모 (40kt/year) 의공정가동시예상투자비용및이익 Capacity 40 kton/year (Glycerol, 50wt%), kton/year (Acrylic acid, >95wt%) Total project capital cost $14.1M/year Total operating cost $30.9M/year Total raw materials cost $24.6M/year Total utilities cost $2.34M/year Total product sales $48.1M/year P.O.Period 3.80 year (5) 글리세롤전환반응및 C 4 바이오단량체생산을위한벤치규모의실증화

179

180 그림 116 벤치규모반응기의모습 (a) 반응물주입기, (b) 반응기, (c) 온도및 MFC 컨트롤러, (d) 냉각기, (e) 전기로

181 생산물 수율 유입글리세롤 반응글리세롤 전환율 유입글리세롤 그림 117 성형된촉매의전후모습. (a) HZSM-5, (b) MoV

182 표 26 실험실규모의반응조건 반응요소 수치 반응온도 wt% 글리세롤의공급속도 질소기체의공급속도 헬륨기체의공급속도 2.0ml/hr 2.93ml/min 25ml/min 촉매담지량 0.3g ε ρ ρ

183 표 27 벤치규모의반응조건 반응요소 수치 글리세롤수용액의몰농도 0.6M 글리세롤수용액의공급속도 0.69ml/min 질소기체의공급속도 21.01ml/min 헬륨기체의공급속도 ml/min 승온속도 5 /min 3 본연구의목표

184 표 28 HZSM-5 촉매의질량및그에따른 GHSV 변화 촉매질량반응기부피반응기밀도 (g) (ml) (g/ml) 공극률 GHSV(h -1 ) 표 29 MoV 촉매의질량및그에따른 GHSV 변화 촉매질량 (g) 반응기부피 (ml) 반응기밀도 (g/ml) 공극률 GHSV(h -1 )

185 그림 118 GHSV 변화에따른 HZSM-5 촉매의활성정도

186 그림 119 GHSV 변화에따른 MoV 촉매의활성정도

187 그림 120 산소비율에따른생산물의수율및글리세롤의전환율

188 그림 121 글리세롤 / 산소 =1 일때의생성물의수율및글레세롤의전환율 그림 122 산소비율에따른아크릴산수율의변화양상

189 그림 123 산소비율에따른아크롤레인수율의변화양상 그림 124 산소비율에따른아세트산수율의변화양상

190 그림 125 글리세롤의탈수및산화반응경로 [48]

191 그림 126 반응온도별글리세롤전환반응의생산물별수율및글리세롤의 전환율

192 그림 에서시간에대한반응생성물들의수율및글리세롤전환율 변화

193 그림 에서시간에대한반응생성물들의수율및글리세롤전환 율변화

194 그림 129 반응온도에따른아크롤레인수율의변화양상 그림 130 반응온도에따른아세트산수율의변화양상

195 그림 131 반응온도에따른아크릴산수율의변화양상

196 그림 132 HZSM-5 의반응전후형태 그림 133 MoV 촉매의열중량분석결과

197 그림 134 HZSM-5 촉매의열중량분석결과

198 그림 135 장시간벤치규모반응결과생성물의수율및글리세롤의전환율 그림 136 참여기업 ( 롯데케미칼 ) 에있는병렬반응기 a) 주입부, b) 전기로및반응기, c) 반응물주입기, d) 주입부확대사진

199 표 30 서울대학교 bench-scale 반응기와롯데케미칼병렬반응기비교

200 그림 137 소성전후의몰리브덴 - 바나듐 - 텅스텐성형촉매의모습 그림 138 촉매의성형및소성순서에따른반응결과

201 (6) 글리세롤로부터아크릴산을직접생산하기위한이원기능촉매의개발

202

203 그림 139 이중층반응시스템에서의선택적산화촉매스크리닝결과

204 그림 140 MoV-NbP 촉매의제조방법

205 그림 141 Mo-V-W 촉매의제조방법

206 그림 142 MoV-NbP 촉매들의아크릴산수율 그림 143 MoV-NbP 촉매들의아크롤레인수율

207 그림 144 MoV-Nbp 촉매들의이산화탄소및이산화탄소수율

208 그림 145 다양한 ph 를갖는용액에서제조한 Mo-V-W 촉매의 SEM 사진

209 그림 146 전구체용액의다양한 ph 조건에서합성된 Mo-V-W 촉매의 XRD 패턴

표 31 다양한 ph 조건에서제조된 Mo-V-W 촉매들의 SEM-EDS 결과 Ratio Mo V W 전구체용액 4 1 5 ph 1.0 5.6 1 5.4 ph 2.2 4.

210 표 31 다양한 ph 조건에서제조된 Mo-V-W 촉매들의 SEM-EDS 결과 Ratio Mo V W 전구체용액 ph ph ph ph 그림 147 다양한 ph 조건에서제조된 Mo-V-W 촉매들의 글리세롤산화탈수반응결과

211

212 그림 148 다양한온도에서열처리를거친 Mo-V-W 촉매의 XRD 패턴 그림 149 다양한온도에서열처리를거친 Mo-V-W 촉매의반응결과

213 그림 150 이성분계와삼성분계촉매들의 XRD 패턴

214 그림 151 이성분계와삼성분계촉매들의반응결과비교

215 그림 152 수열합성법을통한 Mo-V-O 촉매생성원리 *Ueda et al., Eur. J. Inorg. Chem. 2013, 그림 153 Mo-V 용액과 Mo-V-W 4:1:5 용액의 UV/Vis 분광기분석결과

216 그림 154 다양한 Mo:V:W 비율을갖는 Mo-V-W 촉매의 XRD 패턴

217 그림 155 Mo-V-W 촉매들의 XRD 패

218 그림 156 Mo-V-W 촉매들의 TEM 사진 림 157 Mo-V-W 촉매들의 HR-TEM 사진

219 그림 158 MoVW 촉매의 W L3-edge 에서의 XANES 피크

220 그림 159 MoVW 촉매들의 FT-IR 과 Raman 분석

표 32 DFT 와 XRD 결과를바탕으로계산한 [100] 방향으로의격자상수값 촉매 격자상수값 (c-direction) DFT 계산결과 XRD를통한실험값 MoVW 4:1:0 4.097 3.995 MoVW 4:1:1 4.071 3.

221 표 32 DFT 와 XRD 결과를바탕으로계산한 [100] 방향으로의격자상수값 촉매 격자상수값 (c-direction) DFT 계산결과 XRD를통한실험값 MoVW 4:1: MoVW 4:1: MoVW 4:1: MoVW 4:1: MoVW 4:1: 그림 160 Mo 을치환한 W 원자로인한 charge density 변화계산결과 a) Mo 원자치환, b) MoVW 4:1:

222 표 33 반응전후 Mo-V-W 촉매들의 XPS 분석결과 촉매 MoVW 4:1:0 Mo-V-W 4:1:1 Mo-V-W 4:1:3 Mo-V-W 4:1:5 Mo-V-W 4:1:7 Mo-V-W 4:1:9 반응전 반응후 Mo 5+ /Mo 6+ V 4+ /V 5+ W 5+ /W 6+ Mo 5+ /Mo 6+ V 4+ /V 5+ W 5+ /W 표 34 Mo-V-W 촉매의산량 촉매 산량 (mmol/g) MoVW 4:1: MoVW 4:1: MoVW 4:1: MoVW 4:1: MoVW 4:1: MoVW 4:1:

223 그림 161. Mo-V-W 촉매들의 NH 3 -TPD 분석결과

224 그림 162 Mo-V-W 촉매들의 TPR 분석결과

225 그림 163 Mo-V-W 촉매들의글리세롤의산화탈수반응결과 그림 164 Mo-V-W 촉매들의글리세롤의산화탈수반응결과

226 그림 165 WO 3 과 MoV 을물리적으로혼합한촉매와 MoVW 4:1:5 촉매와의 활성비교

227 그림 166 Mo-V-W 4:1:5 촉매의장기안정성테스트 (7) 폐글리세롤의특성조사및정제방법확립과이를사용한반응성능평가

228 표 35 폐글리세롤및글리세롤의성분과조성비 (A사제공 ) 성분 폐글리세롤 (wt%) 글리세롤 (wt%) glycerol water Na Cl Mong

229 표 36 각이온교환수지의성분 IRA-410 IRN-97H IRN-150 Ionic form as shipped Cl - H + H + /OH - strong/weak strong base strong acid strong acid/base Total eq/l (H + ) exchange 2.15 eq/l eq/l 1.2 eq/l (OH - ) capacity Moisture holding 45 ~ ~ 51 49~55/54~60 capacity(%) Uniformity coefficient / size(μm) 600 ~ : 0.1 % 600~700 / 580~680 temperature 35 C 120 C 60 C/ Regenerant NaOH HCl x performance(c onversion) 99 % 99 % / 95 %

230 그림 167 이온교환수지의형태. (a) IRN-97H, (b) IRA-410, (c) IRN

그림 168 (a) 등온반응이가능한히팅맨틀, (b) 이온수지를여과시키기위한 진공여과기 표 37 글리세롤수용액의반응조건 반응요소 수치 반응온도 250 1.

231 그림 168 (a) 등온반응이가능한히팅맨틀, (b) 이온수지를여과시키기위한 진공여과기 표 37 글리세롤수용액의반응조건 반응요소 수치 반응온도 M 글리세롤의공급속도 2.0ml/hr 질소기체의공급속도 헬륨기체의공급속도 2.93ml/min 25ml/min 촉매담지량 HZSM-5 0.2g/ MoVW 0.3g

232

233 그림 169 산도조절을거친폐글리세롤

234 표 38 각이온교환수지의반응시간별잔류 나트륨이온농도 name ppm wt% IRN hr IRN hr IRN hr IRN-97H 1 hr IRN-97H 3 hr IRN-97H 5 hr IRA hr IRA hr IRA hr crude glycerol 표 39 폐글리세롤및이온교환수지와 1시 간반응한글리세롤속염소이온농도 name ppm wt% crude glycerol IRA IRN

그림 170 (a) 페글리세롤, (b) IRN-150, (c) IRN-97H, (d) IRA-410 이온수지와반응후의글리세롤 ; (1): 1 시간, (2): 2 시 간, (3): 3 시간 표 40 이온교솬수지의반응시간별전기 전도도변화 Crude glycerol water IRN-150 1hr IRN-150 3hr IRN-150 5hr

235 그림 170 (a) 페글리세롤, (b) IRN-150, (c) IRN-97H, (d) IRA-410 이온수지와반응후의글리세롤 ; (1): 1 시간, (2): 2 시 간, (3): 3 시간 표 40 이온교솬수지의반응시간별전기 전도도변화 Crude glycerol water IRN-150 1hr IRN-150 3hr IRN-150 5hr IRN-97H 1hr IRN-97H 3hr IRN-97H 5hr IRA-410 2hr IRA-410 3hr IRA-410 5hr Conductanse (S) 1.40E E E E E E E E E E E

236

237 표 41 이온교환수지의양에따른나트륨이온 농도 name ppm wt% 1: : crude glycerol

238 표 42 이온교환실험횟수에따른나트륨 이온농도 반복횟수 ppm wt%

239 그림 171 순수글리세롤, 폐글리세롤, 정제글리세롤의반응실험결과

240 그림 172 나트륨이온농도변화에따른아크릴산수율변화

241 그림 173 폐글리세롤전환반응의수율및전환율 ; HZSM-5 : MoV = 3 :

242 그림 174 폐글리세롤전환반응의수율및전환율 ; HZSM-5 : MoV = 2.5 :

243 그림 175 락틱산의반응경로

244 그림 176 고온고압반응기제원

245 그림 177 반응속도결정단계 그림 178 랭뮤어 - 힌셀우드매커니즘

246 그림 179 촉매제조과정 ( 탄소를담지체로한백금 - 금촉매 )

247 표 43 수용액에서전구체의비율과촉매에담지된비율 Cat. Mole % in solution Mole % in sample Pt Au Pt Au P P P P Pt/C Pt-Au(95:5)/C Pt-Au(90:10)/C Pt-Au(85:15)/C Intensity (a.u.) Theta [ deg.] 그림 180 백금 - 금담지촉매의 XRD 그래프 θ

248 그림 181 촉매별 TEM 사진 (a)p1 (b)p2 (c)p3 (d)p

249 그림 182 촉매별전환율및선택도

250 표 44 금속별촉매의전구체및소성환경 촉매 전구체 소성온도 시간 Ag/SiO 2 Cu(NO 3 ) hr Co/SiO 2 Co(NO 3 ) 2 6H 2 O 450 2hr Cr/SiO 2 Cr(NO 3 ) 3 9H 2 O 570 8hr Cu/SiO 2 Cu(NO 3 ) hr Ni/SiO 2 Ni(NO 3 ) 2 6H 2 O 700 2hr Pt/SiO 2 H 2 PtCl hr Ru/SiO 2 RuCl hr 그림 183 다양한금속을담지한촉매의 XRD 그래프

251 표 45 금속촉매별반응조건 촉매 전구체 소성 환원 Ag/SiO 2 Cu(NO 3 ) hr 120-3hr Co/SiO 2 Co(NO 3 ) 2 6H 2 O 450-2hr hr Cu/SiO 2 Cu(NO 3 ) hr hr Ni/SiO 2 Ni(NO 3 ) 2 6H 2 O 700-2hr 500-2hr Pt/SiO 2 H 2 PtCl hr 500-2hr Ru/SiO 2 RuCl hr 450-2hr 아래의그림은위의방법으로제조된여러가지금속촉매에대한 X- 선회절스펙트럼을나 타낸것이다

252 그림 184 다양한금속을담지한촉매의 XRD 그래프 θ

253 그림 185 촉매별 TEM 사진 (a)ag/sio 2 (B)Co/SiO 2 (c)cu/sio 2 (d)ni/sio 2 (e)pt/sio 2 (f)ru/sio

254 표 46 SiO 2 에담지된금속촉매의종류에따른 BET 특성 average metal particle size (nm) surface area (m 2 /g) pore volume (cm 3 /g) Ag/SiO 2 Co/SiO 2 Cu/SiO 2 Ni/SiO 2 Pt/SiO 2 Ru/SiO pore size (nm) 그림 186 금속촉매별전환율비교

255 그림 187 Ru/SiO 2 촉매에서시간에따른전환율, 선 택도및수율

256 그림 188 Ru/SiO 2 촉매에서압력에따른전환율, 선 택도및수율

257 그림 189 Ru/SiO 2 촉매에서온도에따른전환율, 선택 도및수율

표 47 카본담체종류에따른 BET 특성 surface area (m 2 /g) pore volume (cm 3 /g) pore size (nm) vulcan CNT GP KNB CNFs 209.5 225.

258 표 47 카본담체종류에따른 BET 특성 surface area (m 2 /g) pore volume (cm 3 /g) pore size (nm) vulcan CNT GP KNB CNFs 그림 190 (a) XRD 그래프, (b) 투과전자현미경 θ θ θ

259 그림 191 카본담체별반응물의전환율 그림 192 Ru/ketjen black 촉매에서시간에따른전환율, 선택도 및수율

260 그림 193 Ru/ketjen black 촉매에서온도와압력에따른전환율, 선택도및수율

261 γ 그림 194 숙신산의수소화반응경로및활성촉매

262 γ +2H 2 숙신산 -2H 2 O 1,4- 부탄다이올 -2H 2 Reppe Process +3H 2 -H 2 O Davy Mckee Process 감마부티로락톤 말레산무수물 그림 195 감마부티로락톤제조반응경로

263

264 그림 196 폐숙신산의회분식수소화전환반응기설계

265 그림 197 반응압력별숙신산의수소화반응활성 그림 198 반응온도별숙신산의수소화반응활성

266 그림 199 반응시간별, 반응물대비촉매양별숙신산의수소화반응활성

267 그림 200 알루미나제어로젤담체의제조과정모식도

268 표 48 알루미나에담지된팔라듐담지촉매들의물성 팔라듐함량 (wt %) 팔라듐분산도 (wt %) 비표면적 (m 2 /g) 기공부피 (cm 3 /g) 평균기공크기 (nm) AC AX Pd/AC Pd/AX dv/dd (cm 3 /g nm) 흡착부피 (cm 3 /g) Pore size (nm) 50 알루미나제어로젤 알루미나제어로젤에담지된팔라듐촉매 상대압력 (P/P 0 ) 그림 201 알루미나제어로젤담체 (AX) 와알루미나제어로젤담체 에담지된팔라듐담지촉매 (Pd/AX) 의질소흡착 - 탈착실험결과

269 그림 202 알루미나담체와팔라듐담지촉매의 XRD 그래프 θ θ θ

270 그림 203 팔라듐담지촉매의 HR-TEM 이미지

271 그림 204 팔라듐담지촉매의온도별전환율및선택도 그림 205 팔라듐담지촉매의온도별수율

272 그림 206 반응부피별반응활성

273 그림 207 교반속도에따른반응활성

274 그림 208 숙신산으로부터감마부티로락톤제조반응메커니즘

275 θ θ 그림 209 소성온도별제조된알루미나제어로젤담체에담지된팔라듐담지 촉매의 X- 선회절스펙트럼분석결과

276 표 49 소성온도별제조된알루미나제어로젤담체에담지된팔라듐담지촉매의 물리화학적특성 비표면적 (m 2 /g-cat.) 총산량 (μmol NH 3 /g-cat.) 표면산밀도 (μmol NH 3 /m 2 ) 팔라듐분산도 (%) Pd/AX700 Pd/AX750 Pd/AX800 Pd/AX850 Pd/AX θ

277 그림 210 소성온도별제조된알루미나제어로젤담체에담지된 팔라듐담지촉매의질소흡착 - 탈착분석결과

278 표 50 소성온도별제조된알루미나제어로젤담체에담지된팔라듐담지촉매을 이용한폐숙신산수소화반응결과 감마부티로락톤숙신산무수물숙신산전환율감마부티로락톤선택도 (%) 선택도 (%) (%) 수율 (%) Pd/AX Pd/AX Pd/AX Pd/AX Pd/AX

279 그림 211 소성온도별제조된알루미나제어로젤담체에담지된팔 라듐담지촉매의숙신산수소화반응활성과산특성의상관관계

280 그림 212 졸 - 겔법에의한팔라듐 - 알루미나복합체촉매의제조과정

281 그림 213 졸 - 겔법에의한팔라듐 - 알루미나복합체촉매의 질소흡착 - 탈착분석곡선결과 표 51 팔라듐 - 알루미나복합체촉매의물리화학적특성 Pd-A650 Pd-A750 Pd-A850 비표면적 (m 2 /g) 기공부피 (cm 3 /g) 평균기공크기 (nm) 팔라듐분산도 (%)

282 그림 214 환원된팔라듐 - 알루미나복합체촉매 (Pd-A650, Pd-A750, Pd-A850) 의 X- 선회 절스펙트럼 θ θ θ θ 표 52 팔라듐 - 알루미나복합체촉매의폐숙신산수소화반응활성 반응온도 Pd-A650 Pd-A750 Pd-A850 숙신산전환율 (%) 감마부티로락톤선택도 (%) 감마부티로락톤수율 (%)

283 그림 215 팔라듐 - 알루미나복합체촉매와팔라듐 / 알루미나담 지촉매와의폐숙신산수소화활성비교

284 그림 216 팔라듐 / 알루미나담지촉매의소성온도에따른팔라듐표면적과촉매활성비교

285 그림 217 계면활성 - 주형법을이용하여제조된기공성탄소 담체및그비교군으로써구형탄소담체와주형법으로제 조된기공성탄소담체의제조과정

286

287 그림 218 계면활성 - 주형법을이용하여제조된기공성탄소담체및그비교군으로 써구형탄소담체와주형법으로제조된기공성탄소담체의전계방출주사전자현미 경이미지 표 53 Ru/SC, Ru/TC, Ru/STC 촉매들의물리화학적특성 Ru/SC Ru/TC Ru/STC 비표면적 (m 2 /g) 기공부피 (cm 3 /g) 평균기공크기 (nm) 루테늄촉매성분표면적 (m 2 /g) 루테늄분산도 1.6 % 4.0 % 13.7 %

288 그림 219 Ru/SC, Ru/TC, Ru/STC 촉매들의질소흡착 - 탈착분석곡선

289 그림 220 Ru/SC, Ru/TC, Ru/STC 촉매들의 X- 선회절 스펙트럼 θ θ θ θ θ 그림 221 Ru/SC, Ru/TC, Ru/STC 촉매들의고배율투과전자현미경 (HR-TEM) 이미지

290 표 54 Ru/SC, Ru/TC, Ru/STC 촉매들의폐숙신산수소화반응활성 반응온도 Ru/SC Ru/TC Ru/STC 숙신산전환율 (%) 감마부티로락톤선택도 (%) 감마부티로락톤수율 (%)

291

292

293

294

295 표 55. Re/MC 촉매들의물리화학적특성 Re/MC-0 Re/MC-0.2 Re/MC-0.4 Re/MC-0.6 Re/MC-0.8 Re/MC-1.0 비표면적 (m 2 /g) 미세기공면적 (m 2 /g) 기공부피 (cm 3 /g)

296

297 표 56. Re/MC 촉매들의수소흡착량과레늄입자크기 수소흡착량 (mmol/g-cat. ) 레늄입자크기 (nm) Re/MC-0 Re/MC-0. 2 Re/MC-0. Re/MC-0. Re/MC-0. Re/MC

298

299 표 57. Re/MC 촉매둘의폐숙신산수소화반응활성 숙신산 사수소화퓨란 감마부티로락 1,4-부탄디올 생성물수율 전환율 (%) 수율 (%) 톤수율 (%) 수율 (%) 합계 (%) Re/MC Re/MC Re/MC Re/MC Re/MC Re/MC

300 그림 228. Re/MC 촉매에서레늄금속의입자크기와숙신산수소화 반응활성간의상관관계도

301 반응횟수 숙신산전환율 (%) 사수소화퓨란 수율 (%) 레늄용출 (ppm) 재이용성 % % 표 58. Re/MC-0.4 촉매의재생실험결과 촉매 사수소화퓨란 수율 (%) 감마부티로락톤 1,4- 부탄디올 숙신산전환율 (%) Re/MC 표 59. Re/MC-0.4 촉매의 12 시간반응실험결과

302 표 60 Re/MC 촉매의폐숙신산수소화반응활성 숙신산 전환율 (%) 사수소화퓨란감마부티로락수율 (%) 톤수율 (%) 1,4- 부탄디 올 수율 (%) 생성물수율 합계 (%) 4 h h h h h h

303 표 61 Re/MC-0.4 촉매의재생실험결과 반응횟수 숙신산전환율 (%) 사수소화퓨란 수율 (%) 레늄용출 (ppm) 재이용성 % % 그림 229 메탄올을이용하여숙신산으로부터 1,4- 부탄디올을생산하는비고리 수소화반응경로

304

305 그림 230 구리가포함된기공성탄소담체에담지된레늄담지촉매

306 표 62 Re/Cu-MC 촉매의물리화학적특성 비표면적 기공부피 레늄 구리 (m 2 /g) (cm 3 /g) 수소흡착량 수소흡착량 (mmol/g-cat) (mmol/g-cat) Re/8.0Cu-MC Re/12.7Cu-MC Re/15.9Cu-MC Re/23.3Cu-MC Re/26.8Cu-MC

307 표 63 Re/Cu-MC 촉매의반응활성 Re/8.0Cu-M C Re/12.7Cu-M C Re/15.9Cu-M C Re/23.3Cu-M C Re/26.8Cu-M C 감마부티로락 숙신산메틸숙시네이톤 1,4-부탄디올 전환율 (%) 트수율 (%) 수율 (%) 수율 (%)

