R-2003-A-042-0-00 (KAERI/CR-245/2005) 원전폐수지처리기술 (C-14 제거 ) 개발 위탁기관 한국원자력연구소 산업자원부
Yes 양이온교환수지 원전폐수지저장용기 원전폐수지특성분석 양이온 Yes 음이온교환수지분리특성 저장탱크내 C-14 방사능분포 음이온교환수지 C-14 선택적분리 위탁과제연구범위 14 CO 2 기체휘발특성고효율제거공정흡착제개발개발및모델링 기존개발된흡착제성능개선 ( 감용비증대 ) 포집된 14 C 재활용 ( 의약, 제약, 농업용 ) 폐흡착제 공정개선을통한감용비향상및공정설계자료도출 시멘트, 폴리머 ( 플라스틱 ) 고화기술개선 대체매질개발 부피증가최소화
불활성가스산용액 C-12 C-13 C-14 고화점이하냉각 금속휘발반응 냉각 고체상이산화탄소이산화탄소가스 일산화탄소 액화일산화탄소 폐수지 C-12 Rich 산화 분별증류 C-14 탄산염 수산화금속용액과반응 이산화탄소 C-14 Rich
60 50 0.005N NaHCO3 2L/IRN150 40g 0.005N NaHCO3 2L/IRN150 30g C Ion Conc.(ppm) 40 30 20 10 0 0 5 10 15 20 25 30 Time(hr) 18 Ion-exchange capacity (mg-c/g-irn-150) 16 14 12 10 8 6 4 2 0 0 10 20 30 40 50 60 70 80 Equlibrium Concentration (ppm) 70 도건조시료 110 도건조시료 IRN( 원료 ) Langmuir-70 Langmuir-110 Langmuir-IRN( 원료 )
1.6 1.4 Ion-exchanged Capacity, Qeq (meq/g) 1.2 1.0 0.8 0.6 0.4 0.2 H2PO4 NO3 HCO3 Langmuir-C Langmuir-N Langmuir-P 0.0 0.000 0.002 0.004 0.006 0.008 0.010 0.012 Equilibrium Concentration of each Ions, Ceq (mol/l)
Ion-exchanged Capacity, Qeq (meq/g) 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 HCO3 NO3 0.0 0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 Equilibrium Concentration of each Ions, Ceq (mol/l) Ion-exchanged Capacity, Qeq (meq/g) 1.2 1.0 0.8 0.6 0.4 0.2 NO3 H2PO4 0.0 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 Equilibrium Concentration of each Ions, Ceq (mol/l)
1.8 Ion-exchange capacity, meq/g 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 Co Cs Na NH 4 Co Cs Na NH4 0.0E+00 2.5E-03 5.0E-03 7.5E-03 1.0E-02 1.3E-02 1.5E-02 1.8E-02 2.0E-02 Ce (mol/l)
7.5 7.0 6.5 6.0 Co Cs Na NH4 5.5 ph 5.0 4.5 4.0 3.5 3.0 0.000 0.002 0.004 0.006 0.008 0.010 0.012 0.014 0.016 0.018 0.020 Ce, mol/l
탈착율 탈착후용액내 총량 농도 용액부피 탈착전수지내 총량 흡착량 수지 수지양
Mixing Tank Resin or Solution N2 gas Sampling G C N2 Analysis System (Data Acquisition) Heating mantle
100 90 80 Desorption Efficiency, % 70 60 50 40 30 20 10 0 0 1 2 3 4 5 6 7 8 9 N addition /C sorbent molar ratio
Moderator Coolant 1.0 0.8 Carbon Fraction 0.6 0.4 H 2 CO 3 * HCO 3 - CO 3 2-0.2 0.0 0 2 4 6 8 10 12 14 ph
120% 100% Desorption % ph 8 7 6 Desorption percent, % 80% 60% 40% 20% 5 Solution ph 4 3 2 1 0% 0.1 0.2 0.3 0.4 0.5 0.7 1 2 3 5 10 20 stirring shaking 0.1N HNO 3 Volume, ml 0
CO2 Conc.(ppm) 55,000 50,000 45,000 40,000 35,000 30,000 25,000 20,000 15,000 10,000 5,000 0 0 20 40 60 80 100 120 140 160 180 200 Time(min) HNO3-18 mmol