308

309 Volume adsorbed (cm 3 /g) MC Re-Cu-MC Re/Cu-MC Cu/Re-MC Re/Cu/MC Relative pressure (P/P 0 ) 그림 231 레늄과구리가포함된탄소복합체촉매의 BET 분석결과 표 64 레늄과구리가포함된탄소복합체촉매의물리화학적특성 레늄함량 구리함량 비표면적 기공부피 기공크기 (wt%) (wt%) (m 2 /g) (cm 3 /g) (nm) MC Re-Cu-M C Re/Cu-MC Cu/Re-MC Re-Cu/MC

그림 232 레늄과 구리가 포함된 탄소복합체 촉매의 HR-TEM 이미지 50 nm 50 nm Re Cu Electron 그림 233 중형기공성

310 의경 속 자들이 우 금 입 응집 되지 않고 고 게 잘 분 르 포된 것으로 나타났다. (a) MC (b) Re/Cu/MC (c) Cu/Re-MC 50 nm 50 nm 50 nm (d) Re/Cu-MC (e) Re-Cu-MC 50 nm 50 nm 그림 232 레늄과 구리가 포함된 탄소복합체 촉매의 HR-TEM 이미지 50 nm 50 nm Re Cu Electron 그림 233 중형기공성 레늄-구리-탄소복합체 촉매의 STEM-EDX 이미지 중형기공성 늄-구리-탄소 합체 촉매의 개 적인 속 분산도를 확인하기 위하여 - X 분석을 수행하였다. 이미지상에서 속 자들이 10 이하의 크기로 레 STEM ED 복 별 STEM 금 금 입 nm

311 표 65 레늄과구리가포함된탄소복합체촉매의 CO 화학흡착분석결과 금속표면적 (m 2 /g) 금속분산도 (%) 평균입자크기 (nm) Re-Cu-MC Re/Cu-MC Cu/Re-MC Re-Cu/MC

312 표 66 레늄과구리가포함된탄소복합체촉매를이용한숙신산의수소화반응 숙신산 전환율 (%) 디메틸숙시네 이트수율 (%) 감마부티로락 톤 수율 (%) 1,4- 부탄디올 수율 (%) Re-Cu-MC Re/Cu-MC Cu/Re-MC Re/Cu/MC

313 Total yield for GBL and BDO (%) Recycle run 1 Recycle run 2 Recycle run 3 0 Re-Cu-MC Re/Cu/MC 그림 234 Re-Cu-MC 와 Re/Cu/MC 촉매에대한재이용성 테스트결과

314 표 67 레늄과구리가포함된탄소복합체촉매를이용한벤치규모실증화 반응시간 숙신산전환율 (%) 생산량 (kg/1day 1b atch) Re-Cu-MC Re/Cu-MC Cu/Re-MC Re/Cu/MC 비고 7 batch 가동시 10 kgh/day 생산가능 9 batch 가동시 10 kgh/day 생산가능 9 batch 가동시 10 kgh/day 생산가능 14 batch 가동시 10 kgh/day 생산가능

315

316 제 3 장목표달성도및관련분야기여도

317

318

319 < 본연구의기대효과 >

320 제 4 장연구개발결과의활용계획등 [1] 폐식용유등폐자원으로부터글리세롤전환기술개발

321 < 글리세롤전환기술개발결과의장 / 단기활용방안도식화 > < 글리세롤전환기술의타응용분야 > 종류활용분야활용주체대상 글리세롤로부터 생산된아크롤레인, 아크릴산 식품 식품가공업 가공용제 정밀화학 화학공장 플라스틱가소제, 유화안정제, 방부제 화장품 화학공장 보습, 습윤용첨가제, 윤할제첨가물 자동차용첨가물 자동차산업 친환경부동액 섬유 섬유산업 Sorona 섬유 [2] 폐숙신산유래 C4 바이오단량체제조기술개발

322 < C4 바이오단량체제조기술의타응용분야 > 종류활용분야활용주체대상 정밀화학반도체, 수지스판덱스. PBT 수지 숙신산으로부터 제조된 C4 단량체 제약의약품향정신성의약품 용제화학공장, 연구소 Polyol, Pyrrolidine 제조 이연구가성공적으로진행되어, 기업들과지속적인자문과토론을거쳐기 술개발의상업화를이루는방향으로진행될것으로기대. 참여기업의연구진, 경제성평가위원및엔지니어들과심도깊은토론과경 제성판단을통해경제성평가집중. (1) 사업화계획 폐식용유등폐자원으로부터글리세롤전환기술개발 구분 개발계획품목 사업화연도 2015 년도 2018 년도 2020 년도 20,000 ton/yr 급상용생산공정건설을위한 pilot plant 20,000 ton/yr 급상용생산공정건설 20,000 ton/yr 급상용생산 소요인원 투자계획 제조시설 시험시설 생산계획 ( 톤 ) 2,000 20,000 판매계획 ( 억원 ) 내수 수출 184 계 214 글리세롤유래 PDO 생산량 : 20,000 톤 / 년,

323 국내판매 : 2000톤 ( 국내시장수요 2 만톤의 10 %, 근거자료 : 화학저널 ) 해외수출 : 18,000 톤 PDO 가격 ( 근거자료, ICIS Pricing) 국내가격 : 1,500,000원 /ton, 해외가격 : $ 1,000/ton PDO 판매금액 : 264억 / 년국내판매 : 2000톤 / 년 1,500,000원 / 톤 = 30억원 / 년해외판매 : 18,000 톤 / 년 $ 1,000/ 톤 1,020원 ( 현재환율 ) = 184억 글리세롤로부터아크릴산제조기술개발 구분 개발계획품목 사업화연도 2015 년도 2018 년도 2020 년도 20,000 ton/yr 급상용생산공정건설을위한 pilot plant 20,000 ton/yr 급상용생산공정건설 20,000 ton/yr 급상용생산 소요인원 투자계획 제조시설 시험시설 생산계획 ( 톤 ) 6,000 20,000 판매계획 ( 억원 ) 내수 수출 358 계 466 판매계획의내수 / 수출비율약 7:3 기준 아크릴산생산량 : 20,000 톤 / 년, 국내판매 : 6,000톤해외수출 : 14,000 톤 아크릴산가격 ( 근거자료, 관세청, ICIS Pricing) 국내가격 : 1,807,663원 /ton, 해외가격 : $ 2,513/ton 아크릴산판매금액 : 466억원 / 년국내판매 : 6,000톤 / 년 1,836,673원 / 톤 = 108억원 / 년해외판매 : 14,000 톤 / 년 $ 2,513/ 톤 1020원 ( 현재환율 ) = 358억원 / 년

324 폐락틱산및숙신산유래 C3 및 C4 바이오단량체제조기술개발 구분 사업화연도 2015년도 2020년도 2025년도 개발계획품목 C4 바이오단량체 scale-up을위한 Pilot Plant 건설및가동 C4 바이오단량체 C4 바이오단량체 소요인원 10 명 20 명 50 명 투자계획 제조시설 50,000 천원 500,000 천원 1,000,000 천원 시험시설 500,000 천원 200,000 천원 200,000 천원 생산계획 ( 톤 ) 1,000 4,500 판매계획 ( 억원 ) 내수 수출 계 각단량체의평균가격 2,500$/ 톤기준, 1$=1,020 원기준 판매계획의내수 / 수출비율약 7:3 기준 C3, C4 유도체는가장대표적인아크릴산, BDO, GBL, NMP 기준, 2008년국내시장규모 227천톤기준 2008년 C3, C4 유도체세계시장성장률은 4.85% 이고, 국내시장성장률도이와같다고가정 (Tecnon Orbichem, CJ제일제당, 덕성화학 ( 주 ) 자료를근거하여산출 ) 이를근거로 2025년국내시장의 1% 달성목표 판매계획의내수 / 수출비율약 7:3 기준

325 (2) 사업화가능성 SWOT 분석 보안등급분류 해당하는곳에 체크 결정사유 보안과제인경우작성 보안과제 일반과제

326 국가연구개발사업의관리등에관한규정 제 24 조의 4( 분류기준 ) 1 연구개발과제보안등급은다음각호와같이분류한다. 1. 보안과제 : 연구개발결과물등이외부로유출될경우기술적 재산적가치에상당한손실이예상되어보안조치가필요한경우로서다음각목의어느하나에해당하는과제가. 세계초일류기술제품의개발과관련되는연구개발과제나. 외국에서기술이전을거부하여국산화를추진중인기술또는미래핵심기술로서보호의필요성이인정되는연구개발과제다. 산업기술의유출방지및보호에관한법률 제 2 조제 2 호의국가핵심기술과관련된연구개발과제라. 대외무역법 제 19 조제 1 항및같은법시행령제 32 조의 2 에따른수출허가등의제한이필요한기술과관련된연구개발과제마. 그밖에중앙행정기관의장이보안과제로분류되어야할사유가있다고인정하는과제 2. 일반과제 : 보안과제로지정되지아니한과제 2 연구개발과제수행과정중산출되는모든문서에는제 1 항에따라분류된보안등급을표기하여야한다. 3 보안업무규정 에따른 Ⅰ 급비밀, Ⅱ 급비밀, Ⅲ 급비밀또는이에준하는대외비로분류된과제와 군사기밀보호법시행령 에따른군사 Ⅰ 급비밀, 군사 Ⅱ 급비밀, 군사 Ⅲ 급비밀또는이에준하는대외비로분류된과제에대해서는제 1 항및제 2 항에도불구하고관련법령에서정하는바에따른다

327 제 5 장참고문헌

328

329 β

330

331 부록 [1] SCI 논문 [2] 국내특허 [3] 수상실적

332 3570 Macromolecules 2010, 43, DOI: /ma Facile Synthesis of Thermally Stable Core-Shell Gold Nanoparticles via Photo-Cross-Linkable Polymeric Ligands Misang Yoo, Seyong Kim, Jongmin Lim, Edward J. Kramer, Craig J. Hawker, Bumjoon J. Kim,*, and Joona Bang*, Department of Chemical and Biological Engineering, Korea University, Seoul , Republic of Korea, Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Daejeon , Republic of Korea, and Department and Materials and Materials Research Laboratory, University of California, Santa Barbara, California Received January 5, 2010; Revised Manuscript Received March 1, 2010 Polymer/nanoparticle hybrid materials have attracted significant attention in a variety of applications including photonic bandgap materials, nanostructured solar cells, light-emitting diodes, and memory devices. 1-4 In addition, the bulk properties of polymeric materials such as mechanical strength, conductivity, and rheological properties can be greatly enhanced by introducing nanoparticles into the polymer matrix. 5-8 For all of these applications, it is a critical requirement to achieve compatibility between the nanoparticles and polymers, suppressing macrophase separation of nanoparticles and inducing a complete dispersion of the particles within the polymer matrix. A promising strategy for improving dispersion is to modify the interface between the nanoparticle surface and the polymer matrix by introducing a compatibilizing polymeric shell to the inorganic nanoparticle core. Several research groups have successfully shown that the dispersion of the nanoparticles as well as their precise location within a composite blend can be achieved by tuning the enthalpic interaction between the nanoparticles and matrix through the judicious choice of the polymer chains in the shell including homopolymers, random copolymers, block copolymers, or mixtures of different polymers From the wide range of nanoparticles used in the preparation of nanocomposites, gold nanoparticles (Au NPs) have attracted significant research interest due to their potential applications in catalyst, sensors, and biomedicine and the ability to accurately control their size from 1 to 100 nm Another advantage of Au nanoparticles is the tunability of the surface through the facile grafting of thiol end groups (-SH) to yield a controlled polymer ligand areal density on the gold nanoparticle surface. 33 In addition, the strong contrast between Au NPs and polymers under electron microscopy as well as their ability of light absorption in the visible regime makes them well suited for model studies on the effect of nanoparticles in compatibilizing polymer blends. Despite these advantages, a major challenge with all studies involving thiol ligand stabilized Au nanoparticles is the reversible nature of the Au-thiol bond, which allows ligand escape above 60 C. 34 This serious limitation prevents their use in most of aforementioned applications. In recent studies, the stability of the Au-thiol bond could be improved through the shell cross-linking of polymeric micelles surrounding the Au NPs or the introduction of more than two thiol-anchoring groups at the polymer chain ends However, these methods still suffer from a lack of thermal stability and require multistep synthetic approaches. Matyjaszewski recently demonstrated the synthesis *Corresponding authors. joona@korea.ac.kr (J.B.); bumjoonkim@kaist.ac.kr (B.J.K.). of stable polymer coated Au NPs by a grafting-from approach involving the formation of copolymer brushes consisting of monomers and cross-linkers. 38 However, the degree of control with this one-step procedure is limited, and the thermal stability of the resulting nanoparticles was increased to only 110 C. Herein, we report a simple, yet powerful strategy for preparing thermally stable Au NPs by introducing photo-cross-linkable azide groups (-N 3 ) into the polymeric ligands attached to the Au core. Thiol end-functionalized block copolymers consisting of polystyrene (PS) and azido-polystyrene (PS-N 3 ) blocks were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization technique, and the resulting polymergrafted Au NPs were efficiently cross-linked by exposure to UV light. Consequently, it was observed that the cross-linked Au NPs were thermally stable in both solution and nanocomposite films at elevated temperatures. The selection of azido groups as the photocross-linkable units in this strategy was driven by prior success in utilizing these units for the fabrication of various polymeric nanostructures, such as multilayers or vertically aligned block copolymers Although it is known that photolysis of benzyl azidescanleadtotheirrearrangementtoimines, 43,44 we demonstrated that they can be effectively used as cross-linkers in the polymer system via UV irradiation or heating. In this case, it was suggested that the bimolecular coupling reaction can be facilitated by triplet sensitization of the azide unit instead of the normal rearrangement of singlet nitrenes to the imine. 45 A second critical aspect of the ligand design was that the short PS-N 3 block is placed adjacent to the thiol group, and hence Au cores can be protected, in principle, by cross-linked shells after in situ photo-cross-linking to give core-shell nanostructures with well-defined linear polymer chains surrounding a cross-linked polymer shell (Scheme 1a). A low molecular weight P(S-b-S-N 3 )-SH block copolymer was synthesized by RAFT polymerization (Scheme 1b) with the total molecular weight (M n ) being 3000 g/mol, which allows a large number of polymer chains to be grafted to the gold surface, according to previous studies. 13,14 The block molecular weights were 2000 and 900 g/mol for PS and PS-N 3 block, respectively (Figure S1). Therefore, it can be regarded that there are 9-10 crosslinkable units per polymer chain. As a control experiment, PS-SH was also synthesized with the same molecular weight, 3000 g/ mol, and the polydispersities (PDIs) of both polymers were narrow (1.09 and 1.11 for PS-SH and P(S-b-S-N 3 )-SH, respectively (Figure S1)). The PS-SH and P(S-b-S-N 3 )-SH coated Au NPs, denoted as PS-Au and P(S-b-S-N 3 )-Au, respectively, were synthesized by the two-phase method, 13,14 and the unbound polymers and residual reducing agents were then removed by membrane filtration. The size of Au core measured by transmission pubs.acs.org/macromolecules Published on Web 03/10/2010 r 2010 American Chemical Society

333 3574 Macromolecules, Vol. 43, No. 7, 2010 Note Figure 4. TEM images and the corresponding droplet size distribution of PS/PMMA(50:50) blends with cross-linked Au NPs as compatibilizer, after annealing at 180 C for 48 h. The amounts of cross-linked Au NPs in blends are (a) 0.0, (b) 5.0, and (c) 10.0 wt %. P(S-b-S-N 3 )-Au NPs are nonselective to both the PS and PMMA phases but are localized to the interface to reduce the interfacial tension between the PS and PMMA phases and to avoid the entropic penalty of polymer matrix chains if the NPs are dispersed in either PS or PMMA domain. This feature suggests that the cross-linked Au NPs can function as compatibilizers in polymer blends. To promote small droplet phase sizes in polymer blends, block copolymers whose blocks are each miscible with one of the homopolymers have been widely used as compatibilizers For PS/PMMA blends, it has been well established that addition of PS-b-PMMA block copolymers as compatibilizers can effectively reduce the size of droplets, as they are located at the PS/PMMA interface thus reducing the interfacial tension and retarding droplet coalescence In this vein, the effect of cross-linked Au NPs as compatibilizers in PS/PMMA blends was examined by determining the size of droplets, as shown in Figure 4. Since the volume fractions of PS and PMMA are the same, both PS and PMMA droplets are observed in all samples. In the absence of cross-linked Au NPs, the droplet size spans from submicrometers to several micrometers, with an average size of 0.92 ( 0.33 μm. However, as the cross-linked Au NPs are added to the PS/PMMA blends, it can be clearly observed that the size of droplets decreases significantly. In this case, average sizes of droplets were 0.46 ( 0.14 and 0.32 ( 0.09 μm for addition of 5.0 and 10.0 wt % of cross-linked Au NPs, respectively. Furthermore, we did not observe any aggregation of Au NPs into larger particles within the polymer domain during the thermal annealing of these polymer blends. Therefore, it can be concluded that most of cross-linked Au NPs are located at the interface of PS/PMMA blends and effectively retard droplet phase coarsening. 54 In summary, we have designed thermally stable Au NPs using well-defined photo-cross-linkable block copolymers, P(S-b-S- N 3 )-SH, as polymeric ligands. The thermal stability was achieved via a formation of cross-linked PS-N 3 shell on the Au surface, preventing aggregation and thermal dissociation between Au core and thiol group upon heating coupled with the presence of a PS brush layer attached to the cross-linked shell. These covalently stabilized nanostructures exhibited remarkable thermal stability with no aggregation being observed on heating to 200 C for extended periods of time in both solution and the solid state. This allows the cross-linked Au NPs to serve as compatibilizers for thermally annealed PS/PMMA blends with the cross-linked Au NPs being located at the PS/PMMA interface resulting in the reduction in the droplet size. Since the design of the photocross-linkable polymeric ligands is modular, the surface property of the Au NPs can be readily tuned and applied to other functional metal nanoparticles, providing a versatile route to the fabrication of a variety of nanocomposite systems. Acknowledgment. This work was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF D00235, , , , ), the Korea Ministry of Environment as The Eco-technopia 21 project, and the National Science Foundation through the Materials Research Laboratory at UCSB (MRSEC program DMR ). Supporting Information Available: Size exclusion chromatography traces of PS-SH, PS-RAFT macroinitiator, and P(Sb-S-N 3 )-SH, UV-vis spectra, and additional TEM images. This material is available free of charge via the Internet at References and Notes (1) Beek, W. J. E.; Wienk, M. M.; Janssen, R. A. J. Adv. Mater. 2004, 16, (2) Bockstaller, M. R.; Thomas, E. L. J. Phys. Chem. B 2003, 107, (3) Liu, J. S.; Tanaka, T.; Sivula, K.; Alivisatos, A. P.; Frechet, J. M. J. J. Am. Chem. Soc. 2004, 126, (4) Tseng, R. J.; Huang, J. X.; Ouyang, J.; Kaner, R. B.; Yang, Y. Nano Lett. 2005, 5, (5) Rittigstein, P.; Torkelson, J. M. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, (6) Rittigstein, P.; Priestley, R. D.; Broadbelt, L. J.; Torkelson, J. M. Nat. Mater. 2007, 6, 278. (7) Tjong, S. C. Mater. Sci. Eng., R 2006, 53, 73. (8) Bansal, A.; Yang, H. C.; Li, C. Z.; Cho, K. W.; Benicewicz, B. C.; Kumar, S. K.; Schadler, L. S. Nat. Mater. 2005, 4, 693. (9) Corbierre, M. K.; Cameron, N. S.; Sutton, M.; Mochrie, S. G. J.; Lurio, L. B.; Ruhm, A.; Lennox, R. B. J. Am. Chem. Soc. 2001, 123, (10) Bockstaller, M. R.; Lapetnikov, Y.; Margel, S.; Thomas, E. L. J. Am. Chem. Soc. 2003, 125, (11) Chiu, J. J.; Kim, B. J.; Kramer, E. J.; Pine, D. J. J. Am. Chem. Soc. 2005, 127, (12) Kim, B. J.; Chiu, J. J.; Yi, G. R.; Pine, D. J.; Kramer, E. J. Adv. Mater. 2005, 17, 2618.

334 Top Catal (2010) 53: DOI /s ORIGINAL PAPER The Promotion Effect of Cr on Copper Catalyst in Hydrogenolysis of Glycerol to Propylene Glycol Nam Dong Kim Seogil Oh Ji Bong Joo Kwang Seop Jung Jongheop Yi Published online: 1 April 2010 Ó Springer Science+Business Media, LLC 2010 Abstract Binary Cu/Cr catalysts, containing various molar ratios of copper to chromium, were synthesized and their catalytic activities were examined for the hydrogenolysis of glycerol to propylene glycol. When catalyst containing Cu and Cr ratio of 1:2, it was mainly composed of CuCr 2 O 4 phase. And it was found to have the highest catalytic activity in this reaction, due to its favorable reduction properties. Keywords Hydrogenolysis Copper catalyst Promotion effect Glycerol Propylene glycol 1 Introduction In recent years, biodiesel has been considered as a renewable and environmentally friendly energy source [1, 2]. During the biodiesel production via transesterification of vegetable oils and animal fats, considerable amount of glycerol by-product are formed in a ratio of about 1 kg of glycerol out of every 9 kg biodiesel. As the amount of glycerol production is greatly increased due to the increasing production of biodiesel, necessity of new methods for the production of value-added chemical from glycerol is also increasing. N. D. Kim S. Oh J. B. Joo J. Yi (&) School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , Republic of Korea jyi@snu.ac.kr K. S. Jung GS Caltex Corporation, Munji-dong, Yusung-ku, Daejeon , Republic of Korea Lots of catalytic conversion processes have been reported to convert glycerol into other useful chemicals and broad overview are presented in a recent review [3, 4]. Among the value-added chemicals, propylene glycol is a major commodity that is widely used in the production of unsaturated polyester resins, functional fluids (antifreeze, de-icing, and heat transfer), pharmaceuticals, foods, cosmetics, liquid detergents, tobacco humectants, flavors and fragrances, personal care, paints and animal feed [5]. The majority of propylene glycol is produced via petroleum routes in industry at present [6]. Because of the cost of these process, production of propylene glycol from renewable sources, biodiesel by-product glycerol, has great potential for the cost effective processes. Several researches have been reported on the catalytic conversion of glycerol to propylene glycol. Hydrogenolysis of glycerol to propylene glycol requires high hydrogenation activity for C O bonds and poor hydrogenolytic activity toward C C bonds. For this reason, copper based catalyst, such as Cu/Cr and Cu/Zn catalyst [5, 7 11], showed high catalytic performance compared to the other transition metal catalyst [12], among the various heterogeneous catalysts previously reported. Copper based catalysts are also economical compared to noble metal such as Ru, Pt and Au, which are reported before to have moderate catalytic activity in this reaction [13 15]. Among the copper based catalysts, Cu/Cr catalysts showed exceptionally high catalytic activity in hydrogenolysis of glycerol to propylene glycol. Dasari et al. [5] reported that Cu/Cr catalyst exhibited high selectivity of 85.0% at ca. 55% conversion at 473 K and 1.4 MPa which is much mild condition than that of previously reported. Liang et al. [7] synthesized Cu/Cr catalyst with high surface area by template method using carbon template giving almost 100% of selectivity to yield propylene glycol. Although significant 123

335 522 Top Catal (2010) 53: ,2-PDO yield (%) that CuCr-0.33 catalyst maintains its high catalytic activity throughout the long term reactions, which means that it possibly can be utilized for the industrial production of propylene glycol from glycerol. 4 Conclusion Time (hr) Fig. 8 Results of time on stream in the reaction test over CuCr-0.33 catalyst for 24 h Copper catalysts promoted by chromium, containing various molar ratios (1:0, 1:1, 1:2, 1:3 and 0:1) were synthesized and their catalytic activities were evaluated for the hydrogenolysis of glycerol to propylene glycol. Cr was found to have only a promotion effect and showed negligible catalytic activity itself. As Cr was introduced to Cu catalyst, the CuCr 2 O 4 tetragonal spinel phase began to be produced. The resulting CuCr 2 O 4 tetragonal spinel phase was transformed into the CuCr 2 O 4 cubic spinel phase during the reduction process and hydrogen atoms were occluded inside its crystal structure. Such reduced binary Cu/Cr catalysts were found to have strong acidic property and contain large amount of occluded hydrogen species, which are beneficial for dehydration of glycerol to acetol and hydrogenation of acetol to propylene glycol, respectively. Among the catalysts tested, the CuCr-0.33 catalyst showed the best catalytic performance. It can be concluded that the CuCr-0.33 catalyst, which had the highest fraction of CuCr 2 O 4 spinel phase among the catalysts studied here, showed the best catalytic performance with an 80.3% of conversion, an 83.9% selectivity and gave a 67.4% total yield. Acknowledgements The authors wish to acknowledge support from the GS Caltex Corporation. This research was partially supported by WCU (World Class University) program through the Korea science and Engineering Foundation funded by the Ministry Of Education, Science and Technology ( ) and Korea Ministry of Environment as The Eco-technopia 21 project. References 1. Chheda JN, Huber GW, Dumesic JA (2007) Angew Chem Int Ed 46: McKendry P (2002) Bioresour Technol 83:37 3. Pagliaro M, Ciriminna R, Kimura H, Rossi M, Pina CD (2007) Angew Chem Int Ed 46: Behr A, Eilting J, Irawadi K, Leschinski J, Lindner F (2008) Green Chem 10:13 5. Dasari MA, Kiatsimkul PP, Sutterlin WR, Suppes GJ (2005) Appl Catal A 281: van Haveren J, Scott EL, Sanders J (2008) Biofuels Bioproducts Biorefining 2:41 7. Liang C, Ma Z, Ding L, Qiu J (2009) Catal Lett 130: Meher LC, Gopinath R, Naik SN, Dalai AK (2009) Ind Eng Chem Res 48: Jalowiecki L, Daage M, Bonnelle JP, Tchen AH (1985) Appl Catal 16:1 10. Wang S, Liu H (2007) Catal Lett 117: Balaraju M, Rekha V, Prasad PSS, Prasad RBN, Lingaiah N (2008) Catal Lett 126: Perosa A, Tundo P (2005) Ind Eng Chem Res 44: Miyazawa T, Koso S, Kunimori K, Tomishige K (2007) Appl Catal A 318: Miyazawa T, Kusunoki Y, Kunimori K, Tomishige K (2006) J Catal 240: Balaraju M, Rekha V, Prasad PSS, Devi BLAP, Prasad RBN, Lingaiah N (2009) Appl Catal A 354: Kawamoto AM, Pardini LC, Rezende LC (2004) Aerosp Sci Technol 8: Moretti E, Storaro L, Talon A, Patrono P, Pinzari F, Montanari T, Ramis G, Lenarda M (2008) Appl Catal A 344: Makarova OV, Yureva TM, Kustova GN, Ziborov AV, Plyasova LM, Minyukova TP, Davydova LP, Zaikovskii VI (1993) Kinet Catal 34: Plyasova LM, Solovyeva LP, Krieger TA, Makarova OV, Yurieva TM (1996) J Mol Catal A 105: Makarova OV, Yureva TM, Plyasova LM, Kriger TA, Zaikovskii VI (1994) Kinet Catal 35: Bechara R, Wrobel G, Daage M, Bonnelle JP (1985) Appl Catal 16:15 123

336 Catal Lett (2010) 138:28 33 DOI /s Hydrogenation of Succinic Acid to c-butyrolactone over Palladium Catalyst Supported on Mesoporous Alumina Xerogel Ung Gi Hong Sunhwan Hwang Jeong Gil Seo Jongheop Yi In Kyu Song Received: 17 February 2010 / Accepted: 7 May 2010 / Published online: 20 May 2010 Ó Springer Science+Business Media, LLC 2010 Abstract Mesoporous alumina xerogel (AX) was prepared by a sol gel method for use as a support for palladium catalyst. Palladium catalyst supported on mesoporous alumina xerogel (Pd/AX) was then prepared by an impregnation method. For comparison, commercial alumina (AC) was also used to prepare Pd/AC catalyst by an impregnation method. Liquid-phase hydrogenation of succinic acid to c-butyrolactone (GBL) was carried out using supported palladium catalysts (Pd/AC and Pd/AX). The supported palladium catalysts (Pd/AC and Pd/AX) were characterized by XRD, BET, HR-TEM, and hydrogen chemisorption analyses. In the hydrogenation of succinic acid to GBL, Pd/AX catalyst showed a better catalytic performance than Pd/AC catalyst. Fine dispersion of palladium of Pd/AX catalyst was responsible for its high catalytic activity. Keywords Hydrogenation Succinic acid c-butyrolactone Alumina xerogel Palladium catalyst 1 Introduction Succinic acid is a promising alternative chemical feedstock that can replace maleic anhydride in the production of c- butyrolactone (GBL) (Fig. 1). GBL has been widely used in fine chemical and pharmaceutical industries as a solvent [1 3]. Conventionally, GBL has been produced by direct hydrogenation of maleic anhydride [4 6]. However, U. G. Hong S. Hwang J. G. Seo J. Yi I. K. Song (&) School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , South Korea inksong@snu.ac.kr demand for finding a new and cheap bio-based platform chemical to produce GBL has been continuously increased. Therefore, direct hydrogenation of succinic acid is predicted to be one of the economical chemical processes for the production of GBL, because of the increase of succinic acid production in the biorefinery process [7 10]. Liquid-phase hydrogenation of succinic acid can produce not only GBL but also tetrahydrofuran (THF) via consecutive hydrogenation of GBL. For selective production of GBL, therefore, it is important to control hydrogenation activity of the catalyst to avoid consecutive hydrogenation of GBL. In the liquid-phase hydrogenation of succinic acid, noble metal catalysts such as palladium, platinum, and ruthenium have been generally used [11, 12]. Although ruthenium-based catalysts are very effective as oxidative hydrogenation catalysts, they might completely reduce carbonyl groups in the succinic acid, leading to the formation of THF [13 15]. On the other hand, palladiumbased catalysts retaining moderate activity can be potential candidates for selective production of GBL in the liquidphase hydrogenation of succinic acid [16 18]. Many researches on palladium catalysts have been focused on finding suitable supporting materials. Among various support materials, aluminas have found successful applications in many areas due to their thermal and mechanical stability. Aluminas with narrow pore size distribution, uniform pore structure, and high pore volume are generally desirable as supporting materials. In this work, mesoporous alumina xerogel (AX) support was prepared by a sol gel method. Palladium catalyst supported on mesoporous alumina xerogel (Pd/AX) was then prepared by an impregnation method. For comparison, commercial alumina (AC) was also used to prepare Pd/AC catalyst by an impregnation method. The supported palladium catalysts (Pd/AC and Pd/AX) were characterized by 123

337 Hydrogenation of Succinic Acid to c-butyrolactone 33 dispersed on the AX support. In the hydrogenation of succinic acid, Pd/AX catalyst showed a higher yield for GBL than Pd/AC catalyst. The enhanced catalytic performance of Pd/AX catalyst compared to Pd/AC catalyst was due to fine dispersion of palladium. Thus, palladium dispersion played a key role in the liquid-phase hydrogenation of succinic acid over supported palladium catalyst. It is concluded that GBL could be efficiently produced from a bio-based platform chemical (succinic acid) using Pd/AX catalyst. Acknowledgement This work was supported by Korea Ministry of Environment as The Eco-Technopia 21 Project. References 1. Jung SM, Godard E, Jung SY, Park K-C, Choi JU (2003) J Mol Catal A 198: Gao CG, Zhao YX, Liu DS (2007) Catal Lett 118: Budroni G, Corma A (2008) J Catal 257: Chaudhari RV, Jaganathan R, Vaidya SH, Chaudhari ST, Naik RV, Rode CV (1999) Chem Eng Sci 54: Hara Y, Takahashi K (2002) Catal Surv Jpn 6: Wang Q, Cheng H, Liu R, Hao J, Yu Y, Cai S, Zhao F (2009) Catal Commun 10: Glassner DA, Elankovan P, Beacom DR, Berglund KA (1995) Appl Biochem Biotechnol 51: Song H, Lee SY (2006) Enzym Microb Technol 39: Bechthold I, Bretz K, Kabasci S, Kopitzky R, Springer A (2008) Chem Eng Technol 31: Li Q, Xing J, Li W, Liu Q, Su Z (2009) Ind Eng Chem Res 48: Delhomme C, Weuster-Botz D, Kühn FE (2009) Green Chem 11: Cukalovic A, Stevens CV (2008) Biofuel Bioprod Biorefin 2: Deshpande RM, Buwa VV, Rode CV, Chaudhari RV, Mills PL (2002) Catal Commun 3: Luque R, Clark JH, Yoshida K, Gai PL (2009) Chem Commun Schwartz JAT (1995) US Patent 5,478, Pillai UR, Sahle-Demessie E, Young D (2003) Appl Catal B 43: Jeong H, Kim TH, Kim KI, Cho SH (2006) Fuel Process Technol 87: Werpy T, Frye JJG, Wang Y, Zacher AH (2002) US Patent 6,670, Seo JG, Youn MH, Lee H-I, Kim JJ, Yang E, Chung JS, Kim P, Song IK (2008) Chem Eng J 141: Seo JG, Youn MH, Park S, Chung JS, Song IK (2009) Int J Hydrogen Energy 34: Cho KM, Park S, Seo JG, Youn MH, Baeck S-H, Jun K-W, Chung JS, Song IK (2008) Appl Catal B 83: Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquérol J, Siemieniewska T (1985) Pure Appl Chem 57: Kim P, Kim Y, Kim H, Song IK, Yi J (2004) Appl Catal A 272: Seo JG, Youn MH, Cho KM, Park S, Song IK (2007) J Power Sources 173: Suh DJ, Park T-J, Kim J-H, Kim K-L (1997) Chem Mater 9:

338 Korean J. Chem. Eng., 27(6), (2010) DOI: /s x INVITED REVIEW PAPER Simple one-pot synthesis of a mesoporous superacidic catalyst for the dehydration of glycerol to acrolein Lina Yang*,, Ji Bong Joo**,, Nam Dong Kim**, Kwang Seop Jung***, and Jongheop Yi**, *Department of Petrochemical Engineering, Liaoning Shihua University, Fushun , China **School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, 599 Gwanak-ro, Gwanak-gu, Seoul , Korea ***GS Caltex Corporation, 104-4, Munji-dong, Yusung-gu, Daejeon , Korea (Received 28 October 2009 accepted 19 January 2010) 2 Abstract Mesoporous silica containing a ZrO 2 /SO 4 superacid catalyst (SZS) was synthesized via a simple one-pot 2 process. ZrO 2 /SO 4 (SZ) was introduced during the synthesis of the SBA-15. When the molar ratio of Zr to Si was less than 0.37 : 1, a 2D-hexagonal pore structure was maintained. The superacidic SZ was successfully supported on mesoporous silica resulting in superacidity. The prepared SZS catalysts were applied to the conversion of glycerol to acrolein by dehydration and had considerable catalytic activity. The present study describes the first attempt to utilize mesoporous silica-supported superacid catalysts in the dehydration of glycerol to produce acrolein. 2 Key words: Mesoporous Silica, ZrO 2 /SO 4, One-pot Synthesis, Superacid, Acrolein INTRODUCTION Solid superacids are potentially useful as solid catalysts for chemical reactions that require very strong acid sites under mild conditions. Acidic sulfated zirconia (ZrO 2 /SO 4 2 ), a well known superacid, has attracted a great deal of attention because of its excellent catalytic activity and strong acidic properties [1,2]. Sulfated zirconia is highly useful in that it can be used to promote chemical reactions that involve proton transfer. However, its low surface area limits its applications [3]. An effective solution to the problem of the low surface area of sulfated zirconia would be to synthesize a supported catalyst using support materials which have a high surface area. For this purpose, a number of materials, including silica, alumina and a microporous zeolite, have been investigated as possible substrates [4-10]. Mesoporous materials such as MCM-x, SBA-x and CMK-x have advantageous characteristics, which include a high surface area, relatively large mesopores and a uniform pore structure resulting in low hindrance to diffusion. The use of mesoporous materials in supported ZrO 2 /SO 4 2 catalysts would greatly expand the scope of applications of this superacid catalyst [3,11-16]. Hua et al. [14] demonstrated the use of mesoporous silica SBA- 15 as a supporting material for a supported superacid catalyst. Other researchers also have reported the introduction of zirconia during the SBA-15 synthesis using a two-step procedure that requires two types of inorganic-organic complexes [17]. Although substantial progress has been made in the synthesis of a sulfated zirconia (ZrO 2 / SO 4 2 ) catalyst on a mesoporous silica support, the development of a new straightforward route is needed, because existing synthetic processes are complicated and time-consuming. Glycerol is the one of the main by-products produced during the production of bio-diesel and it promises to become more widely available as the biodiesel industry continues to develop [18]. It is expected that the cost of glycerol will decrease soon with the current increase in biodiesel production. Thus, glycerol could be converted to high-value chemicals such as propandiols, glycerolcarbonate, acrolein and other compounds. Among the above chemicals, acrolein constitutes an important intermediate in the chemical industry, as it is frequently used as a raw material in the synthesis of acrylic acid and pharmaceuticals. The catalytic conversion of glycerol to acrolein via dehydration might be an important route to achieving the complete utilization of available glycerol [19]. Various acidic catalysts have been investigated in homogeneous and heterogeneous systems for the production of acrolein by the dehydration of glycerol [19-21]. Although many studies have investigated the use of various acidic catalysts in dehydration reactions, the activities of such catalysts are insufficient for the practical dehydration of glycerol. Thus, more efficient acidic catalysts, which function under mild conditions, are needed for this reaction. In this work, we describe a method for the simple synthesis of superacid catalysts supported on mesoporous silica (SZS). The method is much simpler and less time-consuming than either the conventional impregnation method or the introduction method in which two types of inorganic-organic complexes are employed. The prepared catalysts (SZS-x) were examined as acidic catalysts for the dehydration of glycerol to acrolein. To our knowledge, this is the first report of the use of a mesoporous silica-supported superacid catalyst in the conversion of glycerol to acrolein. EXPERIMENTAL To whom correspondence should be addressed. jyi@snu.ac.kr The authors (Lina Yang and Ji Bong Joo) contributed equally to this work Catalyst Preparation The unsupported superacid catalyst was synthesized by precipitation, followed by sulfated treatment as previously reported [14,22-

339 Simple one-pot synthesis of a mesoporous superacidic catalyst for the dehydration of glycerol to acrolein 1699 via a simple one-pot synthesis and the prepared SZS showed superacidic properties with an ordered mesostructure. In addition, we first attempted to apply the SZS catalyst to the dehydration of glycerol to acrolein. From the experimental results, although SZS has superacidic characteristics and considerable catalytic activity as a heterogeneous acidic catalyst, it is still insufficient for practical use in terms of acrolein productive yields and catalyst reusability. Detailed investigations on the above results of mesoporous superacid catalysts are currently underway. CONCLUSIONS Mesoporous superacid catalysts (SZS) with highly ordered mesostructures were synthesized by a one-pot synthetic procedure during the synthesis of mesoporous silica. When the molar ratio of Zr to Si is less than 0.37 : 1, the prepared SZS samples have the typical mesoporous structure with a regular 2D hexagonal array of channels and a uniform pore size. The active SZ was highly dispersed on the mesoporous silica support. The prepared SZS also showed superacidic characteristics that are similar to bulk SZ. The prepared SZS catalyst was applied to the dehydration of glycerol to produce acrolein. In the production of acrolein from glycerol, the supported SZS (0.19 : 1) catalyst showed considerable catalytic activities and the SZS (0.19 : 1) catalyst could be easily separated from the reaction media at the end of the reaction. Detailed investigations dealing with enhancing of acrolein production and evaluating catalyst stability using mesoporous superacid catalysts are currently underway. ACKNOWLEDGEMENT The authors wish to thank the Korean Foundation for Advanced Studies (KFAS) and the GS Caltex Corporation for financial support. This research was supported by WCU (World Class University) program through the Korea Science and Engineering Foundation funded by the Ministry of Education, Science and Technology ( ). This subject is supported by Korea Ministry of Environment as The Eco-technopia 21 project. REFERENCES 1. M. Hino, S. Kobayashi and K. Arata, J. Am. Chem. Soc., 101, 6439 (1979). 2. K. Arata, Adv. Catal., 37, 165 (1990). 3. Y. Sun, L. Zhu, H. J. Lu, R. W. Wang, S. Lin, D. Z. Jiang and F. S. Xiao, Appl. Catal. A: Gen., 237, 21 (2002). 4. G. D. Yadav and J. J. Nair, Micro. Meso. Mater., 33, 1 (1999). 5. Y. D. Xia, W. M. Hua, Y. Tang and Z. Gao, Chem. Commun., 1899 (1999). 6. T. Jin, T. Yamaguchi and K. Tanabe, J. Phys. Chem., 90, 4797 (1986). 7. G. D. Yadav and N. Kirthivasan, J. Chem. Soc., Chem. Commun., 203 (1995). 8. M. Hino and K. Arata, J. Chem. Soc., Chem. Commun., 851 (1980). 9. F. R. Chen, G. Coudurier, J. F. Joly and J. C. Vederine, J. Catal., 143, 616 (1993). 10. T. Lei, J. S. Xu, Y. Tang, W. M. Hua and Z. Gao, Appl. Catal. A: Gen., 192, 181 (2000). 11. Q. H. Xia, K. Hidajat and S. Kawi, Chem. Commun., 2229 (2000). 12. C. L. Chen, S. F. Cheng, H. P. Lin, S. T. Wong and C. Y. Mou, Appl. Catal. A: Gen., 215, 21 (2001). 13. C. P. Wei, S. Z. Li, B. Zhou, C. J. Peng and K. J. Zhen, Chem. Res. Chinese U., 22, 371 (2006). 14. W. M. Hua, Y. H. Yue and Z. Gao, J. Mol. Catal. A: Chem., 170, 195 (2001). 15. H. Matsuhashi, M. Tanaka, H. Nakamura and K. Arata, Appl. Catal. A: Gen., 208, 1 (2001). 16. M. A. Ecormier, A. F. Lee and K. Wilson. Micro. Meso. Mater., 80, 301 (2005). 17. F. Li, F. Yu, Y. Li, R. Li and K. Xie, Micro. Meso. Mater., 101, 250 (2007). 18. G. J. Suppes, M. A. Dasari, E. J. Doskocil, P. J. Mankidy and M. J. Goff, Appl. Catal. A: Gen., 257, 213 (2004). 19. S. H. Chai, H. P. Wang, Y. Liang and B. Q. Xu, J. Catal., (2007). 20. L. Ott, M. Bicker and H. Vogel, Green Chem., 8, 214 (2006). 21. E. Tsukuda, S. Sato, R. Takahashi and T. Sodesawa, Catal. Commun., 8, 1349 (2007). 22. G. X. Yu, X. L. Zhou, C. L. Li, L. F. Chen and J. A. Wang, Catal. Today, 148, 169 (2009). 23. A. Permsubscul, T. Vitidsant and S. Damronglerd, Korean J. Chem. Eng., 24, 37 (2007). 24. C. X. Ciao and Z. Gao, Mater. Chem. Phys., 50, 15 (1997). 25. A. Corma, V. Fornés, M. I. Juan-Rajadell and J. M. López Nieto, Appl. Catal. A: Gen., 116, 151 (1994). 26. T. Yamamoto, T. Tanaka, S. Takenaka, S. Yoshida, T. Onari, Y. Takahashi, T. Kosaka, S. Hasegawa and M. Kudo, J. Phys. Chem. B., 103, 2385 (1999). 27. E. Rodríguez-Castellón, A. Jiménez-López, P. Maireles-Torres, D. J. Jones, J. Rozière, M. Trombetta, G. Busca, M. Lenarda and L. Storaro, J. Solid State Chem., 175, 159 (2003). 28. G. D. Yadav and A. D. Murkute, J. Catal., 224, 218 (2004). 29. H. Yan, Y. Yang, D. Tong, X. Xiang and C. Hu, Catal. Commun., 10, 1588 (2009). 30. R. Li, F. Yu, F. Li, M. Zhou, B. Xu and K. Xie, J. Solid State Chem., 182, 991 (2009). Korean J. Chem. Eng.(Vol. 27, No. 6)

Journal of Molecular Catalysis A: Chemical 335 (2011) 82 88 Contents lists available at ScienceDirect Journal of Molecular Catalysis A: Chemical journal homepage: www.elsevier.