2,400 2,200 2,000 NH4H2PO4 Na3PO4 NaNO3 CO2 Conc.(ppm) 1,800 1,600 1,400 1,200 1,000 800 600 400 200 0 0 10 20 30 40 50 60 Time(min) 90,000 80,000 70,000 Na3PO4-No bubbling Na3PO4-Bubbling NaNO3 CO2 Conc.(ppm) 60,000 50,000 40,000 30,000 20,000 10,000 0 0 20 40 60 80 100 120 140 160 180 산용액주입 Time(min)
200,000 180,000 160,000 HNO3-3ml(pH=6.5) HNO3-5ml(pH=2.1) HNO3-8ml(pH=0.1) 140,000 CO2 Conc.(ppm) 120,000 100,000 80,000 60,000 40,000 20,000 0 0 10 20 30 40 50 60 Time(min)
200,000 180,000 160,000 HNO3-1ml(pH=6) HNO3-2ml(pH=0.7) HNO3-4ml(pH=0.3) 140,000 CO2 Conc.(ppm) 120,000 100,000 80,000 60,000 40,000 20,000 0 0 10 20 30 40 50 60 Time(min)
40000 35000 30000 4g-No Bubbling 4g-Bubbling 6g-Bubbling CO2 C onc.(ppm ) 25000 20000 15000 10000 5000 0 0 20 40 60 80 100 120 140 160 180 Time(min)
16000 14000 NH4H2PO4 0.45 mmol NH4H2PO4 0.9 mmol NH4H2PO4 1.35 mmol NH4H2PO4 1.8 mmol HNO3 3mol 12000 CO 2 conc., ppm 10000 8000 6000 4000 2000 0 0 10 20 30 40 50 60 70 Time(min)
120 100 Desorption percent of HCO 3 ion, % 80 60 40 20 0 0 10 20 30 40 50 60 70 80 Time, min 50% 100% 150% 200% HNO3 120 100 Desorption percent of HCO 3 ion, % 80 60 40 20 0 50% 100% 150% 200% HNO3 0 10 20 30 40 50 60 70 80 Time, min
120 100 Desorption percent of HCO3 ion, % 80 60 40 50% 100% 20 150% 200% HNO3 0 0 10 20 30 40 50 60 70 80 Time, min
120 100 Desorption percent of HCO 3 ion, % 80 60 40 20 0 30% loaded 50% loaded 100% loaded 50 100 150 200 HNO3 H 2 PO 4 /C molar percent, %
100,000 80,000 CO2 Concentration, ppm 60,000 40,000 20,000 20ml 10ml 5ml 0 0 10 20 30 40 50 60 70 Time, min 120 100 Desorption percent of HCO 3 ion, % 80 60 40 NH4H2PO4 50% NH4H2PO4 100% 20 NH4H2PO4 150% NH4H2PO4 200% HNO3 1mol 0 0 10 20 30 40 50 60 70 Time (min)
120 Desorption percent of HCO 3 ion, % 100 80 60 40 20 0 0 10 20 30 40 50 60 70 Time, min NH4H2PO4 50% NH4H2PO4 100% NH4H2PO4 150% NH4H2PO4 200% HNO3 1mol C-14 amount of IRN78 resin, mg-c/g-irn78 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 : C-14 amount : HCO3 amount 0 100 200 300 400 500 600 Average activity per IRN-78 spent resin(ci/m 3 -IRN78)
80,000 70,000 60,000 CO 2 conc., ppm 50,000 40,000 30,000 20,000 10,000 H3PO4 2.25 mmol H3PO4 4.5 mmol H3PO4 6.75 mmol H3PO4 9 mmol HNO3 1mol 0 0 10 20 30 40 50 60 70 Time(min)
120 g g 100 Desorption percent of HCO 3 ion, % 80 60 40 20 H3PO4 50% H3PO4 100% H3PO4 150% H3PO4 200% HNO3 1mol 0 0 10 20 30 40 50 60 70 Time (min)