340 Journal of Molecular Catalysis A: Chemical 335 (2011) Contents lists available at ScienceDirect Journal of Molecular Catalysis A: Chemical journal homepage: Shape effect of ceria in Cu/ceria catalysts for preferential CO oxidation Jaeman Han a, Hyung Jun Kim b, Sangwoon Yoon b, Hyunjoo Lee a, a Department of Chemical and Biomolecular Engineering, The Specialized Graduate School of Hydrogen & Fuel Cell, Yonsei University, Seoul , South Korea b Department of Chemistry, Dankook University, Gyeonggi , South Korea article info abstract Article history: Received 3 September 2010 Received in revised form 11 November 2010 Accepted 14 November 2010 Available online 21 November 2010 Keywords: Ceria Shape Copper PROX Long-term stability Copper was deposited on different shapes of ceria supports (i.e., rods, cubes, and octahedra) and used as catalysts for preferential CO oxidation in excess amounts of hydrogen. When the same amount of copper was deposited, the copper content on the surface measured by X-ray photoelectron spectroscopy differed significantly, with more copper on the ceria octahedra. Copper seemed to migrate into the bulk ceria to a greater degree on the rods. The Cu/ceria-octahedra showed the highest activity of 95% at 140 C among the three shapes, whereas the Cu/ceria-rods showed higher CO conversion than the Cu/ceria-octahedra at higher temperatures. The Cu/ceria-octahedra showed no activity degradation for CO conversion at 140 C over 100 h, whereas the activity decreased by 13% for Cu/ceria-rod and 32% for Cu/ceria-cube at the same temperature. The metals Au and Pt were also deposited on the different shapes of ceria, and their activity and selectivity were evaluated Elsevier B.V. All rights reserved. 1. Introduction Catalytic properties of activity and selectivity can be controlled by changing the shapes of the catalysts [1,2]. In the case of metallic catalysts, different shapes of nanoparticles have distinct surface atomic arrangements, such as a square arrangement for a {100} surface, a hexagonal arrangement for a {111} surface, or a grooved arrangement for a {110} surface. The change in surface atomic arrangement causes differences in the geometry and binding strength of reactants adsorbed on the surface, resulting in differences in activity and selectivity [3 5]. Metal oxide catalysts with various surface crystalline structures also have different formation energies for oxygen vacancy, leading to differences in oxidation activity. Ceria with different surface crystalline structures, in particular, have been actively investigated [6,7]. The formation and migration of oxygen vacancy and CO adsorption have been estimated for ceria by theoretical simulation [8,9]. For example, when CO is adsorbed on {110}, {100}, and {111} surfaces, a CO molecule bridges two surface oxygen atoms on the surface of {110} or {100}, pulling the atoms out of the lattice sites and forming CO 3 species. In this case, the surface structure is deformed due to mild reduction. However, a CO molecule is weakly bound to the {111} surface, preserving the surface structure [9]. The effect of ceria shape has been investigated for the water gas shift reaction (H 2 O+CO H 2 +CO 2 ) by using gold-deposited ceria rods, cubes, Corresponding author. Tel.: ; fax: address: azhyun@yonsei.ac.kr (H. Lee). and polyhedra [10]. The rod shape of a ceria nanocrystal has {110} and {100} surfaces, the cubic shape has a {100} surface, and the polyhedral shape mainly has a {1 1 1} surface. CO conversion was evaluated within a range of C. The rod with the smallest oxygen vacancy formation energy showed the highest activity in all ranges of temperature. Hydrogen, which is the main energy source for fuel cells, has been produced from the water gas shift reaction or the steam reformation of fossil fuel. In this process, a small amount of CO inevitably remains in the product gas. The residual CO severely poisons the platinum catalyst inside the fuel cell assembly. Therefore, removing CO from hydrogen gas prior to fuel cell operation is essential, and this is usually achieved by the preferential oxidation (PROX) reaction. In the PROX reaction, CO is selectively oxidized to CO 2 in the presence of excessive amounts of hydrogen. Because the oxidation of hydrogen into water is thermodynamically favorable at higher temperatures, the selective CO oxidation can occur at low temperatures [11]. The noble metal catalysts Au, Pt, and Ru have been used to achieve this effect, but high costs hinder their practical use [12 14]. Recently, Cu/ceria was reported to show good results for PROX reactions, and the effects of dopant and nanostructure have been actively investigated [15 20]. In this study, copper was deposited on three different shapes of ceria nanocrystals: rods, cubes, and octahedra. The activity, selectivity and long-term stability of Cu/ceria catalysts with various ceria shapes were evaluated for the PROX reaction. Copper was deposited more on the surface for octahedra while copper seemed to migrate more into lattice for rod. Although oxygen vacancies was formed more on ceria rod, Cu/ceria-octahedra with more surface copper /$ see front matter 2010 Elsevier B.V. All rights reserved. doi: /j.molcata

341 88 J. Han et al. / Journal of Molecular Catalysis A: Chemical 335 (2011) deposited, the activity was similar to or lower than the 1 wt% cases. For both Au and Pt cases, the rods showed the highest activity at low temperatures while the activity was similar for rods and octahedra at high temperatures. These noble metals showed higher activity than Cu/ceria at the lower temperature region, but their maximum activity was lower than Cu/ceria, being 84% at 40 C for Au/ceria and 74% at 80 C for Pt/ceria compared to 95% at 140 C for Cu/ceria. The surface defects of ceria play a role as anchoring sites of metals [32], and the interactions of the ceria surface defects and the anchored metals would vary for different kinds of metal. Consequently, the PROX properties were greatly affected by the kind of deposited metal. 4. Conclusion Copper was deposited on different shapes of ceria nanocrystals (rods, cubes, and octahedra). The activity, selectivity and long-term stability of the Cu/ceria catalysts were evaluated for the PROX reaction. When the copper was deposited on the ceria support, the surface content of the copper significantly differed depending on the ceria shapes, with more copper on the octahedra. Copper seemed to incorporate inside the ceria lattice more in ceria rods. The CO adsorption increased greatly upon copper deposition. The Cu/ceria-rods showed greater CO adsorption in high temperatures above 250 C, whereas the Cu/ceria-octahedra showed slightly more CO adsorption at low temperatures. Copper incorporated inside the ceria lattice would move back to the ceria surface more at high temperatures, resulting in more CO oxidation. The oxygen vacancy increased significantly after copper deposition. The Cu/ceria catalysts showed no apparent shape degradation after the PROX reaction. The high activity of the Cu/ceria-octahedra, especially, remained unchanged over 100 h while the other shapes showed degradation. Au or Pt was also deposited on the different ceria shapes, and their PROX activity and selectivity were evaluated. Acknowledgements This work was supported by the DAPA/ADD of Korea, the National Research Foundation of Korea Grant Funded by the Korean Government (MEST) (NRF-2009-C1AAA ) and the Korean Ministry of Environment as Converging technology project ( ). References [1] A.R. Tao, S. Habas, P. Yang, Small 4 (2008) 310. [2] Y. Xia, Y.J. Xiong, B. Lim, S.E. Skrabalak, Angew. Chem., Int. Ed. 48 (2009) 60. [3] K.M. Bratlie, H. Lee, K. Komvopoulos, P. Yang, G.A. Somorjai, Nano Lett. 7 (2007) [4] S.E. Habas, H. Lee, V. Radmilovic, G.A. Somorjai, P. Yang, Nat. Mater. 6 (2007) 692. [5] C. Kim, H. Lee, Catal. Commun. 11 (2009) 7. [6] E. Aneggi, J. Llorca, M. Boaro, A. Trovarelli, J. Catal. 234 (2005) 88. [7] K.B. Zhou, X. Wang, X.M. Sun, Q. Peng, Y.D. Li, J. 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342 Catal Lett (2011) 141: DOI /s Hydrogenation of Succinic Acid to c-butyrolactone (GBL) Over Palladium-Alumina Composite Catalyst Prepared by a Single-Step Sol Gel Method Ung Gi Hong Joongwon Lee Sunhwan Hwang In Kyu Song Received: 22 October 2010 / Accepted: 10 November 2010 / Published online: 23 November 2010 Ó Springer Science+Business Media, LLC 2010 Abstract Mesoporous palladium-alumina (Pd-A) composite catalysts prepared by a single-step sol gel method were calcined at various temperatures to control palladium surface area and acidity. The Pd-A catalysts were characterized by XRD, BET, N 2 adsorption desorption isotherm, H 2 chemisorption, 27 Al MAS NMR, NH 3 -TPD, and HR- TEM analyses. Liquid-phase hydrogenation of succinic acid to c-butyrolactone (GBL) was carried out over Pd-A catalyst in a batch reactor. The effect of calcination temperature of Pd-A catalyst on the palladium surface area and catalytic performance was investigated. In the hydrogenation of succinic acid, conversion of succinic acid increased with increasing palladium surface area of Pd-A catalyst. Selectivity for GBL depended on the formation of succinic anhydride (an intermediate product formed by acid catalysis) and by-products (formed by hydrogenolysis). Nevertheless, yield for GBL also increased with increasing palladium surface area of Pd-A catalyst. Thus, palladium surface area played an important role in enhancing the catalytic performance of Pd-A catalyst in the hydrogenation of succinic acid to GBL. Keywords Hydrogenation Succinic acid c-butyrolactone Palladium-alumina Sol gel method U. G. Hong J. Lee S. Hwang I. K. Song (&) School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , South Korea inksong@snu.ac.kr 1 Introduction Succinic acid (SA) is a new bio-derived platform material that can produce useful C 4 chemicals, such as c-butyrolactone (GBL), 1,4-butanediol (BDO), and tetrahydrofuran (THF) (Fig. 1) [1 3]. In particular, GBL is used as a starting material for the synthesis of THF, N-methyl-2- pyrrolidone (NMP), and 2-pyrrolidone which are widely used in chemical and pharmaceutical industries [4 6]. Figure 1 shows the reaction pathway for various C 4 chemicals from succinic acid (SA). Hydrogenation of SA follows some consecutive reaction steps. GBL is formed by hydrogenation of SA. However, further hydrogenation of GBL leads to the formation of BDO and THF. Therefore, it is very important to find a suitable catalyst to increase selectivity for GBL and avoid formation of fully hydrogenated products. It is known that palladium-based catalyst is one of the efficient catalysts for selective formation of GBL through hydrogenation of succinic acid [7, 8]. Many researches on palladium catalysts have been focused on finding suitable supporting materials. Among various support materials, alumina has been widely employed due to its thermal and mechanical stability. We have previously investigated the liquid-phase hydrogenation of SA to GBL over palladium catalyst impregnated on alumina xerogel support prepared by a sol gel method (denoted as Pd/AX catalyst) [9]. We found that alumina prepared by a sol gel method retained hydroxyl-rich surface, leading to the unique chemical and physical properties compared to that prepared by a conventional method. For this reason, Pd/AX catalyst showed excellent reusability and stability in the hydrogenation of SA to GBL, as reported in our previous work [9]. However, Pd/AX catalyst prepared by an impregnation method required a number of calcination and drying steps, and 123

343 338 U. G. Hong et al. Conversion of succinic acid (%) Pd-A950 Pd-A950 Figure 8 shows the correlations between palladium surface area of Pd-A catalyst and catalytic performance in the hydrogenation of succinic acid. Conversion of succinic acid over Pd-A catalyst increased with increasing palladium surface area of Pd-A catalyst. Although selectivity for GBL is dependent on the amount of SAN formed by acid catalysis, yield for GBL also roughly increased with increasing palladium surface area. Thus, palladium surface area of Pd-A catalyst served as an important factor determining the catalytic performance of Pd-A catalyst in the hydrogenation of succinic acid to GBL. 4 Conclusions Pd-A850 Pd-A850 Pd-A450 Pd-A Palladium surface area (m 2 /g-cat.) Pd-A550 Pd-A750 Pd-A450 Pd-A650 Pd-A750 Pd-A550 Mesoporous palladium-alumina (Pd-A) composite catalysts prepared by a single-step sol gel method were calcined at various temperatures to control palladium surface area and acidity. It was revealed that palladium surface area and acidity of Pd-A catalyst could be controlled by changing calcination temperature of Pd-A catalyst. Palladium surface area of Pd-A catalyst increased with decreasing calcination temperature, while acidity of Pd-A catalyst showed a volcano-shaped trend with respect to calcination temperature. In the hydrogenation of succinic acid, Pd-A catalyst prepared by a single-step sol gel method showed better catalytic performance than Pd/AX catalyst prepared by an impregnation method. Conversion of succinic acid increased with increasing palladium surface area of Pd-A catalyst. Although selectivity for GBL is dependent on hydrogenolysis and acid-catalyzed reactions of succinic acid, yield for GBL also increased with increasing palladium surface area. Thus, palladium surface area of Pd-A catalyst played an important role in enhancing the catalytic Yield for GBL (%) Fig. 8 Correlations between palladium surface area of Pd-A catalyst and catalytic performance in the hydrogenation of succinic acid performance of Pd-A catalyst in the hydrogenation of succinic acid to GBL. Acknowledgement This subject is supported by Korea Ministry of Environment as Converging Technology Project ( ). References 1. Deshpande RM, Buwa VV, Rode CV, Chaudhari RV, Mills PL (2002) Catal Commun 3: Cukalovic A, Stevens CV (2008) Biofuels Bioprod Bioref 2: Bechthold I, Bretz K, Kabasci S, Kopitzky R, Springer A (2008) Chem Eng Technol 31: Jung SM, Godard E, Jung SY, Park K-C, Choi JU (2003) J Mol Catal A Chem 198: Budroni G, Corma A (2008) J Catal 257: Gao CG, Zhao YX, Liu DS (2007) Catal Lett 118: Luque R, Clark JH, Yoshida K, Gai PL (2009) Chem Commun Mihn DP, Besson M, Pinel C, Fuertes P, Petitjean C (2010) Top Catal 53: Hong UG, Hwang S, Seo JG, Yi J, Song IK (2010) Catal Lett 138: Seo JG, Youn MH, Lee H-I, Kim JJ, Yang E, Chung JS, Kim P, Song IK (2008) Chem Eng J 141: Seo JG, Youn MH, Cho KM, Park S, Lee SH, Lee J, Song IK (2008) Korean J Chem Eng 25: Cho KM, Park S, Seo JG, Youn MH, Nam I, Baeck S-H, Chung JS, Jun K-W, Song IK (2009) Chem Eng J 146: Seo JG, Youn MH, Park S, Song IK (2008) Int J Hydrogen Energy 33: Seo JG, Youn MH, Cho KM, Park S, Song IK (2007) J Power Sour 173: Cho KM, Park S, Seo JG, Youn MH, Baeck S-H, Jun K-W, Chung JS, Song IK (2008) Appl Catal B Environ 83: Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquérol J, Siemieniewska T (1985) Pure Appl Chem 57: Cai S-H, Rashkeev SN, Pantelides ST, Sohlberg K (2003) Phys Rev B 67: Rinaldi R, Schuchardt U (2005) J Catal 236: Krokidis X, Raybaud P, Gobichon A-E, Rebours B, Euzen R, Toulhoat H (2001) J Phys Chem B 105: Sohlberg K, Pantelides ST, Pennycook SJ (2001) J Am Chem Soc 123: Kim Y, Kim C, Kim P, Yi J (2005) J Non-Cryst Solids 351: O Dell LA, Savin SLP, Chadwick AV, Smith ME (2007) Solid State Nucl Mag 31: Kim DH, Woo SI, Yang O-B (2000) Appl Catal B Environ 26: Iwamoto R, Fernadez C, Amoureux JP, Grimblot J (1998) J Phys Chem B 102: Chuah GK, Jaenicke S, Xu TH (2000) Micropor Mesopor Mater 37: Delhomme C, Weuster-Botz D, Kühn FE (2009) Green Chem 11: Novakova EK, McLaughlin L, Burch R, Crawford P, Griffin K, Hardacre C, Hu PJ, Rooney DW (2007) J Catal 249: Tsuji J (1986) Pure Appl Chem 58:

Journal of Industrial and Engineering Chemistry 17 (2011) 316 320 Contents lists available at ScienceDirect Journal of Industrial and Engineering Chemistry journal homepage: www.elsevier.

Gil Seo, Joongwon Lee, In Kyu Song * School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul 151-744, South Korea

344 Journal of Industrial and Engineering Chemistry 17 (2011) Contents lists available at ScienceDirect Journal of Industrial and Engineering Chemistry journal homepage: Hydrogenation of succinic acid to g-butyrolactone (GBL) over palladium catalyst supported on alumina xerogel: Effect of acid density of the catalyst Ung Gi Hong, Sunhwan Hwang, Jeong Gil Seo, Joongwon Lee, In Kyu Song * School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , South Korea ARTICLE INFO ABSTRACT Article history: Received 9 August 2010 Accepted 11 August 2010 Available online 2 March 2011 Keywords: Hydrogenation Succinic acid g-butyrolactone Alumina xerogel Acid density Mesoporous alumina xerogel (AX) supports prepared by a sol gel method were calcined at various temperatures to control their acid property. Palladium catalysts supported on mesoporous alumina xerogel (Pd/AX) were then prepared by an impregnation method. The Pd/AX catalysts were characterized by XRD, BET, NH 3 -TPD, N 2 adsorption desorption isotherm, and H 2 chemisorption analyses. Liquid-phase hydrogenation of succinic acid to g-butyrolactone (GBL) over Pd/AX catalyst was carried out in a batch reactor. The effect of acid property of Pd/AX catalyst on the catalytic performance was examined. In the hydrogenation of succinic acid, conversion of succinic acid and yield for GBL showed volcano-shaped curves with respect to calcination temperature of AX support. Selectivity for succinic anhydride (an intermediate product formed by acid catalysis) increased with increasing acid density of Pd/AX catalyst. Correlations between acid density of Pd/AX catalyst and catalytic performance also revealed that conversion of succinic acid and yield for GBL increased with increasing acid density of Pd/AX catalyst. Thus, acid density served as an important factor determining the catalytic performance of Pd/AX in the hydrogenation of succinic acid. ß 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. 1. Introduction g-butyrolactone (GBL) has been widely used as a solvent in fine chemical and pharmaceutical industries [1 3]. GBL has also served as an important starting material for the production of C 4 chemicals such as N-methyl-2-pyrrolidone (NMP) and 2-pyrrolidone. Conventionally, GBL has been produced by direct hydrogenation of maleic anhydride [4,5]. However, unstable price of maleic anhydride and its environmental problem have been posed in the production of GBL. For this reason, demand for finding an economical and green platform chemical to produce GBL has been continuously increased. Recently, succinic acid has attracted much attention as a promising feedstock that can replace maleic anhydride [6 8]. Succinic acid is a new and cheap bio-derived chemical that can be converted into GBL by hydrogenation reaction. Hydrogenation of succinic acid to GBL follows two consecutive reaction steps (Fig. 1). First, C O bond in succinic acid is reduced and dehydrated to form succinic anhydride. Second, GBL is formed via oxidative hydrogenation of C5O bond in succinic anhydride. Dehydration of succinic acid occurs on the acid site, while hydrogenation of C5O bond occurs on the novel metal site. Therefore, it is very important * Corresponding author. Tel.: ; fax: address: inksong@snu.ac.kr (I.K. Song). to find a suitable bi-functional catalyst that has both acid property and hydrogenation activity in the hydrogenation of succinic acid to GBL. Alumina has found successful applications in many reactions as supporting material and acid catalyst [9,10]. Acid property of alumina is very important to achieve high dehydration activity in the bi-functional catalytic reaction. It has been reported that acid property of g-alumina prepared by a sol gel method varies depending on calcination temperature [11]. It has also been reported that transition of alumina phase occurs from boehmite (AlOOH) to g-, d-, and u-alumina with increasing calcination temperature [12]. These imply that acid property of alumina xerogel can be controlled by changing calcination temperature. Furthermore, alumina xerogel has excellent structural property and mechanical stability. Therefore, it is expected that alumina xerogel can serve as both acid catalyst and supporting material in the bi-functional catalyst system. Oxidative hydrogenation activity of novel metal is also important to achieve high selectivity for GBL in the hydrogenation of succinic acid. In the oxidative hydrogenation of succinic anhydride, group VIII metal catalysts such as palladium [13] and ruthenium [14] have been used to reduce carbonyl group of succinic anhydride. It is known that palladium catalyst retains moderate activity for selective reduction of carbonyl group of succinic anhydride. On the other hand, ruthenium catalyst may cause complete reduction of carbonyl group of succinic anhydride, X/$ see front matter ß 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. doi: /j.jiec

345 [()TD$FIG] 320 U.G. Hong et al. / Journal of Industrial and Engineering Chemistry 17 (2011) Conversion of succinic acid (%) Pd/AX900 Pd/AX750 Pd/AX700 Pd/AX900 Pd/AX750 Pd/AX850 Pd/AX800 Pd/AX850 Pd/AX Yield for GBL (%) succinic acid to GBL, conversion of succinic acid and yield for GBL showed volcano-shaped curves with respect to calcination temperature of AX support. Conversion of succinic acid, selectivity for succinic anhydride, and yield for GBL increased with increasing acid density of Pd/AX catalyst. High acid density of Pd/AX catalyst increased the formation of SAN, and as a consequence, led to the enhanced formation of GBL. Thus, acid density of Pd/AX catalyst played a key role in determining the catalytic performance in the liquid-phase hydrogenation of succinic acid to GBL. In conclusion, GBL could be efficiently produced from succinic acid by controlling acid density of Pd/AX catalyst. Acknowledgement Pd/AX This subject is supported by Korea Ministry of Environment as Converging Technology Project ( ). Acid density (μmol NH 3 /m 2 ) References Fig. 8. Correlations between acid density of Pd/AX catalyst and catalytic performance in the hydrogenation of succinic acid. acid. Selectivity for SAN (an intermediate product formed by acid catalysis) increased with increasing acid density of Pd/AX catalyst, in good agreement with the previous works [26,27] reporting that dehydration activity strongly depended on acid density of the catalyst. Thus, acid density played an important role in the dehydration of succinic acid to SAN. Fig. 8 shows the correlations between acid density of Pd/AX catalyst and catalytic performance in the hydrogenation of succinic acid. It is noteworthy that conversion of succinic acid and yield for GBL increased with increasing acid density of Pd/AX catalyst. Among the Pd/AX catalysts, Pd/AX850 catalyst with the highest acid density showed the best catalytic performance in the hydrogenation of succinic acid to GBL. High acid density of Pd/ AX catalyst increased the dehydration activity (formation of SAN), and in the long run, led to the enhanced formation of GBL. Thus, acid density of Pd/AX catalyst served as an important factor determining the catalytic performance of Pd/AX in the liquidphase hydrogenation of succinic acid to GBL. 4. Conclusions Mesoporous alumina xerogel (AX) supports prepared by a sol gel method were calcined at various temperatures to control their acid property. Palladium catalysts supported on mesoporous alumina xerogel (Pd/AX) were then prepared by an impregnation method for use in the hydrogenation of succinic acid to GBL. Acid density of Pd/AX catalyst could be controlled by changing calcination temperature of AX support. In the hydrogenation of [1] S.M. Jung, E. Godard, S.Y. Jung, K.-C. Park, J.U. Choi, J. Mol. 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346 Green Chemistry View Article Online / Journal Homepage / Table of Contents for this issue Dynamic Article Links Cite this: Green Chem., 2011, 13, COMMUNICATION Published on 21 June Downloaded by Seoul National University on 24/03/ :40:57. Selective conversion of glycerol to 1,3-propanediol using Pt-sulfated zirconia Jinho Oh, Saswati Dash and Hyunjoo Lee* Received 10th March 2011, Accepted 13th May 2011 DOI: /c1gc15263g Pt-deposited sulfated zirconia was used as a catalyst for the selective hydrogenolysis of glycerol to 1,3-propanediol. The Brønsted acid sites on the catalyst, which were promoted by hydrogen spillover on platinum, were more advantageous for producing 1,3-propanediol than 1,2-propanediol. As the price of petroleum rises, biomass resources have entered the spotlight for the production of fuel and chemicals. 1 2 Recently, biodiesel has been actively investigated as an environmentally friendly alternative fuel. Biodiesel is produced by transesterification of vegetable oil with methanol, generating significant amounts of glycerol as a by-product. The glycerol can be used as a platform chemical for the production of more valuable chemicals. The conversion of glycerol can yield mesoxalic acid, oxalic acid, acrylic acid, etc. by oxidation, oxygenated fuel by esterification, and propanediols by reduction. 3 4 In particular, propanediol is used for the production of antifreeze, aircraft deicer, lubricant, and more valuable polymers. Depending on the location of the removed hydroxyl group, 1,2-propanediol or 1,3-propanediol can be generated. Whereas 1,2-propanediol is used for commodity chemicals, 1,3-propanediol has received much attention because it is the main reactant for the highly valuable polymer, polytrimethyleneterephthalate (PTT), which is a soft and extremely stain-resistant polymer with high strength and stiffness. 5 1,3-Propanediol is generally produced by the hydration of acrolein or by hydroformylation of ethylene oxide to 3-hydroxylpropionaldehyde and subsequent hydrogenation. 6 Dupont recently reported the direct production of 1,3- propanediol from glycerol by fermentation using bacterial strains. 7 However, this biological process has a low metabolic efficiency, and its compatibility with existing chemical plants is rather poor. If 1,3-propanediol can be produced directly from glycerol with a high yield using heterogeneous catalysts, it would be more applicable in current chemical processes. A process for producing 1,2-propanediol from glycerol with a high yield was Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul, , South Korea. azhyun@yonsei.ac.kr; Fax: ; Tel: Electronic supplementary information (ESI) available: Experimental procedure, calculation procedure for M(B)/M(L) and additional data. See DOI: /c1gc15263g reported for various heterogeneous catalysts such as RANEY R nickel, copper chromate, Amberlyst with Ru/C, CuO/ZnO, and Cu/MgAlO x In contrast, the conversion of glycerol to 1,3- propanediol is more difficult. The highest yield reported so far is 38% using an Re Ir oxide catalyst. 14 Other catalysts such as Rh-ReO x /SiO 2, Pt/WO 3 /ZrO 2, Pt/WO 3 /TiO 2 /SiO 2 have been reported, but their yields are quite low, and 1,2-propanediol is often produced in greater quantities In this study, superacids consisting of sulfated zirconia were used as a catalyst for the selective conversion of glycerol to 1,3-propanediol. Especially, when platinum was deposited on the sulfated zirconia, the yield was 55.6%, which is the highest value reported to date to our knowledge. Platinum deposition significantly increased the Brønsted acidity and caused the high yield of 1,3-propanediol. The detailed experimental procedure was described in the ESI. When zirconia is treated with sulfuric acid, super acidic sites are formed, i.e., acid sites even stronger than the liquidphase sulfuric acid as measured by the Hammett acidity indicator. This solid superacid was reported to be effective for butane isomerization and recently applied for various liquidphase reactions. 18 Fig. S1 shows the crystalline structures of zirconia, sulfated zirconia, and Pt-deposited sulfated zirconia. Whereas zirconia has a monoclinic crystalline structure that is thermodynamically more stable than the tetragonal phase, the monoclinic phase was suppressed in sulfated zirconia, with more tetragonal phase present. When platinum was deposited in sulfated zirconia, the monoclinic phase was hardly observed; instead, only tetragonal phase appeared. The suppression of the monoclinic phase by sulfate ions and metal deposition has been previously reported as well. 18,19 The reduction properties of these catalysts were illustrated in temperature-programmed reduction results (TPR, Fig. S2 ). Zirconia showed no reduction peak until 1000 C, but sulfated zirconia had a large peak at 787 C. This peak appeared while the surface sulfate ions were reduced. When platinum was deposited, the location of the reduction peak was significantly lowered to 553 C. The platinum deposition weakened the interaction of sulfate ions and zirconia on the surface. 20 The hydrogenolysis of glycerol was performed using the zirconia-based catalysts. Reaction conversion and selectivity were estimated from the GC data shown in Fig. S3. The yield of direct conversion to 1,3-propanediol was 16.6% for zirconia 2004 Green Chem., 2011, 13, This journal is The Royal Society of Chemistry 2011

347 View Article Online Table 2 Effect of the kind of deposited metal for the hydrogenolysis of glycerol a Yield Catalyst Conversion (%) 1,3-PDO 1,2-PDO 1-PrOH EG Published on 21 June Downloaded by Seoul National University on 24/03/ :40:57. Ru-Sulfated ZrO Ni-Sulfated ZrO Cu-Sulfated ZrO Ni/Cu-Sulfated ZrO Fe-Sulfated ZrO Mn-Sulfated ZrO Al-Sulfated ZrO Pt/STA/ZrO Pt/PTA/ZrO a 1,3-PDO: 1,3-propanediol, 1,2-PDO: 1,2-propanediol, 1-PrOH: 1-propanol, EG: ethylene glycol, STA: silicotungstic acid, PTA: phosphotungstic acid. All the major liquid products observed in GC are shown in the table. Brønsted acid sites favors the removal of the hydroxyl group from the secondary carbon in glycerol, generating much more 1,3-propanediol. The quantities of sulfate ions and platinum in Pt-sulfated zirconia affected the final yield of 1,3-propanediol significantly. When 9.7 ml of 0.5 M sulfuric acid solution was added to the zirconia precursor solution, the sulfur content in the final catalysts was measured as 2.63 wt% by elemental analysis. When the amount of sulfuric acid was varied by ±25% (Table S2 ), the yield decreased in both cases. In the case that the number of sulfate ions was less than the optimum value, the conversion was increased to as high as 73.2%, although the yields of 1,2- or 1,3-propanediol were reduced, indicating that a more destructive dissociation occurred forming gaseous products of CO (Fig. S4 ). When the number of sulfate ions was decreased, both the yield and conversion decreased. Similarly, when the amount of platinum was changed among 1, 2, or 3 wt% (Table S3 ), the highest yield was obtained with 2 wt%. With platinum deposited on sulfated zirconia, gas-phase hydrogen is adsorbed more easily, and the adsorbed hydrogen moves to the sulfated zirconia surface by hydrogen spillover, generating more Brønsted acid sites. 23 The balance between acidic sites generated by sulfate ions and hydrogen spillover induced by platinum seems to be essential for the best yield of 1,3-propanediol. Table 2 shows the results when other metals or supported anions were used for the zirconia-based catalysts. All the cases showed yields less than of Pt-sulfated zirconia, but the selectivity varied greatly. Ruthenium, which has recently been widely used in biomass conversion, generated a significant amount of ethylene glycol, unlike the other metals. Ru-sulfated zirconia may promote C C bond cleavage in the studied reaction conditions. Whereas Ni/Cu-sulfated zirconia produced only 1,2- propanediol, Fe- or Mn-sulfated zirconia generated only 1,3- propanediol. Because the conversion was much higher in every case, there appeared to be a great deal of destructive dissociation. Al-sulfated zirconia was also quite active for glycerol conversion, producing similar amounts of 1,2- and 1,3-propanediol. When the sulfate ions were replaced with a heteropolyacid such as silicotungstic acid (STA) or phosphotungstic acid (PTA), the yields for 1,3-propanediol were much lower. When the used Pt-sulfated zirconia catalysts were regenerated by heating them at 300 C in air for 1 h to remove the deposited cokes, the sulfur and platinum content in the catalyst showed little difference (S: 2.63 wt% before reaction vs wt% after reaction, Pt: 2.11 wt% before reaction vs wt% after reaction). The conversions and yields were also similar for repeated reactions up to 5 cycles as shown in Fig. S5. In summary, Pt-sulfated zirconia was an effective catalyst for the selective conversion of glycerol to 1,3-propanediol. Platinum and sulfate ions were stabilized in the more active tetragonal zirconia phase. Platinum induced hydrogen spillover, providing more Brønsted acid sites. The abundant Brønsted acid sites promoted the removal of the hydroxyl group from the secondary carbon of glycerol, preferentially generating 1,3-propanediol. The selectivity was highly affected by the type of metal and supported anions. This work was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology ( ) and the Korean Ministry of Environment as Converging technology project ( ), and DAPA/ADD of Korea. References 1 J. N. Chheda, G. W. Huber and J. A. Dumesic, Angew. Chem., Int. Ed., 2007, 46, G. W. Huber and A. Corma, Angew. Chem., Int. Ed., 2007, 46, A. Behr, J. Eilting, K. Irawadi, J. Leschinski and F. Lindner, Green Chem., 2008, 10, A. Corma, G. W. Huber, L. Sauvanauda and P. O Connor, J. Catal., 2008, 257, C. H. C. Zhou, J. N. Beltramini, Y. X. Fan and G. Q. M. Lu, Chem. Soc. Rev., 2008, 37, M. Besson, P. Gallezot, A. Pigamo and S. Reifsnyder, Appl. Catal., A, 2003, 250, M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi and C. Della Pina, Angew. Chem., Int. Ed., 2007, 46, T. Miyazawa, Y. Kusunoki, K. Kunimori and K. Tomishige, J. Catal., 2006, 240, A. Perosa and P. Tundo, Ind. Eng. Chem. Res., 2005, 44, M. A. Dasari, P. P. Kiatsimkul, W. R. Sutterlin and G. J. Suppes, Appl. Catal., A, 2005, 281, T. Miyazawa, S. Koso, K. Kunimori and K. Tomishige, Appl. Catal., A, 2007, 329, J. Chaminand, L. Djakovitch, P. Gallezot, P. Marion, C. Pinel and C. Rosier, Green Chem., 2004, 6, Z. Yuan, L. Wang, J. Wang, S. Xia, P. Chen, Z. Hou and X. Zheng, Appl. Catal. B: Environ., 2011, 101, Green Chem., 2011, 13, This journal is The Royal Society of Chemistry 2011

348 Res Chem Intermed (2011) 37: DOI /s x Catalytic conversion of lactic acid into propylene glycol over various metals supported on silica Tae Young Jang Ku Bong Chung Hye Ri Eom Dong Kyun Noh In Kyu Song Jongheop Yi Sung-Hyeon Baeck Received: 31 May 2011 / Accepted: 27 July 2011 / Published online: 17 September 2011 Ó Springer Science+Business Media B.V Abstract Catalytic hydrogenation of lactic acid to propylene glycol was performed over various metals (Ag, Co, Cu, Ni, Pt, and Ru) supported on silica prepared by an incipient wetness impregnation method. The loading amount of each metal was 5 wt%. Crystallinity of the synthesized catalysts was investigated by X-ray diffraction (XRD), and the BET method was utilized to examine the surface area. Pore volume and pore size of catalysts were determined using BJH analysis of the N 2 adsorption isotherm. Particle sizes of various metals were determined from transmission electron microscopy (TEM) images. The catalytic activity was found to be strongly dependent on the supported metal. Among catalysts tested, Ru/SiO 2 showed the highest propylene glycol yield. The yield of propylene glycol increased with pressure, and the highest yield was achieved at 130 C. Keywords Lactic acid Propylene glycol Hydrogenation Ruthenium Introduction Lactic acid has been widely used in food, the medical industry and cosmetic applications. Because the consumption of lactic acid has been steadily increasing, the production of lactic acid by fermentation of biomass is of importance to meet the increase of consumption. In 1987, lactic acid was produced equally by both chemical synthesis and fermentation processes [1], and currently, most lactic acid is being produced by the biotechnological methods or by fermentation of renewable sources such as refined carbohydrates derived from agricultural crops [2, 3] and T. Y. Jang K. B. Chung H. R. Eom D. K. Noh S.-H. Baeck (&) Department of Chemical Engineering, Inha University, Incheon, Korea shbaeck@inha.ac.kr I. K. Song J. Yi Department of Chemical and Biological Engineering, Seoul National University, Seoul, Korea 123

349 Catalytic conversion of lactic acid into propylene glycol (a) yield selectivity Conversion (b) yield selectivity conversion Time (hr) Pressure (bar) (c) yield selectivity conversion Temperature ( C) Fig. 5 Catalytic activity of 5 wt% Ru/SiO 2 with a time on stream (reaction T = 150 C, P = 8 MPa), b reaction pressure (reaction T = 130 C, time = 7 h), c reaction temperature (reaction P = 8 MPa, time = 7h) Conversion of lactic acid and selectivity of propylene glycol increases with pressure over Ru/SiO 2, and the highest yield was achieved at 130 C. High temperature ([150 C) intensifies secondary reactions to by-products. Thus, there exists an optimal reaction temperature for maximizing PG yield. The most promising catalyst was found to be ruthenium supported on silica catalyst. Acknowledgment This subject is supported by Korea Ministry of Environment as Converging technology project ( ). References 1. R. Datta, S.P. Tsai, P. Bonsignor, S. Moon, J. Frank, FEMS Microbiol. Rev. 16, (1995) 2. E.S. Lipinsky, R.G. Sinclair, Chem. Eng. 82, (1986) 3. J.H. Litchfield, Adv. Appl. Microbiol. 42, (1996) 4. P.R. Gruver, et al. U.S. Patent 5,142,023, 25 Aug G.C. Gunter, D.J. Miller, J.E. Jackson, J. Catal. 194, (1994) 6. G.C. Gunter, R.H. Langford, J.E. Jackson, D.J. Miller, Ind. Eng. Chem. Res. 34, (1995) 7. G.C. Gunter, R. Cracium, M.S. Tam, J.E. Jackson, D.J. Miller, J. Catal. 164, (1996) 8. R.A Sawicki, U.S. Patent 4,729,978, 8 March

Journal of Industrial and Engineering Chemistry 18 (2012) 462 468 Contents lists available at SciVerse ScienceDirect Journal of Industrial and Engineering Chemistry jou r n al h o mep ag e: w ww.

350 Journal of Industrial and Engineering Chemistry 18 (2012) Contents lists available at SciVerse ScienceDirect Journal of Industrial and Engineering Chemistry jou r n al h o mep ag e: w ww.elsevier.co m /loc ate/jiec Hydrogenation of succinic acid to g-butyrolactone (GBL) over ruthenium catalyst supported on surfactant-templated mesoporous carbon Ung Gi Hong, Hai Woong Park, Joongwon Lee, Sunhwan Hwang, In Kyu Song * School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , South Korea A R T I C L E I N F O Article history: Received 12 May 2011 Accepted 22 May 2011 Available online 7 November 2011 Keywords: Hydrogenation Succinic acid Mesoporous carbon Ruthenium A B S T R A C T Mesoporous carbon support (denoted as STC) was prepared by a surfactant-templating method for use as a support for ruthenium catalyst. For comparison, porous carbon (denoted as TC), spherical carbon (denoted as SC), and microporous carbon (denoted as DC) supports were also prepared by a templating method, hydrothermal method, and direct carbonization method, respectively. Ruthenium catalysts supported on carbon supports (Ru/C) were then prepared by an incipient wetness impregnation method. The Ru/C (Ru/DC, Ru/SC, Ru/TC, and Ru/STC) catalysts were characterized by FE-SEM, N 2 adsorption desorption isotherm, BET, XRD, and HR-TEM analyses. Liquid-phase hydrogenation of succinic acid to g- butyrolactone (GBL) was carried out over Ru/C catalysts in a batch reactor. In the hydrogenation of succinic acid, Ru/STC catalyst showed the highest conversion of succinic acid and the highest yield for GBL. The superior catalytic performance of Ru/STC catalyst compared to the other catalysts (Ru/TC, Ru/SC, and Ru/DC) was due to fine dispersion of ruthenium (ruthenium surface area). Thus, ruthenium surface area played a key role in determining the catalytic performance in the liquid-phase hydrogenation of succinic acid to GBL over Ru/C catalysts. ß 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. 1. Introduction g-butyrolactone (GBL) and its derivatives such as 1,4-butanediol (BDO), tetrahydrofuran (THF), n-methyl-2-pyrrolidone (NMP), and 2-pyrrolidone are very important chemicals for various industries [1 4]. In particular, GBL is used as a valuable intermediate chemical and as a desirable solvent in pharmaceutical and paint industries [5 7]. GBL is currently produced from maleic anhydride. However, high price of maleic anhydride and its environmental issues have been posed in the production of GBL. Accordingly, demand for finding a cheap and green chemical to replace maleic anhydride has been continuously increased [8,9]. Recently, succinic acid has attracted much attention as a green feedstock that can replace maleic anhydride, because of the increase of succinic acid production in the biorefinery process [10,11]. Succinic acid is a cheap and eco-friendly chemical that can be converted into GBL by hydrogenation reaction. Fig. 1 shows the reaction pathway for the conversion of succinic acid. It is known that noble metal catalysts such as palladium, platinum, and ruthenium are efficient in the hydrogenation of succinic acid [12]. Especially, it has been reported that ruthenium is one of the most efficient catalysts in the hydrogenation of * Corresponding author. Tel.: ; fax: address: inksong@snu.ac.kr (I.K. Song). succinic acid [13,14]. Noble metal catalysts have been generally used as supported catalysts to increase metal dispersion, because of high price of noble metal [15]. Therefore, many researches on ruthenium catalysts have been focused on finding efficient supporting materials. Among various supports, carbon material has been widely employed due to its excellent thermal and mechanical stability [16 18]. In particular, mesoporous carbon can be potentially available as a supporting material due to its high surface area, non-toxicity, and availability [19,20]. In the hydrogenation of succinic acid, furthermore, carbon support can lead to selective hydrogenation reaction due to its non-polar and hydrophobic property [21,22]. We have previously investigated the hydrogenation of succinic acid over noble metal catalyst supported on alumina [23,24]. We found that acid property of alumina increased the formation of by-products, leading to the decrease of GBL selectivity. If a carbon support is prepared to have controllable pore structure for increasing ruthenium dispersion, therefore, it can serve as an excellent support for ruthenium catalyst to obtain hydrogenation product with high selectivity in the hydrogenation of succinic acid. Conventionally, porous carbon materials have been prepared by a templating method with silica template. Although many ordered porous carbons have been developed by a templating method, a number of calcination and drying steps are generally needed in the preparation of porous carbons. To solve this problem, a surfactanttemplating method has been proposed [25 27]. Porous carbons X/$ see front matter ß 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. doi: /j.jiec

351 468 U.G. Hong et al. / Journal of Industrial and Engineering Chemistry 18 (2012) impregnation method. Among the prepared catalysts, ruthenium particles were most finely dispersed on the STC support due to well-developed mesoporous structure of STC. In the hydrogenation of succinic acid, conversion of succinic acid and yield for GBL increased with increasing ruthenium surface area of Ru/C (Ru/DC, Ru/SC, Ru/TC, and Ru/STC) catalysts. Ru/STC catalyst showed the highest conversion of succinic acid and highest yield for GBL. The superior catalytic performance of Ru/STC catalyst compared to the other catalysts (Ru/TC, Ru/SC, and Ru/DC) was due to fine dispersion of ruthenium (ruthenium surface area). Thus, ruthenium surface area (ruthenium dispersion) played a key role in determining the catalytic performance in the liquid-phase hydrogenation of succinic acid over supported ruthenium catalyst. Ru/STC catalyst served as an efficient and reusable catalyst in the hydrogenation of succinic acid to GBL. Acknowledgement This subject is supported by Korea Ministry of Environment as Converging Technology Project ( ). References [1] C.G. Gao, Y.X. Zhao, D.S. Liu, Catal. Lett. 118 (2007) 50. [2] Y.-S. Yoon, H.K. Shin, B.-S. Kwak, Catal. Commun. 3 (2002) 349. [3] T.M. Lammens, M.C.R. Franssen, E.L. Scott, J.P.M. Sanders, Green Chem. 12 (2010) [4] A. Mehdina, A. Ghassempour, H. Rafati, R. Heydari, Anal. Chim. Acta 587 (2007) 82. [5] U.R. Pillai, E. Sahle-Demessie, Y. Douglas, Appl. Catal. B: Environ. 43 (2003) 131. [6] U.G. Hong, S. Hwang, J.G. Seo, J. Yi, I.K. Song, Catal. Lett. 138 (2010) 28. [7] Y.-L. Zhu, H.-W. Xiang, G.-S. Wu, L. Bai, Y.-W. Li, Chem. Commun. (2002) 254. [8] C. Delhomme, D. Weuster-Botz, F.E. Kühn, Green Chem. 11 (2009) 13. [9] A. Cukalovic, C.V. Stevens, Biofuels Bioprod. Bioref. 2 (2008) 505. [10] I. Bechthold, K. Bretz, S. Kabasci, R. Kopitzky, A. Springer, Chem. Eng. Technol. 31 (2008) 647. [11] C. Du, S.K.C. Lin, A. Koutinas, R. Wang, C. Webb, Appl. Microbiol. Biotechnol. 76 (2007) [12] D.P. Mihn, M. Besson, C. Pinel, P. Fuertes, C. Petitjean, Top. Catal. 53 (2010) [13] L. Rosi, M. Frediani, P. Frediani, J. Org. Chem. 695 (2010) [14] R. Luque, J.H. Clark, K. Yoshida, P.L. Gai, Chem. Commun. (2009) [15] J.G. Seo, M.H. Youn, K.M. Cho, S. Park, S.H. Lee, J. Lee, I.K. Song, Korean J. Chem. Eng. 25 (2008) 41. [16] J.-Y. Miao, D.W. Hwang, C.-C. Chang, S.-H. Lin, K.V. Narasimhulu, L.-P. Hwang, Diamond Relat. Mater. 12 (2003) [17] J.L. Zimmerman, R. Williams, V.N. Khabashesku, J.L. Margrave, Nano Lett. 1 (2001) 731. [18] Q. Wang, H. Li, L. Chen, X. Huang, Carbon 39 (2001) [19] P. Kim, J.B. Joo, W. Kim, J. Kim, I.K. Song, J. Yi, Catal. Lett. 112 (2006) 213. [20] H. Kim, J.C. Jung, D.R. Park, S.-H. Baeck, I.K. Song, Appl. Catal. A: Gen. 320 (2007) 159. [21] H. Zhu, W. Han, H. Liu, Catal. Lett. 115 (2007) 13. [22] D.J. Suh, T.J. Park, Ind. Eng. Chem. Res. 31 (1992) [23] U.G. Hong, J. Lee, S. Hwang, I.K. Song, Catal. Lett. 141 (2011) 332. [24] U.G. Hong, J.G. Seo, S. Hwang, J. Lee, I.K. Song, J. Ind. Eng. Chem. 17 (2011) 316. [25] D.S. Yuan, J. Zeng, J. Chen, Y. Liu, Int. J. Electrochem. Sci. 4 (2009) 562. [26] S.B. Yoon, J.Y. Kim, J.S. Yu, Chem. Commun. (2002) [27] S. Zhu, H. Zhou, M. Hibino, I. Honma, M. Ichihara, Mater. Chem. Phys. 88 (2004) 202. [28] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquérol, T. Siemieniewska, Pure Appl. Chem. 57 (1985) 602. [29] J. Kim, J. Lee, T. Hyeon, Carbon 42 (2004) [30] L. Li, H. Song, X. Chen, Micropor. Mesopor. Mater. 94 (2006) 9. [31] Z.Q. Li, C.J. Lu, Z.P. Xia, Y. Zhou, Z. Luo, Carbon 45 (2007) [32] Z.-Z. Lin, T. Okuhara, M. Misono, J. Phys. Chem. 92 (1988) 723. [33] P. Betancourt, A. Rives, R. Hubaut, C.E. Scott, J. Goldwasser, Appl. Catal. A: Gen. 170 (1998) 307. [34] P.C.H. Mitchell, A.J. Ramirez-Cuesta, S.F. Parker, J. Tomkinson, D. Thompsett, J. Phys. Chem. 107 (2003) [35] C. Prado-Burguete, A. Linares-Solano, F. Rodríguez-Reinoso, C. Salinas-Martínez De Lecea, J. Catal. 128 (1991) 397. [36] J. Okal, M. Zawadzki, L. Kępiński, L. Krajczyk, W. Tylus, Appl. Catal. A: Gen. 319 (2007) 202. [37] P. Scherrer, Gőttinger Nachr. Ges. 2 (1918) 98. [38] A.L. Patterson, Phys. Rev. 56 (1939) 978. [39] J.J.F. Scholten, A.P. Pijpers, A.M.L. Hustings, Catal. Rev. 27 (1985) 151. [40] A. Borodziński, M. Bonarowska, Langmuir 13 (1997) [41] K. Tahara, E. Nagahara, Y. Itoi, S. Nishiyama, S. Tsuruya, M. Masai, J. Mol. Catal. A: Chem. 110 (1996) L5. [42] J. Feng, H. Fu, J. Wang, R. Li, H. Chen, X. Li, Catal. Commun. 9 (2008) 1458.