ph >11 Cathode High ph ph 7 f feeding = f rex, out f ph ad in f rex, in ph < 5 f ph ad out f rex, out Adjusted ph (ph<3) Anode Feeding tank ph adjust tank
Na + Na + HCO - 3 (A) - Na + HCO - 3 H 2 O H + 1/2 H 2 OH - Na + Na + OH - CEM Na + Na + 1/2H 2 O 1/4 O 2 HCO - 3 HCO - 3 Na + + Na + H + H + (B) - 2Na + 2HCO - Na + 3 2H 2 O 2H + H 2 Na + Na + 2Na + OH - 2Na + 2HCO - 3 2Na + 2Na 2OH - H 2 O 1/2 O 2 CEM HCO - 3 2Na + OH - 2H + H + 2HCO - 3 Na + OH - 2Na + 2Na + + J i = - D i dci dx n if - DiC RT i dφ dx
Anodic cell Cathodic cell Mesh type electrode Flow path in cell Interior flow path of cell frame Membrane
14 12 Cathode soltion ph 18 16 Solution p H 10 8 6 4 2 0 Soltion Temperature Sampl 1 Sampl 2 Sampl 3 14 12 10 8 6 4 Anode soltion ph 2 0 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 Time(min) Solution Tem p.( o C )
14 12 10 4.0V, 10V, 20rpm 0.1N-NaHCO 3 + 0.1N-NaNO 3 음극방 Solution ph 8 6 washing 양극방 4 2 4V 10V 0 0:00 1:00 2:00 3:00 4:00 5:00 6:00 Time, hr
14 12 Solution ph 10 8 6 6.0V, 20rpm, 0.1N-NaHCO 3 + 0.1N-NaNO 3 음극방 양극방 4 2 0 0:00 0:30 1:00 1:30 2:00 Time, hr 14 12 10 8.0V, 20rpm(3ml/min) 0.1N-NaNO 3 +0.1N-NaHCO 3 Solution ph 8 6 음극방 양극방 4 2 0 0:00 0:30 1:00 1:30 2:00 Time, hr
14 12 Solution ph 10 8 6 8.0V, 0.1N-NaHCO3 + 0.1N-NaNO3 음극방 양극방 4 3 ml/min 6 ml/min 9 ml/min 2 0 0:00 1:00 2:00 3:00 4:00 Time, hr
14 start 12 10 Solution ph 8 6 1st 2nd 4 washing 7.5V, 20rpm, 5g(10%) 0.1N-NaNO3 음극방 양극방 2 0 0:00 2:00 4:00 6:00 8:00 Time, hr
14 12 10 Solution ph 8 6 4 7.5V, 20rpm, 5, 10g(10%) 0.1N-NaNO3 음극방 -10 g 음극방 -5 g 양극방 -10 g 양극방 - 5 g 2 0 0:00 1:00 2:00 3:00 4:00 5:00 Time, hr 30,000 5 g 10 g 25,000 20,000 CO 2 conc., ppm 15,000 10,000 5,000 0 0 10 20 30 40 50 60 Time(min)
용액내 이온몰수 용액내금속핵종몰수 이온교환 용액내양이온양 수지의이온교환용량
340 60 320 300 280 260 240 220 200 180 160 140 120 100 080 060 040 020 000 NW W SW 60 N C S NE E SE 60 Units : cm
1200 1100 1000 900 C-14 Conc.(Bq/ml) 800 700 600 500 400 300 : 1 단 -H3PO4 : 2 단 -H3PO4 : 1 단 -NH4H2PO4 : 2 단 -NH4H2PO4 200 100 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 Time(min)
Cumulative total C-14 amount (mci x 10-2 ) 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 Time(min) : 1 단 -H3PO4 : 2 단 -H3PO4 : 1 단 -NH4H2PO4 : 2 단 -NH4H2PO4
70000 65000 60000 C-14 Conc.(Bq/ml) 55000 50000 45000 40000 35000 30000 25000 : SR200-NaOH 1 단 : SR100-NaOH 1 단 : SRB-NaOH 1 단 : SR200-NaOH 2 단 : SR100-NaOH 2 단 : SRB-NaOH 2 단 20000 15000 10000 5000 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 Time(min)