352 Applied Catalysis A: General (2012) Contents lists available at SciVerse ScienceDirect Applied Catalysis A: General j ourna l ho me page: Hydrogenation of succinic acid to tetrahydrofuran (THF) over rhenium catalyst supported on H 2 SO 4 -treated mesoporous carbon Ung Gi Hong, Hai Woong Park, Joongwon Lee, Sunhwan Hwang, Jongheop Yi, In Kyu Song School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , South Korea a r t i c l e i n f o Article history: Received 30 September 2011 Received in revised form 7 December 2011 Accepted 13 December 2011 Available online 21 December 2011 Keywords: Hydrogenation Succinic acid Mesoporous carbon Rhenium Tetrahydrofuran a b s t r a c t Mesoporous carbon (MC) prepared by a surfactant-templating method was treated with different H 2 SO 4 concentration (X = 0, 0.2, 0.4, 0.6, 0.8, and 1.0 M) for use as a support (MC-X) for rhenium catalyst. Rhenium catalysts supported on H 2 SO 4 -treated mesoporous carbons (Re/MC-X) were then prepared by an incipient wetness impregnation method, and they were applied to the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF). The effect of H 2 SO 4 treatment on the physicochemical properties and catalytic activity of Re/MC-X catalysts (X = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) was investigated. It was observed that MC-X supports showed different pore characteristics depending on H 2 SO 4 concentration. As a result, Re/MC-X catalysts showed different rhenium particle size. In the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF), conversion of succinic acid and yield for THF showed volcano-shaped curves with respect to H 2 SO 4 concentration. Thus, an optimal H 2 SO 4 concentration was required to achieve maximum catalytic performance of Re/MC-X. Yield for THF in the hydrogenation of succinic acid increased with decreasing rhenium particle size of Re/MC-X catalysts. Among the catalysts tested, Re/MC-0.4 with the smallest rhenium particle size showed the highest yield for THF Elsevier B.V. All rights reserved. 1. Introduction Tetrahydrofuran (THF) is widely used as a solvent in various industries. Polymerization of THF gives a raw material for manufacturing polytetramethylene ether glycol (PTMEG), thermoplastic polyesters, and polyurethane elastomers [1 3]. THF is currently produced via several routes including hydrogenation of maleic anhydride (MAN) [4], dehydration of 1,4-butanediol (BDO) [5], and oxidation of butadiene (BD) [6]. However, all these feedstocks (MAN, BDO, and BD) are obtained from fossil fuels, leading to unstable price and environmental problems. Therefore, demand for finding a cheap and green chemical that can replace these feedstocks has continuously increased [7 9]. Recently, conversion of succinic acid to THF has attracted much attention, because of the increase of succinic acid production in the biorefinery process [10,11]. Succinic acid is a cheap and bio-based chemical that can be converted into THF by hydrogenation reaction. Hydrogenation of succinic acid (SA) to THF follows two consecutive reaction steps (Fig. 1). First, cyclization occurs by hydrogenation of carboxyl group in succinic acid to form -butyrolactone (GBL). Second, THF is formed via oxidative hydrogenation of carbonyl group in GBL. It is known that noble metal Corresponding author. Tel.: ; fax: address: inksong@snu.ac.kr (I.K. Song). catalysts such as platinum, palladium, ruthenium, and rhenium are efficient in the hydrogenation of succinic acid to GBL [12,13]. For the production of THF, however, strong activity for hydrogenation of carbonyl group is also required. Therefore, it is important to find a suitable noble metal catalyst that has both cyclization activity (SA GBL) and oxidative-hydrogenation activity (GBL THF) in the hydrogenation of succinic acid to THF. It is known that rhenium catalyst causes complete reduction of both carboxyl and carbonyl groups, leading to further hydrogenation of GBL [14]. Therefore, rhenium catalyst can be a potential candidate for selective production of THF in the hydrogenation of succinic acid. Noble metal catalysts have been generally used as supported catalysts to increase metal dispersion, because of high price of noble metal [15]. Therefore, it is also important to find efficient supporting materials. Among various supporting materials, ordered mesoporous carbon has found successful applications in many reactions due to its well-developed porosity, non-toxicity, and hydrophobic property [16 18]. In particular, regularly developed mesoporosity of carbon support is a very important property to increase metal dispersion in the supported noble metal catalyst system. If carbon support is prepared to have a controllable pore structure for increasing rhenium dispersion, therefore, it can serve as an excellent support for rhenium catalyst to obtain hydrogenation product of succinic acid with high catalytic activity. It has been reported that surface area and pore volume of mesoporous carbon material prepared by a surfactant-templating X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi: /j.apcata

353 148 U.G. Hong et al. / Applied Catalysis A: General (2012) Conclusions Mesoporous carbon (MC) prepared by a surfactant-templating method was treated with different H 2 SO 4 concentration (X = 0, 0.2, 0.4, 0.6, 0.8, and 1.0 M). Rhenium catalysts supported on H 2 SO 4 - treated mesoporous carbons (Re/MC-X) were then prepared by an incipient wetness impregnation method. Among the Re/MC- X (X = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) catalysts, Re/MC-0.4 catalyst showed the smallest rhenium particle size due to the regularly developed mesoporous structure of MC-0.4. In the hydrogenation of succinic acid, both conversion of succinic acid and yield for THF showed volcano-shaped curves with respect to H 2 SO 4 concentration. Thus, an optimal H 2 SO 4 concentration for the treatment of MC was required to achieve maximum yield for THF. Yield for THF in the hydrogenation of succinic acid increased with decreasing rhenium particle size of Re/MC-X catalysts. Thus, rhenium particle size played a key role in determining the catalytic performance in the hydrogenation of succinic acid to THF over Re/MC-X catalysts. In the recycle test, Re/MC-0.4 catalyst served as a stable and reusable catalyst for hydrogenation of succinic acid to THF. Furthermore, Re/MC-0.4 catalyst showed a better catalytic performance than Re/CA-0.4 and Re/PC-0.4 catalysts in the hydrogenation of succinic acid to THF. Acknowledgment This subject is supported by Korea Ministry of Environment as Converging Technology Project ( ). References [1] J. Keneta, T. Asano, S. Masamune, Ind. Eng. Chem. 62 (1970) [2] V. Pallassana, M. Neurok, G. Coulston, Catal. Today 50 (1999) [3] S.P. Müller, M. Kucher, C. Ohlinger, B. Kraushaar-Czarnetzkyi, J. Catal. 218 (2003) [4] S.M. Jung, E. Godard, S.Y. Jung, K.-C. Park, J.U. Choi, J. Mol. Catal. A 198 (2003) [5] S.E. Hunter, C.E. Ehrenberger, P.E. Savage, J. Org. Chem. 71 (2006) [6] M.D. Wildberger, M. Maciejewski, J.-D. Grunwaldt, T. Mallat, A. Baiker, Appl. Catal. A 179 (1999) [7] U.G. Hong, S. Hwang, J.G. Seo, J. Yi, I.K. Song, Catal. Lett. 138 (2010) [8] C. Delhomme, D. Weuster-Botz, F.E. Kühn, Green Chem. 11 (2009) [9] A. Cukalovic, C.V. Stevens, Biofuels Bioprod. Bioref. 2 (2008) [10] I. Bechthold, K. Bretz, S. Kabasci, R. Kopitzky, A. Springer, Chem. Eng. Technol. 31 (2008) [11] C. Du, S.K.C. Lin, A. Koutinas, R. Wang, C. Webb, Appl. Microbiol. Biotechnol. 76 (2007) [12] L. Rosi, M. Frediani, P. Frediani, J. Org. Chem. 695 (2010) [13] R. Luque, J.H. Clark, K. Yoshida, P.L. Gai, Chem. Commun. (2009) [14] D.P. Mihn, M. Besson, C. Pinel, P. Fuertes, C. Petitjean, Top. Catal. 53 (2010) [15] J.G. Seo, M.H. Youn, K.M. Cho, S. Park, S.H. Lee, J. Lee, I.K. Song, Korean J. Chem. Eng. 25 (2008) [16] P. Kim, J.B. Joo, W. Kim, J. Kim, I.K. Song, J. Yi, Catal. Lett. 112 (2006) [17] H. Kim, J.C. Jung, D.R. Park, S.-H. Baeck, I.K. Song, Appl. Catal. A 320 (2007) [18] U.G. Hong, D.R. Park, S. Park, J.G. Seo, Y. Bang, S. Hwang, M.H. Youn, I.K. Song, Catal. Lett. 132 (2009) [19] J. Kim, J. Lee, T. Hyeon, Carbon 42 (2004) [20] L. Li, H. Song, X. Chen, Micropor. Mesopor. Mater. 94 (2006) [21] Y.J. Lee, J.C. Jung, J. Yi, S.-H. Baeck, J.R. Yoon, I.K. Song, Curr. Appl. Phys. 10 (2010) [22] H.W. Park, U.G. Hong, Y.J. Lee, I.K. Song, Appl. Catal. A (2011) [23] D.W. Wang, F. Li, H.T. Fang, M. Liu, G.Q. Lu, H.M. Cheng, J. Phys. Chem. B 110 (2006) [24] H. Kim, P. Kim, K.-Y. Lee, S.H. Yeom, J. Yi, I.K. Song, Catal. Today 111 (2006) [25] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquérol, T. Siemieniewska, Pure Appl. Chem. 57 (1985) [26] J.J.F. Scholten, A.P. Pijpers, A.M.L. Hustings, Catal. Rev. 27 (1985) [27] A. Borodziński, M. Bonarowska, Langmuir 13 (1997) [28] E. Antolini, Appl. Catal. B 88 (2009) [29] R.L. Augustine, Heterogeneous Catalysis for the Synthetic Chemists, Marcel Dekker, New York, [30] J.F. Le Page, Applied Heterogeneous Catalysis: Design, Manufacture, Use of Solid Catalysts, Editions Technip, Paris, [31] H.S. Broadbent, Ann. N.Y. Acad. Sci. 145 (1967)

Catalysis Communications 24 (2012) 90 95 Contents lists available at SciVerse ScienceDirect Catalysis Communications journal homepage: www.elsevier.

Park, Yang Sik Yun, Jongheop Yi World Class University (WCU) Program of Chemical Convergence for Energy & Environment (C 2 E 2 ), School of Chemical and Biological Engineering, Institute of Chemical

354 Catalysis Communications 24 (2012) Contents lists available at SciVerse ScienceDirect Catalysis Communications journal homepage: Short Communication Preparation and characterization of nanocrystalline CuAl 2 O 4 spinel catalysts by sol gel method for the hydrogenolysis of glycerol Byoung Kyu Kwak, Dae Sung Park, Yang Sik Yun, Jongheop Yi World Class University (WCU) Program of Chemical Convergence for Energy & Environment (C 2 E 2 ), School of Chemical and Biological Engineering, Institute of Chemical Processes, College of Engineering, Seoul National University (SNU), Daehak-dong, Gwanak-gu, Seoul , Republic of Korea article info abstract Article history: Received 11 January 2012 Received in revised form 17 March 2012 Accepted 23 March 2012 Available online 1 April 2012 Keywords: Citric acid CuAl 2 O 4 Glycerol Hydrogenolysis Sol gel method Samples of nanocrystalline copper aluminate (CuAl 2 O 4 ) were prepared using various calcination temperatures and surfactant concentrations of citric acid via a sol gel method for the hydrogenolysis of glycerol. A variety of techniques, including TPR, H 2 -TPD, XRD and XPS, were used to characterize the samples. Crystallized CuAl 2 O 4 was initially observed after calcination at the temperature of 600 C and only peaks corresponding to CuAl 2 O 4 spinel crystal were observed at 800 C. The citric acid concentration influenced the size of the CuAl 2 O 4 crystal (ca nm) and the electron state of Cu after reduction, which optimized the ratio of metal precursor cations and citric acid with 1 to 2. Catalytic activities of the prepared catalysts were examined for the hydrogenolysis of glycerol to 1,2-PDO. CuAl 2 O 4 catalyst calcined at 800 C, which contains only the CuAl 2 O 4 crystalline phase, showed the highest catalytic performance with over a 90% conversion and selectivity. This can be attributed to the exceptional reducibility of Cu species and hydrogen adsorption/ desorption ability among the catalysts studied. Crown Copyright 2012 Published by Elsevier B.V. All rights reserved. 1. Introduction Biomass represents a sustainable resource that can be useful for the next generation. Of the available biomass derivatives, glycerol is produced in the biodiesel industry and represents approximately 10% of the total biodiesel production as a by-product [1,2]. As the amount of glycerol production has increased due to the increased production of biodiesel, developing new technologies for utilizing this glycerol by converting it into valuable chemicals has become a priority. Among the value-added chemicals, propylene glycol, i.e. 1,2-propanediol (1,2-PDO), can be used as biodegradable functional fluids in applications such as de-icing reagents, antifreeze and coolants, and as precursors in the syntheses of unsaturated polyester molecules and pharmaceuticals [3]. Therefore, the catalytic hydrogenolysis of glycerol to 1,2-PDO has great potential for a cost effective process. Several studies have been reported on glycerol hydrogenolysis using a number of solid-state catalysts, including noble metals, such as Cu, Pt, Ru, Rh, and Pd catalysts [4 6]. Among the metal catalysts, Cu based catalysts were found to show superior performance in terms of the selectivity of the hydrogenolysis reaction due to its efficiency for cleaving C\O bonds in the presence of H 2 and relatively low activity for C\C bond cleavage [7]. Dasari et al. explored the use of CuCr catalysts in the hydrogenolysis of glycerol to 1,2-PDO and reported a high selectivity of 85% under conditions of 473 K and a hydrogen Corresponding author. Tel.: address: jyi@snu.ac.kr (J. Yi). pressure of 200 psi for a 24 h reaction [8]. Yi et al. reported that a spinel type copper chromite (CuCr 2 O 4 ) catalyst showed good activities for this reaction with a high selectivity and conversion of ~80% [9]. However, increasing concerns over green chemistry make these Cu Cr catalysts undesirable because the toxicity associated with the chromium content of such catalysts. Among the many types of spinel structured catalysts, Cu based spinel structured catalysts show a high performance in hydrogenation due to the fact that they contain occluded hydrogen in their structure. Copper aluminate (CuAl 2 O 4 ) spinels also have a high thermal stability, high mechanical resistance, hydrophobicity, and low surface acidity [10 12]. However, metal aluminates are typically prepared using a high calcination temperature above 1000 C for several days. CuAl 2 O 4 has recently been prepared by the following methods: co-precipitation [13,14], hydrothermal synthesis [15,16], sol gel method [17,18], in attempts to overcome these disadvantages in preparation. Compared with other techniques, the sol gel method is a useful and attractive technique for the preparation of CuAl 2 O 4 because of the fact that pure and ultrafine powders can be produced at relatively low temperatures. Herein, we report on a method for the synthesis of nanocrystalline CuAl 2 O 4 with a spinel structure by means of a modified sol gel method. The citric acid-assisted sol gel synthesis of nanocrystalline CuAl 2 O 4 was achieved and the effect of different factors on controlling the crystalline phase, size and electron state of CuAl 2 O 4 was investigated. The citric acid concentration and calcination temperature were chosen as controllable input factors in this study. The prepared nanocrystalline CuAl 2 O 4 catalyst was used as a catalyst in /$ see front matter. Crown Copyright 2012 Published by Elsevier B.V. All rights reserved. doi: /j.catcom

355 B.K. Kwak et al. / Catalysis Communications 24 (2012) and desorption ability of the spinel structure of CuCr 2 O 4 catalysts are determinants of catalytic activity in the case of this reaction. 4. Conclusions Nanocrystalline CuAl 2 O 4 spinel catalysts were synthesized using metal nitrates and a citric acid complex via a sol gel method. The crystallinity of the CuAl 2 O 4 powders increased directly proportional to the calcination temperature used. The xerogel precursor was completely transferred into spinel CuAl 2 O 4 when heat treatment temperature was 800 C. The citric acid concentration influenced both the crystalline size and the electron state of CuAl 2 O 4 under the conditions employed here. The nanocrystalline size was spherical and the dimensions were determined to be nm, which is consistent with the XRD data. The citric acid-assisted sol gel route is believed to be a very attractive and promising method for the synthesis of CuAl 2 O 4 under mild conditions. The influence of the nanocrystalline CuAl 2 O 4 catalysts on the hydrogenolysis of glycerol to 1,2-PDO was studied by varying the heat-treatment temperature used in the catalyst preparation. The findings showed that the yield of 1,2-PDO increased with increasing calcination temperature, indicating that the CuAl 2 O 4 phase increased. Among the prepared catalysts, the CA800 catalysts showed only a CuAl 2 O 4 phase and had the highest reducibility and hydrogen adsorption and desorption ability, as evidenced by TPR and H 2 -TPD. It can be thus concluded that the nanocrystalline CuAl 2 O 4, which had the highest reducibility and hydrogen mobility, showed the best catalytic performance for the hydrogenolysis of glycerol to 1, 2-PDO. Acknowledgments This work was financially supported by Korea Ministry of Environment (MOE) as Converging technology project ( ). This research was supported by WCU (World Class University) program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (R ). References [1] G.J. Suppes, M.A. Dasari, E.J. Doskocil, P.J. Mankidy, M.J. Goff, Applied Catalysis A: General 257 (2004) [2] C.W. Chiu, L.G. Schumacher, G.J. Suppes, Biomass and Bioenergy 27 (2004) [3] R.D. Cotright, M. Sanchez-Castillo, J.A. Dumestic, Applied Catalysis B: Environmental 39 (2002) [4] C. Montassier, J.C. Menezo, L.C. Hoan, C. Renaud, J. Barbier, Journal of Molecular Catalysis 70 (1991) [5] Y. Kusunoki, T. Miyazawa, K. Kunimori, K. Tomishige, Catalysis Communications 6 (2005) [6] S. Bolado, R.E. Trevino, T. Garcia-Cubero, G. Gonzalez-Benito, Catalysis Communications 12 (2010) [7] S. Wang, H. Liu, Catalysis Letters 117 (2007) [8] M.A. Dasari, P.P. Kiatsimkul, W.R. Sutterlin, G.J. Suppes, Applied Catalysis A: General 281 (2005) [9] N.D. Kim, S. Oh, J.B. Joo, K.S. Jung, J. Yi, Topics in Catalysis 53 (2010) [10] A. Saberi, F. Golestani-Fard, H. Sarpoolaky, M. Willert-Porada, T. Gerdes, R. Simon, Journal of Alloys and Compounds 462 (2008) [11] M. Zawadzki, Journal of Alloys and Compounds 439 (2007) [12] K. Faungnawakij, N. Shimoda, T. Fukunaga, R. Kikuchi, K.I. Eguchi, Applied Catalysis A: General 341 (2008) [13] L.T. Chen, C.S. Hwang, I.G. Chen, S.J. Chang, Journal of Alloys and Compounds 426 (2006) [14] T. Aitasalo, A. Durygin, J. Holsa, M. Lastusaari, J. Niittykoski, A. Suchocki, Journal of Alloys and Compounds 380 (2004) 4 8. [15] J. Wrzyszcz, M. Zawadzki, J. Trawczynski, H. Grabowska, W. Mi'sta, Applied Catalysis A: General 210 (2001) [16] M. Zawadzki, J. Wrzyszcz, W. Strek, D. Hreniak, Journal of Alloys and Compounds 323 (2001) [17] A.R. Phani, M. Passacantando, S. Santucci, Materials Chemistry and Physics 68 (2001) [18] C.O. Arean, B.S. Sintes, G.T. Palomino, C.M. Carbonell, E.E. Platero, J.B.P. Soto, Microporous Materials 8 (1997) [19] S. Sato, F. Nozaki, T. Nakayama, Applied Catalysis A: General 139 (1996) L1 L4. [20] Z. Zhong, K. Chen, Y. Ji, Q. Yan, Applied Catalysis A: General 156 (1997) [21] J. Yanyan, L. Jinggang, S. Xiaotao, N. Guiling, W. Chengyu, G. Xiumei, Journal of Sol-Gel Science and Technology 42 (2007) [22] A. Saberi, F.G. Fard, H. Sarpoolaky, M.W. Porada, T. Gerdes, T. Simon, Journal of Alloys and Compounds 462 (2008) [23] M.S. Niasari, F. Davar, M. Farhadi, Journal of Sol-Gel Science and Technology 51 (2009) [24] N.D. Kim, S. Oh, J.B. Joo, K.S. Jung, J. Yi, Korean Journal of Chemical Engineering 27 (2010) Appendix A. Supplementary data Supplementary data to this article can be found online at doi: /j.catcom

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356 ChemComm COMMUNICATION View Article Online View Journal View Issue Published on 23 April Downloaded by Seoul National University on 01/05/ :50:16. Cite this: Chem. Commun., 2013, 49, 5204 Received 4th March 2013, Accepted 22nd April 2013 DOI: /c3cc41627e Rayleigh scattering spectra of high-index {730} elongated tetrahexahedral gold nanoparticles and low-index {100}, {110}, and {111} gold nanorods were collected in real time in the reduction of 4-nitrophenol. The high-index facets are capable of accepting electrons seven times faster and emitting electrons two-and-a-half times faster than low-index facets. The in situ monitoring of a heterogeneous catalytic reaction at the single particle level would be a powerful tool for understanding the precise kinetics because individual catalytic particles show different reaction rates depending on particle shape, size, and crystal facets. 1 It has been experimentally demonstrated that catalysts with higher-index facets are more potent because they possess more atoms at the kink and step edges which are chemically active compared to those with low-index facets. 2,3 However, the use of analytical tools such as UV-Vis spectroscopy, 4,5 in situ IR, 6 and cyclic-voltammetry (CV) 2,7 for verifying this phenomenon has limitations due to ensemble averaging effects. Recent technical advances have made it possible to study nanoparticle catalysis at a single particle level by removing such ensemble averaging effects. 8,9 Novo et al. reported the direct observation of a scattering band shift arising from electron transfer in catalytic reactions using dark-field microscopy (DFM). 10 On the basis of this experimental result, it would be expected that DFM would be a powerful tool for observing catalytic redox reactions at the singleparticle level with high-resolution detection. Here, we report on the direct monitoring of heterogeneous redox catalysis using DFM combined with surface plasmon spectroscopy (SPS) in an attempt to clarify the effects of surface facets on catalytic activity in the case of two separate welldefined gold nanocatalysts: elongated tetrahexahedral (THH) World Class University Program of Chemical Convergence for Energy & Environment, Institute of Chemical Processes, School of Chemical and Biological Engineering, College of Engineering, Seoul National University, Seoul , Republic of Korea. jyi@snu.ac.kr; Tel: Electronic supplementary information (ESI) available: Experimental details, UV-Vis data, dark-field microfluidic systems, control tests, and electrochemical analysis (CV) data. See DOI: /c3cc41627e These authors contributed equally to this work. Quantification of electron transfer rates of different facets on single gold nanoparticles during catalytic reactions Moonjung Eo,z Jayeon Baek,z Hyeon Don Song, Suseung Lee and Jongheop Yi* Fig. 1 Experimental scheme for the reduction of 4-nitrophenol, catalyzed by gold nanoparticles with ammonia borane as the reducing agent. Electrons are transferred from ammonia borane to the gold catalyst and are then used for the reduction of 4-nitrophenol. gold nanoparticles (high-index facets) and gold nanorods (lowindex facets). Since the movement of electrons into and from gold nanoparticles is directly related to the plasma frequency of the metal, in situ monitoring of the scattering profile allows one to quantify the amount of electrons during a catalytic reaction using the modified Rayleigh equation based on Mie-theory. As a model reaction, we selected the reduction of 4-nitrophenol (4-NIP). The reaction scheme based on the Langmuir Hinshelwood mechanism demonstrated in previous reports is shown in Fig. 1. 5,11 The reaction is frequently used to estimate the catalytic activity of synthesized noble metal nanoparticles as the reaction proceeds readily at ambient pressure and temperature. 12 The reduction of 4-NIP to 4-aminophenol (4-AMP) involves the transfer of surface hydrogen species and electrons via gold nanoparticles which have been previously supplied by ammonia borane (AB) as a strong reducing agent. Gold nanorods and elongated THH gold nanoparticles were synthesized by seed-mediated method. 2,13 AsshowninFig.2,thesurfaces of the single crystalline gold nanoparticles were defined using high-resolution transmission electron microscopy (HR-TEM) in combination with selective area electron diffraction (SAED). The side facets of gold nanorods were identified as {110} and {100} with the tip 5204 Chem. Commun., 2013, 49, This journal is c The Royal Society of Chemistry 2013

357 View Article Online ChemComm Communication Table 1 Quantification results for transferred electron rates during two sequential steps: the electron transfer from AB to gold nanoparticles and electron transfer from gold nanoparticles to 4-nitrophenol (4-NIP) Catalysts d c step (atoms per cm 2 ) Gold nanorods 46 electrons per s 32 electrons per s 0 Elongated THH gold nanoparticles 328 electrons per s 80 electrons per s R charge a R discharge b a Electron charging rate from AB to gold nanoparticles. b Electron discharging rate from gold nanoparticles to 4-NIP. c Density of stepped atoms; the lattice constant for gold (Au) is nm. Published on 23 April Downloaded by Seoul National University on 01/05/ :50:16. observe the gold-catalyzed 4-NIP reduction. If 4-NIP is reduced by gold nanocatalysts, the electrons stored on the surfaces of the gold nanoparticles would be transferred to 4-NIP and, as a result, the gold nanoparticle scattering spectrum should be red shifted. As showninfig.3candd,phase3,aredshiftwasobservedfortwo faceted gold nanoparticles. A 1 nm red shift was verified for a gold nanorod and 1.2 nm for an elongated THH gold nanoparticle, respectively. The results also support the conclusion that in the case of gold nanoparticles with high-index facets, elongated THH gold nanoparticles catalyze with a more rapid conversion of 4-NIP into 4-AMP with respect to the amount of electrons transferred. To more quantitatively examine each step of electron movement, we calculated the amount of electrons using the modified Rayleigh equation based on Mie theory. 10 The equation correlates the experimental band shift (Dl) in the SP band wavelength with the quantity of electrons used (changes in electron density, DN) in the chemical reaction (see the equation in ESI ). The rates of electron transfer on the particle surface could be influenced by two-step mechanisms as follows: 16 Based on these mechanisms, the amount of electrons transferred in each reaction step was calculated and is summarized in Table 1. For elongated THH gold nanoparticles, the electron charging rate was seven times faster (328 electrons per s) than the corresponding value for gold nanorods (46 electrons per s). In terms of movement of electrons from the gold catalyst to 4-NIP, the same tendency as that described above was found. For elongated THH gold nanoparticles, the catalytic reaction rate was nearly twoand-a-half times faster (80 electrons per s) as compared with gold nanorods (32 electrons per s). This also enables one to determine the number of product molecules produced. These results can also be supported by CV measurements (Fig. S6, ESI ). The CV traces for the elongated THH gold nanoparticles exhibit a higher peak current of around 0.86 V (oxidation peak voltage) and 1.32 V (reduction peak voltage) than those for gold nanorods, indicating that more electrons are transferred when oxidation and reduction occur via the elongated THH gold nanoparticles. The findings presented here clearly demonstrate that higher-index facets of novel metal catalysts having high density of stepped atoms ( atoms per cm 2,Table1) result in an increased rate in chemical catalytic reactions. In conclusion, we have demonstrated the direct comparison of catalytic reaction rates in terms of electron transfer in 4-NIP reduction using two kinds of gold nanoparticles: high-index {730} elongated THH gold nanoparticle and low-index {100}, {110}, and {111} gold nanorods. Direct monitoring of time-resolved Rayleigh scattering spectra of a single nanocatalyst allowed one to conclude that higher-index facets function more efficiently in 4-NIP catalytic reduction, as evidenced by quantification of the amount of electrons that participate in the reaction. Furthermore, our approach of using DFM equipped with SPS paves the way for a potential tool for the accurate comparison of electron transfer rates in redox heterogeneous catalytic reactions using various metal nanocatalysts. This research was supported by WCU (World Class University) program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (R ). This work was also supported by Korea Ministry of Environment as Converging technology project ( ). Notes and references 1 R. Narayanan and M. A. El-Sayed, Nano Lett., 2004, 4, ; Y. Li, E. Boone and M. A. El-Sayed, Langmuir, 2002, 18, ; M. Chirea, A. Freitas, B. S. Vasile, C. Ghitulica, C. M. Pereira and F. Silva, Langmuir, 2011, 27, T. Ming, W. Feng, Q. Tang, F. Wang, L. Sun, J. Wang and C. Yan, J. Am. Chem. Soc., 2009, 131, N. Tian, Z. Zhou, S. Sun, Y. Ding and Z. L. Wang, Science, 2007, 316, S. Wunder, Y. Lu, M. Albrecht and M. Ballauff, ACS Catal., 2011, 1, ; Y. Deng, Y. Cai, Z. Sun, J. Liu, C. Liu, J. Wei, W. Li, C. Liu, Y. Wang and D. Zhao, J. Am. Chem. Soc., 2010, 132, ; S. Panigrahi, S. Basu, S. Praharaj, S. Pande, S. Jana, A. Pal, S. K. Ghosh and T. Pal, J. Phys. Chem. C, 2007, 111, S. Wunder, F. Polzer, Y. Lu, Y. Mei and M. Ballauff, J. Phys. Chem. C, 2010, 114, E. Stavitski, M. H. F. Kox, I. Swart, F. M. F. Groot and B. M. Weckhuysen, Angew. Chem., Int. Ed., 2008, 47, ; V. Johanek, S. Schauermann, M. Laurin, J. Libuda and H. Freund, Angew. Chem., Int. Ed., 2003, 42, H. G. Liao, Y. S. Jiang, Z. Y. Zhou, S. P. Chen and S. G. Sun, Angew. Chem., Int. Ed., 2008, 47, ; X. Huang, Z. Zhao, J. Fan, Y. Tan and Z. Zheng, J. Am. Chem. Soc., 2011, 133, M. L. Tang, N. Liu, J. A. Dionne and A. P. Alivisatos, J. Am. Chem. Soc., 2011, 133, ; X. Zhou, W. Xu, G. Liu, D. Panda and P. Chen, J. Am. Chem. Soc., 2010, 132, D. Seo, G. Park and H. Song, J. Am. Chem. Soc., 2012, 134, C. Novo, A. M. Funston and P. Murvaney, Nat. Nanotechnol., 2008, 3, L. Ai, H. Yue and J. Jiang, J. Mater. Chem., 2012, 22, J. Guo and K. S. Suslick, Chem. Commun., 2012, 48, ; A. Shivhare, S. J. Ambrose, H. Zhang, R. W. Purves and R. W. J. Scott, Chem. Commun., 2013, 49, T. K. Sau and C. J. Murphy, Langmuir, 2004, 20, E. C. Argibay, B. R. González, S. G. Graña, A. G. Martínez, I. P. Santos, J. P. Juste and L. M. L. Marzán, Angew. Chem., Int. Ed., 2010, 49, C. Novo and P. Murvaney, Nano Lett., 2007, 7, S. Chen and K. Huang, Langmuir, 2000, 16, ; H. Tsutsumi, S. Furumoto, M. Morita and Y. Matsuda, J. Colloid Interface Sci., 1995, 171, Chem. Commun., 2013, 49, This journal is c The Royal Society of Chemistry 2013

358 Copyright 2013 American Scientific Publishers All rights reserved Printed in the United States of America Journal of Nanoscience and Nanotechnology Vol. 13, , 2013 Hydrogenation of Succinic Acid to 1,4-Butanediol Over Rhenium Catalyst Supported on Copper-Containing Mesoporous Carbon RESEARCH ARTICLE Ung Gi Hong 1, Hai Woong Park 1, Joongwon Lee 1, Sunhwan Hwang 1, Jimin Kwak 2, Jongheop Yi 1, and In Kyu Song 1 1 School of Chemical and Biological Engineering, Institute of Chemical Processes, World Class University Program of Chemical Convergence for Energy and Environment, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , South Korea 2 Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, BC, Vancouver V6T 1Z3, Canada Copper-containing mesoporous carbon (Cu-MC) was prepared by a single-step surfactanttemplating method. For comparison, copper-impregnated mesoporous carbon (Cu/MC) was also prepared by a surfactant-templating method and a subsequent impregnation method. Rhenium catalysts supported on copper-containing mesoporous carbon and copper-impregnated mesoporous carbon (Re/Cu-MC and Re/Cu/MC, respectively) were then prepared by an incipient wetness method, and they were applied to the liquid-phase hydrogenation of succinic acid to 1,4-butanediol (BDO). It was Delivered observed by Publishing that copper Technology in the Re/Cu-MC to: Dental catalyst Library was well Seoul incorporated Natl Univ into carbon framework, resulting IP: in higher surface areaon: and larger Mon, pore 24 Mar volume 2014 than 04:36:44 those of Re/Cu/MC catalyst. Therefore, Re/Cu-MC catalyst Copyright: showedamerican higher copper Scientific dispersion Publishers than Re/Cu/MC catalyst, although both catalysts retained the same amounts of copper and rhenium. In the liquid-phase hydrogenation of succinic acid to BDO, Re/Cu-MC catalyst showed a better catalytic activity than Re/Cu/MC catalyst. Fine dispersion of copper in the Re/Cu-MC catalyst was responsible for its enhanced catalytic activity. Keywords: Copper-Containing Mesoporous Carbon, Succinic Acid, 1,4-Butanediol, Supported Rhenium Catalyst. 1. INTRODUCTION 1,4-Butanediol (BDO) is widely used as a solvent in the production of plastics, elastic fibers, and polyurethanes. 1 2 BDO is currently produced via several routes, including hydrogenation of maleic anhydride (MAN), high pressure reaction of acetylene, and hydrogenation from propylene oxide (PO). 3 5 However, all these feedstocks (MAN, acetylene, and PO) are obtained from fossil fuels, leading to unstable price and environmental problems. 6 Therefore, demand for finding a cheap and green chemical that can replace these feedstocks has continuously increased. Recently, conversion of succinic acid (SA) to BDO has attracted much attention, because of the increase of succinic acid production in the biorefinery process. 7 Succinic Author to whom correspondence should be addressed. acid is a cheap and bio-based chemical that can be converted into BDO by hydrogenation reaction. 8 9 It has been reported that reaction of dicarboxylic acid with alcohol can produce diol via alkyl oxalate. 10 Similarly, succinic acid (SA) can react with methanol to produce BDO via dimethyl succinate (DMS) as shown in Figure 1. First, methylation of succinic acid to DMS occurs by dehydration of carboxyl group in succinic acid. Second, BDO is formed via demethylation of carbonyl group in DMS. It is known that rhenium-based catalysts are efficient for the hydrogenation of succinic acid to DMS. 11 For the production of BDO, however, strong activity for demethylation is also required. Therefore, it is important to find a suitable catalyst that has both methylation activity (SA DMS) and demethylation activity (DMS BDO) in the hydrogenation of succinic acid to BDO. It is known that copper-based catalysts are 7448 J. Nanosci. Nanotechnol. 2013, Vol. 13, No /2013/13/7448/006 doi: /jnn

359 Hydrogenation of Succinic Acid to 1,4-Butanediol Over Rhenium Catalyst Supported on Cu-MC Hong et al. RESEARCH ARTICLE Table II. Amount of hydrogen uptake and metal particle size of supported rhenium catalysts (Re/Cu-MC and Re/Cu/MC). Amount of Rhenium Amount of Copper hydrogen uptake particle hydrogen uptake particle of rhenium size of copper size (mmol/g-cat.) (nm) (mmol/g-cat.) (nm) Re/Cu-MC Re/Cu/MC Table III. Catalytic performance of supported rhenium catalysts (Re/Cu-MC and Re/Cu/MC) in the liquid-phase hydrogenation of succinic acid (reaction temperature = 200 C, reaction pressure = 80 bar, reaction time = 20 h). Conversion Selectivity (%) Yield for of SA (%) BDO DMS GBL BDO (%) Re/Cu-MC Re/Cu/MC of succinic acid (SA) is shown in Table III. 1,4- Butanediol (BDO) was produced as a target product, while -butyrolactone (GBL) was produced as a by-product via direct hydrogenation of succinic acid. Dimethyl succinate (DMS) was also produced as an intermediate via methylation of succinic acid with methanol. Both Re/Cu-MC and Delivered Re/Cu/MC by Publishing catalysts Technology exhibited to: References Dental Library andseoul Notes Natl Univ complete conversion (100%) ofip: succinic acid (SA), On: andmon, 24 Mar :36:44 Copyright: American Scientific 1. H. Haitao, Publishers Y. Zhao, C. Gao, Y. Wang, Z. Sun, and X. Liang, Chem. they showed selectivity for DMS of 79.9% and 85.6%, respectively. On the other hand, Re/Cu-MC catalyst showed higher selectivity for BDO than Re/Cu/MC catalyst. As a consequence, yield for BDO over Re/Cu-MC catalyst was higher than that over Re/Cu/MC catalyst. The enhanced catalytic performance of Re/Cu-MC catalyst compared to Re/Cu/MC catalyst might be due to fine dispersion of copper. It has been reported that metal particle size plays a key role in determining the catalytic performance in the liquid-phase hydrogenation of succinic acid. It has also been reported that dealkylation of alkyl oxalate is a rate-determining step in the hydrogenation of dicarboxylic acid with alcohol. 27 Although rhenium particle size between Re/Cu-MC and Re/Cu/MC showed no great difference (Fig. 3 and Table II), copper dispersion of Re/Cu-MC was much higher than that of Re/Cu/MC. This implies that copper dispersion played a key role in the liquid-phase hydrogenation of succinic acid to BDO via DMS. Thus, Re/Cu-MC catalyst served as a more efficient catalyst than Re/Cu/MC for the hydrogenation of succinic acid to BDO. 4. CONCLUSIONS Copper-containing mesoporous carbon (Cu-MC) was prepared by a single-step surfactant-templating method. Rhenium catalysts supported on copper-containing mesoporous carbon (Cu-MC) and copper-impregnated mesoporous carbon (Cu/MC) were then prepared by an incipient wetness method. Rhenium catalyst supported on Cu-MC (Re/Cu-MC) showed higher copper dispersion than rhenium catalyst supported on Cu/MC (Re/Cu/MC), although Re/Cu-MC and Re/Cu/MC catalyst retained the same amounts of copper and rhenium. In the liquid-phase hydrogenation of succinic acid (SA) to 1,4-butanediol (BDO), Re/Cu-MC catalyst showed higher yield for BDO than Re/Cu/MC catalyst. The enhanced catalytic performance of Re/Cu-MC catalyst compared to Re/Cu/MC catalyst was due to fine dispersion of copper in the Re/Cu-MC catalyst. Thus, copper dispersion played a key role in the liquid-phase hydrogenation of succinic acid to BDO over rhenium catalyst supported on copper-containing mesoporous carbon. Acknowledgments: This subject is supported by Korea Ministry of Environment as Converging Technology Project ( ). This work was also supported by WCU (World Class University) program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (R ). Eng. J. 181, 501 (2012). 2. R. Marín, A. Alla, A. M. de Ilarduya, and S. Muñoz-Guerra, J. Appl. Polym. Sci. 123, 986 (2012). 3. C. I. Meyer, A. J. Marchi, A. Monzon, and T. F. Garetto, Appl. Catal. A:Gen. 367, 122 (2009). 4. L.-F. Chen, P.-J. Guo, L.-J. Zhu, M.-H. Qiao, W. Shen, H.-L. Xu, and K.-N. Fan, Appl. Catal. A: Gen. 356, 129 (2009). 5. Z. Xu and B.-H. Guo, Biotechnol. J. 5, 1149 (2010). 6. U. G. Hong, S. Hwang, J. G. Seo, J. Yi, and I. K. Song, Catal. Lett. 138, 28 (2010). 7. D. P. Minh, M. Besson, C. Pinel, P. Fuertes, and C. Petitjean, Top Catal. 53, 1270 (2010). 8. R. Luque, J. H. Clark, K. Yoshida, and P. L. Gai, Chem. Commun (2009). 9. P. Gallezot, Chem. Soc. Rev. 41, 1538 (2012). 10. L. Rosi, M. Frediani, and P. Frediani, J. Org. Chem. 695, 1314 (2010). 11. J. R. Budge, T. G. Attig, and R. A. Dubbert, U. S. Patent No. 5, 969, 164 (1999). 12. C. Ohlinger and B. Kraushaar-Czarnetzki, Chem. Eng. Sci. 58, 1453 (2003). 13. G. Ding, Y. Zhu, H. Zheng, H. Chen, and Y. Li, J. Chem. Technol. Biotechnol. 86, 231 (2011). 14. J. H. Schlander and T. Turek, Ind. Eng. Chem. Res. 38, 1264 (1999). 15. J. G. Seo, M. H. Youn, K. M. Cho, S. Park, S. H. Lee, J. Lee, and I. K. Song, Korean J. Chem. Eng. 25, 41 (2008). 16. K. Nam, S. Lim, S.-K. Kim, D. Peck, and D. Jung, J. Nanosci. Nanotechnol. 11, 5716 (2011). 17. R. Logudurai, C. Anand, V. V. Balasubramanian, K. Ariga, P. Srinivasu, and A. Vinu, J. Nanosci. Nanotechnol. 10, 329 (2010). 18. Y.-G. Hu, K. M. Liew, and Q. Wang, J. Nanosci. Nanotechnol. 11, (2011) J. Nanosci. Nanotechnol. 13, , 2013

Applied Catalysis A: General 469 (2014) 466 471 Contents lists available at ScienceDirect Applied Catalysis A: General j ourna l h omepa ge: www.elsevier.

360 Applied Catalysis A: General 469 (2014) Contents lists available at ScienceDirect Applied Catalysis A: General j ourna l h omepa ge: Hydrogenation of succinic acid to tetrahydrofuran (THF) over ruthenium carbon composite (Ru C) catalyst Ung Gi Hong, Jeong Kwon Kim, Joongwon Lee, Jong Kwon Lee, Ji Hwan Song, Jongheop Yi, In Kyu Song School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , South Korea a r t i c l e i n f o Article history: Received 11 July 2013 Received in revised form 12 October 2013 Accepted 15 October 2013 Available online 27 October 2013 Keywords: Hydrogenation Succinic acid Tetrahydrofuran Ruthenium Mesoporous carbon a b s t r a c t Ruthenium carbon composite (Ru XC) catalysts prepared by a single-step surfactant-templating method were pre-graphitized at different temperature (X = 200, 250, 300, 350, and 400 C), and they were applied to the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF). The effect of pregraphitization temperature on the catalytic performance of Ru XC catalysts (X = 200, 250, 300, 350, and 400 C) was investigated. It was observed that Ru XC composite catalysts showed different textural properties depending on pre-graphitization temperature. In the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF), conversion of succinic acid and yield for THF showed volcano-shaped trends with respect to pre-graphitization temperature. In other words, an optimal pre-graphitization temperature was required to achieve maximum catalytic performance of Ru XC catalysts. Yield for THF in the hydrogenation of succinic acid increased with decreasing ruthenium particle size of Ru XC catalysts. Among the catalysts tested, Ru-300C, which had the smallest ruthenium particle size, showed the highest yield for THF Elsevier B.V. All rights reserved. 1. Introduction Tetrahydrofuran (THF) is a very important chemical in various polymer industries. THF can be converted into polytetramethylene ether glycol (PTMEG) and tetrahydrothiophene [1 3]. THF is also widely used as a solvent in the production of polyvinyl chloride (PVC) and paints. THF is currently produced via several petrochemical processes such as hydrogenation of maleic anhydride (MAN) [4], dehydration of 1,4-butanediol (BDO) [5], and oxidation of butadiene (BD) [6]. However, all these feedstocks (MAN, BDO, and BD) are obtained from fossil fuels, leading to several problems such as unstable price and environmental contamination. Therefore, demand for finding a new and clean platform that can replace these feedstocks has continuously increased [7 9]. Recently, conversion of succinic acid to THF has attracted much attention, because of the increase of succinic acid production in the biorefinery process [10,11]. Succinic acid is a cheap and bio-based chemical that can be converted into THF by hydrogenation reaction. It is known that ruthenium-based catalyst is one of the efficient catalysts for selective formation of THF through hydrogenation of succinic acid [12 14]. Many researches on ruthenium catalysts have been focused on finding suitable supporting Corresponding author. Tel.: ; fax: address: inksong@snu.ac.kr (I.K. Song). materials. Among various supporting materials, carbon has been widely employed due to its well-developed porosity, non-toxicity, and hydrophobic property [15 17]. We have previously investigated the liquid-phase hydrogenation of succinic acid over novel metal catalyst impregnated on mesoporous carbon prepared by a surfactant-templating method [14,18]. We found that carbon support prepared by a surfactanttemplating method retained high surface area and large pore volume, leading to excellent physical properties. For this reason, novel metal catalyst impregnated on mesoporous carbon showed a considerable catalytic performance in the hydrogenation of succinic acid to THF [18]. However, novel metal catalyst impregnated on mesoporous carbon required a number of filtration and drying steps. Furthermore, novel metal particles did not well interact with carbon framework. It has been reported that structure of carbon framework prepared by a self-assembly method can be controlled by pregraphitization treatment [19,20]. If metal carbon interaction is properly formed, therefore, metal dispersion of metal carbon composite prepared by a single-step surfactant-templating method may be controlled. In other words, metal particle size of metal carbon composite can be controlled by changing pregraphitization temperature. Furthermore, metal carbon composite prepared by a single-step surfactant-templating method with pre-graphitization can not only achieve a fine metal dispersion but also provide a simple preparation route. Therefore, it is X/$ see front matter 2013 Elsevier B.V. All rights reserved.

361 U.G. Hong et al. / Applied Catalysis A: General 469 (2014) volcano-shaped trends with respect to pre-graphitization temperature; an optimal pre-graphitization temperature for the treatment of Ru XC composites was required to achieve maximum yield for THF. Yield for THF in the hydrogenation of succinic acid increased with decreasing ruthenium particle size of Ru XC catalysts. Thus, ruthenium particle size played a key role in determining the catalytic performance in the hydrogenation of succinic acid to THF over Ru XC catalysts. In the recycle test, Ru-300C catalyst served as a stable and reusable catalyst for hydrogenation of succinic acid to THF. Acknowledgements This subject is supported by Korea Ministry of Environment as Converging Technology Project ( ) References [1] J. Keneta, T. Asano, S. Masamune, Ind. Eng. Chem. 62 (1970) [2] V. Pallassana, M. Neurok, G. Coulston, Catal. Today 50 (1999) [3] S.P. Müller, M. Kucher, C. Ohlinger, B. Kraushaar-Czarnetzkyi, J. Catal. 218 (2003) [4] S.M. Jung, E. Godard, S.Y. Jung, K.-C. Park, J.U. Choi, J. Mol. Catal. A 198 (2003) [5] S.E. Hunter, C.E. Ehrenberger, P.E. Savage, J. Org. Chem. 71 (2006) [6] M.D. Wildberger, M. Maciejewski, J.-D. Grunwaldt, T. Mallat, A. Baiker, Appl. Catal. A 179 (1999) [7] B.K. Ly, D.P. Minh, C. Pinel, M. Besson, B. Tapin, F. Epron, C. Especel, Top. Catal. 55 (2012) [8] C. Delhomme, D. Weuster-Botz, F.E. Kühn, Green Chem. 11 (2009) [9] A. Cukalovic, C.V. Stevens, Biofuels Bioprod. Bioref. 2 (2008) [10] I. Bechthold, K. Bretz, S. Kabasci, R. Kopitzky, A. Springer, Chem. Eng. Technol. 31 (2008) [11] C. Du, S.K.C. Lin, A. Koutinas, R. Wang, C. Webb, Appl. Microbiol. Biotechnol. 76 (2007) [12] L. Rosi, M. Frediani, P. Frediani, J. Org. Chem. 695 (2010) [13] R. Luque, J.H. Clark, K. Yoshida, P.L. Gai, Chem. Commun. (2009) [14] U.G. Hong, H.W. Park, J. Lee, S. Hwang, I.K. Song, J. Ind. Eng. Chem. (2012) [15] P. Kim, J.B. Joo, W. Kim, J. Kim, I.K. Song, J. Yi, Catal. Lett. 112 (2006) [16] H. Kim, J.C. Jung, D.R. Park, S.-H. Baeck, I.K. Song, Appl. Catal. A 320 (2007) [17] U.G. Hong, D.R. Park, S. Park, J.G. Seo, Y. Bang, S. Hwang, M.H. Youn, I.K. Song, Catal. Lett. 132 (2009) [18] U.G. Hong, H.W. Park, J. Lee, S. Hwang, J. Yi, I.K. Song, Appl. Catal. A 415/416 (2012) [19] C.H. Yun, Y.H. Park, C.R. Park, Carbon 39 (2001) [20] M. Kruk, K.M. Kohlhaas, B. Dufour, E.B. Celer, M. Jaroniec, K. Matyjaszewski, R.S. Ruoff, T. Kowalewski, Microporous Mesoporous Mater. 102 (2007) [21] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquérol, T. Siemieniewska, Pure Appl. Chem. 57 (1985) [22] J. Guo, A.C. Lua, J. Therm. Anal. Calorim. 60 (2000) [23] Z.Q. Li, C.J. Lu, Z.P. Xia, Y. Zhou, Z. Luo, Carbon 45 (2007) [24] Z.-Z. Lin, T. Okuhara, M. Misono, J. Phys. Chem. 92 (1988) [25] P. Betancourt, A. Rives, R. Hubaut, C.E. Scott, J. Goldwasser, Appl. Catal. A 170 (1998) [26] P.C.H. Mitchell, A.J. Ramirez-Cuesta, S.F. Parker, J. Tomkinson, D. Thompsett, J. Phys. Chem. 107 (2003) [27] C. Prado-Burguete, A. Linares-Solano, F. Rodríguez-Reinoso, C. Salinas-Martínez De Lecea, J. Catal. 128 (1991) [28] J. Okal, M. Zawadzki, L. Kępiński, L. Krajczyk, W. Tylus, Appl. Catal. A 319 (2007) [29] P. Scherrer, Gőttinger Nachr. Ges. 2 (1918) [30] A.L. Patterson, Phys. Rev. 56 (1939) [31] Y. Bang, S.J. Han, J. Yoo, J.H. Choi, K.H. Kang, J.H. Song, J.G. Seo, J.C. Jung, I.K. Song, Int. J. Hydrogen Energy 38 (2013) [32] Z. Li, X. Hu, L. Zhang, S. Liu, G. Lu, Appl. Catal. A (2012) [33] S.D. Robertson, B.D. McNicol, J.H. de Baas, S.C. Kloet, J. Catal. 37 (1975) [34] J.F. Le Page, Applied Heterogeneous Catalysis: Design, Manufacture, Use of Solid Catalysts, Editors Technip, Paris, 1987, pp [35] H.S. Broadbent, Ann. N.Y. Acad. Sci. 145 (1967)

362 G Model JIEC-1817; No. of Pages 7 Journal of Industrial and Engineering Chemistry xxx (2014) xxx xxx Contents lists available at ScienceDirect Journal of Industrial and Engineering Chemistry jou r n al h o mep ag e: w ww.elsevier.co m /loc ate/jiec Hydrogenation of succinic acid to tetrahydrofuran over ruthenium-carbon composite catalysts: Effect of HCl concentration in the preparation of the catalysts Ung Gi Hong, Jeong Kwon Kim, Joongwon Lee, Jong Kwon Lee, Ji Hwan Song, Jongheop Yi, In Kyu Song * School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul , South Korea A R T I C L E I N F O Article history: Received 5 December 2013 Accepted 27 December 2013 Available online xxx Keywords: Hydrogenation Succinic acid Tetrahydrofuran Mesoporous carbon Ruthenium A B S T R A C T Ruthenium-carbon composite (Ru-C-X) catalysts were prepared by a single-step surfactant-templating method at different HCl concentration (X = 2, 3, 4, 5, 6, and 7 M) to control morphology of Ru-C-X catalysts, i.e., to control ruthenium dispersion. They were then applied to the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF). Ru-C-X catalysts showed different ruthenium particle size depending on HCl concentration. In the reaction, yield for THF increased with decreasing average ruthenium particle size of the catalysts. Ruthenium particle size served as an important factor determining the catalytic performance of Ru-C-X in the hydrogenation of succinic acid to THF. ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. 1. Introduction Tetrahydrofuran (THF) is an important chemical in various polymer industries. THF can be converted into polytetramethylene ether glycol (PTMEG), thermoplastic polyesters, and polyurethane elastomers [1 3]. THF is also widely used as a solvent in the manufacturing of polyvinyl chloride (PVC) and paints. THF is currently produced via several industrial routes such as oxidative hydrogenation of maleic anhydride (MAN), acid-catalyzed dehydration of 1,4-butanediol (BDO), hydroformylation of ally alcohol, and oxidation of butadiene (BD) [4 6]. Because all these feedstocks (MAN, BDO, ally alcohol, and BD) are petrochemical-based chemicals, THF production from these chemicals may lead to several problems such as unstable price and environmental pollution. Therefore, demands for finding a green platform that can solve these problems have continuously increased. Succinic acid has attracted recent attraction as an alternative platform chemical to produce THF because of the increase of succinic acid production in the bio-refinery process [7 10]. Succinic acid is a green and bio-based chemical that can be converted into THF by hydrogenation reaction. Hydrogenation of succinic acid (SA) to THF follows two consecutive reaction steps via * Corresponding author. Tel.: ; fax: address: inksong@snu.ac.kr (I.K. Song). g-butyrolactone (GBL) (Fig. 1). Therefore, it is important to find a suitable noble metal that has both cyclization activity (SA!GBL) and oxidative-hydrogenation activity (GBL!THF) in the hydrogenation of succinic acid to THF. It is known that ruthenium catalyst may cause complete reduction of both carboxyl and carbonyl groups of succinic acid, leading to further hydrogenation of GBL [11 14]. Many researches on ruthenium catalyst supported on carbon have been focused on increasing ruthenium dispersion via carbon support modification. Among various carbon supports, mesoporous carbon has found successful applications due to its high surface area, well-developed porosity, and hydrophobic property [15 17]. However, novel metal catalyst impregnated on mesoporous carbon required a number of filtration and calcination steps, and novel metal particles did not well interact with carbon framework. To solve this problem, we have previously investigated metalcarbon composite catalyst prepared by a single-step surfactanttemplating method [18]. We found that metal-carbon composite catalyst prepared by a single-step surfactant-templating method retained well-developed mesopores and finely dispersed metal particles, leading to excellent catalytic properties. Furthermore, metal-carbon composite prepared by a single-step surfactanttemplating method provides a simple preparation route. It has been reported that morphology of carbon framework prepared using a self-assembled block copolymer can be controlled by changing acid concentration of polymer mixture [19,20]. In the X/$ see front matter ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. Please cite this article in press as: U.G. Hong, et al., J. Ind. Eng. Chem. (2014),

363 G Model JIEC-1817; No. of Pages 7 6 U.G. Hong et al. / Journal of Industrial and Engineering Chemistry xxx (2014) xxx xxx GBL THF By-products catalysts. This result strongly supports that ruthenium particle size of Ru-C-X catalysts served as a key factor determining the catalytic performance in the hydrogenation of succinic acid to THF Stability and reusability of Ru-C-5 catalyst Yield (%) Ru-C-2 Ru-C-3 Ru-C-4 Ru-C-5 Ru-C-6 Ru-C-7 Fig. 8. Catalytic performance of Ru-C-X catalysts in the liquid-phase hydrogenation of succinic acid to THF (reaction temperature = 240 8C, reaction pressure = 80 bar, reaction time = 4 h). To investigate the stability and reusability of the catalyst, recycle tests for hydrogenation of succinic acid over Ru-C-5 catalyst were performed three times. Fig. 10 shows the result for liquid-phase hydrogenation of succinic acid to THF over Ru-C-5 catalyst with respect to recycle run. It was found that there was no great difference in catalytic activity between fresh and spent catalysts (more than 95% recycle efficiency). Furthermore, no significant ruthenium leaching (less than 1.0 ppm) was detected by ICP-AES analysis after each reaction test. Thus, Ru-C-5 catalyst served as a stable and reusable catalyst in the liquid-phase hydrogenation of succinic acid to THF. 4. Conclusions Yield for THF (%) Ru-C-5 Ru-C-4 Ru-C-3 Ru-C-6 Ru-C-2 Ru-C Ruthenium particle size (nm) Ruthenium-carbon composite (Ru-C-X) catalysts were prepared by a single-step surfactant-templating method at different HCl concentration (X = 2, 3, 4, 5, 6, and 7 M) to control morphology of Ru-C-X catalysts, i.e., to control ruthenium dispersion. They were then applied to the liquid-phase hydrogenation of succinic acid to THF. Among the Ru-C-X (X= 2, 3, 4, 5, 6, and 7) catalysts, Ru-C-5 catalyst showed the smallest ruthenium particle size due to welldeveloped mesoporous structure. In the hydrogenation of succinic acid, yield for THF showed a volcano-shaped trend with respect to HCl concentration. Thus, an optimal HCl concentration for the preparation of Ru-C-X composite catalysts was required to achieve maximum yield for THF. Yield for THF in the hydrogenation of succinic acid increased with decreasing ruthenium particle size of Ru-C-X catalysts. Ruthenium particle size (ruthenium dispersion) played a key role in determining the catalytic performance in the hydrogenation of succinic acid to THF over Ru-C-X catalysts. In the recycle test, Ru-C-5 catalyst served as a stable and reusable catalyst for hydrogenation of succinic acid to THF. Acknowledgements Fig. 9. A correlation between ruthenium particle size of Ru-C-X catalysts (determined by XRD) and catalytic activity in the hydrogenation of succinic acid to THF. Percentage (%) Conversion of succinic acid Yield for THF Recycle run Fig. 10. Result for liquid-phase hydrogenation of succinic acid over Ru-C-5 catalyst with respect to recycle run (reaction temperature =240 8C, reaction pressure = 80 bar, reaction time = 4 h). This subject is supported by Korea Ministry of Environment as Converging Technology Project ( ). References [1] A. Küksal, E. Klemm, G. Emig, Appl. Catal. A 228 (2002) 237. [2] J.A.F.F. Rocco, J.E.S. Lima, V.L. Lourenco, N.L. Batista, E.C. Botelho, K. Iha, J. Appl. Polym. Sci. 126 (2012) [3] S.P. Müller, M. Kucher, C. Ohlinger, B. Kraushaar-Czarnetzkyi, J. Catal. 218 (2003) 419. [4] Y. Feng, H., Yin, A., Wang, T., Xie, T. Jiang, Appl. Catal. A (2012) 205. [5] Q. Zhang, Y. Zhang, H. Li, C. Gao, Y. Zhao, Appl. Catal. A 466 (2013) 233. [6] M.D. Wildberger, M. Maciejewski, J.-D. Grunwaldt, T. Mallat, A. Baiker, Appl. Catal. A 179 (1999) 189. [7] H. Choudhary, S. Nishimura, K. Ebitani, Appl. Catal. A 458 (2013) 55. [8] C. Delhomme, D. Weuster-Botz, F.E. Kühn, Green Chem. 11 (2009) 13. [9] A. Cukalovic, C.V. Stevens, Biofuels Bioprod. Bioref. 2 (2008) 505. [10] B. Tapin, F. Epron, C. Especel, B.K. Ly, C. Pinel, M. Besson, ACS Catal. 3 (2013) [11] L. Rosi, M. Frediani, P. Frediani, J. Org. Chem. 695 (2010) [12] R. Luque, J.H. Clark, Catal. Commun. 11 (2010) 928. [13] R.M. Deshpande, V.V. Buwa, C.V. Rode, R.V. Chaudhari, P.L. Mills, Catal. Commun. 3 (2002) 269. [14] U.G. Hong, H.W., Park, J., Lee, S., Hwang, J., Yi, I. K. Song, Appl. Catal. A (2012) 141. [15] P. Kim, J.B. Joo, W. Kim, J. Kim, I.K. Song, J. Yi, Catal. Lett. 112 (2006) 213. [16] H. Kim, J.C. Jung, D.R. Park, S.-H. Baeck, I.K. Song, Appl. Catal. A 320 (2007) 159. [17] U.G. Hong, D.R. Park, S. Park, J.G. Seo, Y. Bang, S. Hwang, M.H. Youn, I.K. Song, Catal. Lett. 132 (2009) 377. [18] U.G. Hong, J.K. Kim, J. Lee, J.K. Lee, J.H. Song, J. Yi, I.K. Song, Appl. Catal. A 469 (2014) 466. [19] N. Liu, H. Song, X. Chen, J. Mater. Chem. 21 (2011) Please cite this article in press as: U.G. Hong, et al., J. Ind. Eng. Chem. (2014),

364 ChemComm COMMUNICATION View Article Online View Journal View Issue Published on 27 May Downloaded by Seoul National University on 25/06/ :57:09. Cite this: Chem. Commun., 2014, 50, 7652 Received 13th March 2014, Accepted 27th May 2014 DOI: /c4cc01881h A facile and efficient approach to prepare hierarchically and radially mesoporous nano-catalysts with tunable acidic properties has been successfully developed. The nanospheres show excellent catalytic performance for the acid catalysed reactions, i.e. cracking of 1,3,5-triisopropylbenzene and hydrolysis of sucrose. Hierarchically porous nanomaterials have attracted a great deal of interest in recent years because of their superior physicochemical properties, such as large surface area, high porosity, and low density. 1,2 However, many hierarchically porous nano-materials, such as silica, are chemically and/or catalytically inactive, making it difficult to meet the needs of these materials for practical applications including catalysis, adsorption, separation, and drug delivery and sensing. 3 The incorporation of heteroatoms into the silica framework by a direct synthesis or post-grafting method has been widely used to create active sites. 4 These conventional methods, however, suffer from some critical limitations, such as the collapse of their structure when a large amount of heteroatoms are introduced, 5 complex and time-consuming processes, 3,6 and difficulty in controlling the amount of grafted heteroatoms. 7 Therefore, the development of simple and efficient strategies for preparing the hierarchically porous nanomaterials with adjustable catalytic functionalities continues to be a great challenge. Herein, we report on a convenient and effective route for the preparation of tunable acid nano-catalysts with a hierarchically and radially mesoporous structure. In this method, referred to as ph-assisted delay addition, an Al precursor was added to a World Class University Program of Chemical Convergence for Energy & Environment, Institute of Chemical Processes, School of Chemical and Biological Engineering, College of Engineering, Seoul National University, Seoul , Republic of Korea. jyi@snu.ac.kr; Tel: Electronic supplementary information (ESI) available: Experimental details, characterization (EPMA, SEM and TEM images, XRD results, NH 3 -TPD, in situ FTIR spectra of adsorbed NH 3, 27 Al MAS NMR spectra N 2 adsorption desorption isotherms, and TG analysis), catalytic activities for the cracking of 1,3,5-TIPB and hydrolysis of sucrose, and hydrothermal stability test. See DOI: /c4cc01881h These authors contributed equally. A facile approach for the preparation of tunable acid nano-catalysts with a hierarchically mesoporous structure Youngbo Choi, Yang Sik Yun, Hongseok Park, Dae Sung Park, Danim Yun and Jongheop Yi* ph adjusted solution containing preformed hierarchically and radially mesoporous (HRM) nanostructures via a hydrothermal treatment. 2 A second hydrothermal treatment was then used to introduce heteroatoms into the silica framework, resulting in the maintenance of the unique structure with acidic properties. In contrast, when a small amount of an Al precursor was included in the initial solution, as in the case of the direct synthesis, HRM nanostructures were not obtained (Fig. S1, ESI ). In the developed procedure, it is noteworthy that the reaction time required to preform the HRM nanostructure and the ph shift prior to the addition of the Al precursor played a crucial role in introducing the functionality while maintaining its nanostructures (Fig. S1, ESI ). Interestingly, by simply changing the ph adjusting agent in the procedure to prepare the aluminosilicate nanospheres (denoted as ASN-X where X indicates the Si/Al molar ratio), we can induce incorporation of P as well as Al into silica framework, leading to the formation of aluminosilicophosphate nanospheres (denoted as ASPN-X where X indicates the Si/Al molar ratio). Furthermore, the Si/Al ratio of both ASN and ASPN samples can be easily controlled by simply changing the concentrations in the initial preparation solution because its ratios in the preparation solution were preserved in the final samples while the content of P in the ASPN samples is about half that of Al (Table S1, ESI ). The morphology and structure of the ASN and ASPN samples with various Si/Al ratios prepared under optimum conditions were investigated using electron microscopy. As shown in the scanning electron microscopy (SEM) images, both ASN and ASPN samples are spherical in shape with a uniform particle size ( nm) (Fig. 1a and b and Fig. S2, ESI ). Magnified SEM images demonstrate that the wrinkled sheets are arranged in three dimensions to form a spherical shape with a pore mouth size of nm. The large diameters of the pores can permit guest molecules to easily access the active sites inside the pores. The transmission electron microscopy (TEM) images indicate that the pores are radially oriented, and their size gradually increases from the center to the outer surface (Fig. 1c and Fig. S2, ESI ). Elemental mapping images demonstrate a highly homogeneous distribution of elemental Si and Al in the 7652 Chem. Commun., 2014, 50, This journal is The Royal Society of Chemistry 2014

View Article Online Published on 27 May 2014. Downloaded by Seoul National University on 25/06/2014 07:57:09. ChemComm (Fig. 3a and Table S3, ESI ).

365 View Article Online Published on 27 May Downloaded by Seoul National University on 25/06/ :57:09. ChemComm (Fig. 3a and Table S3, ESI ). The total amount of acid sites progressively increased with increasing Al content, from mmol g 1 for ASN-60 to mmol g 1 for ASN-15. The peak maximum of the TPD curves shifted to higher temperatures with increasing Al content, indicating an increase in acid strength. The acid strength distribution also showed a positive relation between Al content and densities for both medium and strong acidity. As compared with the ASN samples with the same Si/Al ratio, the total acid amount on the ASPN samples was significantly increased. In order to distinguish between Brønsted and Lewis acid sites on the samples, in situ FTIR spectra for NH 3 adsorbed on the samples were also recorded (Fig. 3b and Table S3, ESI ). In the spectra, two bands at ca and 1705 cm 1 are assigned to NH 3 adsorbed on Brønsted acid sites, and a band at 1640 cm 1 is attributed to NH 3 adsorbed on Lewis acid sites. 14 The ratio of Brønsted to Lewis acid sites (BS/LS ratio) on the ASN samples was gradually enhanced with increasing Al content, from 0.6 for ASN-60 to 5.5 for ASN-15. In the case of the ASPN samples, the BS/LS ratio was noticeably increased compared to the ASN samples with the same Si/Al ratio. The larger acid amount and higher BS/LS ratio of the ASPN samples can be attributed to the OH groups associated with the P atoms which provide additional weak Brønsted acid sites. 9,15 Compared with AlMCM-41, the total amount of acid and the ratio of Brønsted to Lewis acid sites (BS/LS ratio) in ASN-40 were higher by 1.8 and 1.7, respectively (Fig. S4 and Table S3, ESI ). In amorphous aluminosilicates such as ASN and AlMCM-41 (Fig. S5, ESI ), the Brønsted acidity originates from silanol groups, which are strongly influenced by neighboring Al atoms. 16 As shown in Fig. 1d, our method results in the highly homogeneous distribution of Si and Al atoms, which facilitates the creation of silanol groups having neighboring Al, which serves to enhance the acidity. The catalytic performance of the ASN and ASPN samples was evaluated in two acid-catalysed reactions (Fig. 4). The cracking of 1,3,5-triisopropylbenzene (1,3,5-TIPB) and the hydrolysis of sucrose were chosen as model reactions for the transformation of a hydrocarbon and biomass, respectively. By different product distributions of 1,3,5-TIPB cracking and conversions of sucrose over the samples, the tunable acidic properties of ASN and ASPN samples were confirmed (Table S4, ESI ). To demonstrate the versatility of the ASN and ASPN catalysts, AlMCM-41 and HZSM-5 Fig. 4 (a) Time course for 1,3,5-TIPB conversion and (b) sucrose conversion over ASN-40, ASPN-40, AlMCM-41, and HZSM-5. Each line in (a) indicates a fitted curve by the first order deactivation model. with the same Si/Al ratio of 40 were also tested. In the cracking of 1,3,5-TIPB, HZSM-5 showed the lowest activity, since 1,3,5-TIPB is too large to enter the pores of the HZSM-5 and the reaction occurs only on the external surface. 17 AlMCM-41 showed a high initial activity, but was deactivated rapidly. Interestingly, ASN-40 and ASPN-40 not only exhibited a higher activity, but also retained much longer lifetime than the reference catalysts due to high coke resistance originated from their unique pore structure and suitable acidity (Fig. S6, ESI ). 18 The deactivation rate constant calculated from the first order deactivation model 19 was in the order of ASPN-40 (0.01 h 1 ) o ASN-40 (0.02 h 1 ) o HZSM-5 (0.11 h 1 ) { AlMCM-41 (0.75 h 1 ). Furthermore, ASN-40 was revealed to be more stable in terms of hydrothermal stability than AlMCM-41, exhibiting a relatively high activity and maintaining its structure (Fig. S7 and Table S5, ESI ). In the hydrolysis of sucrose, ASN-40 and ASPN-40 showed a higher performance than the reference catalysts (Fig. 4b). In particular, the conversion of sucrose over ASPN-40 was more than 4 times that of AlMCM-41 and HZSM-5, mainly due to the high content and easy accessibility ofthebrønstedacidsitesinaspn In summary, we report on an attractive route for introducing tunable acidic properties into the hierarchical mesoporous nanospheres. These procedures permit the amount, types, and strength of acid sites to be adjusted precisely. These are important properties for solid acids, and textural uniformity can be maintained across various compositions. The excellent catalytic properties of the resulting nanospheres suggest that they have great potential for use as solid acids in the chemical industry and in expanding the scope of hierarchically structured nanomaterials. This research is supported by Korea Ministry of Environment as Converging technology project ( ). Notes and references Communication 1 X. Du and J. He, Nanoscale, 2011, 3, 3984; W. C. Yoo and A. Stein, Chem. Mater., 2011, 23, 1761; H. 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Maes, P. A. W. van der Heide, D. Zhao, R. S. Czernuszewicz and L. Kevan, Chem. Mater., 1999, 11, 3680; Z. Luan, J. Y. Bae and L. Kevan, Chem. Mater., 2000,12, K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. A. Pierotti, J. Rouquérol and T. Siemieniewska, Pure Appl. Chem., 1985, 57, A. Corma, Chem. Rev., 1995, 95, R. Mokaya, Chem. Commun., 2000, A. Yin, X. Guo, W. L. Dai and K. Fan, J. Phys. Chem. C,2010,114, Chem. Commun., 2014, 50, This journal is The Royal Society of Chemistry 2014

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