90.0 Cumulative total C-14 amount (mci x 10-2 ) 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 : SR200-NaOH 1 단 : SR100-NaOH 1 단 : SRB-NaOH 1 단 : SR200-NaOH 2 단 : SR100-NaOH 2 단 : SRB-NaOH 2 단 0.0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 Time(min)
5.0 Generation amount of adsorbent(kg-media) 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Sodalime 0 25 50 75 100 125 150 175 200 225 250 Removal Capacity of Media(g-CO 2 /Kg-media) Volume Reduction % 40 30 20 10 Sodalime 0 0 25 50 75 100 125 150 175 200 225 250 275 300 325 350 Removal Capacity of Media(g-CO2/Kg-media)
Mixing Tank CO2 gas Adsorbent G C N2 CO 2 N2 Adsorbent Analysis System (Data Acquisition) Humidifier Heating mantle
Mixing Tank N2 CO 2 N2 Humidifier Analysis System (Data Acquisition) G C
1.0 0.9 0.8 : Soda lime-0.25g : Ca(OH)2-0.25g :LiOH.H2O-0.25g 0.7 0.6 C/Co 0.5 0.4 0.3 0.2 0.1 0.0 0 20 40 60 80 100 120 140 160 Time(min)
1.0 0.9 0.8 : Soda lime-0.25g : Ca(OH)2-0.25g :LiOH.H2O-0.25g 0.7 0.6 C/Co 0.5 0.4 0.3 0.2 0.1 0.0 0 20 40 60 80 100 120 140 160 Time(min)
1.2 1.1 1.0 0.9 :Soda lime-0.1g : Ca(OH)2-0.1g : LiOH.H2O-0.1g No material 0.8 0.7 C/Co 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 30 60 90 120 150 180 210 240 Time(min)
C/Co 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 : Soda lime-0.25g : Ca(OH)2-0.25g :LiOH.H2O-0.25g 0 30 60 90 120 150 180 210 240 Time(min)
1.0 0.9 0.8 0.7 0.6 C/Co 0.5 0.4 0.3 0.2 Soda lime-0.2g-30000ppm : Soda lime-0.25g-52000ppm Ca(OH)2-0.2g-30000ppm-1st Ca(OH)2-0.2g-30000ppm-2nd : Ca(OH)2-0.25g-52000ppm :LiOH.H2O-0.25g-52000ppm LiOH,H2O-0.2g-30000ppm 0.1 0.0 0 30 60 90 120 150 180 210 240 Time(min)
1.5 1.4 1.3 1.2 1.1 1.0 Soda lime Li(OH) 2.948 kpa Adsorption Capacity : 3.65 mmol/g Carrier : 129 ml/min Evapor : 36 ml/min Sobate : 4.941 ml/min Total flow rate : 169.941 ml/min 0.9 C/Co 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 10 20 30 40 50 60 70 80 90 100 Time, min
1.2 1.1 1.0 0.9 0.8 N 2 (Carrier) : 600 ml/min CO 2 (Evapor) : 70 ml/min Conc., : 13140 ppm(co 2 ) Conc., test C/Co 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 N 2 (Carrier) : 600 ml/min CO 2 (Evapor) : 35 ml/min Conc., : 7046 ppm(co 2 ) N 2 (Carrier) : 600 ml/min CO 2 (Evapor) : 17.5 ml/min Conc., : 3579 ppm(co 2 ) N 2 (Carrier) : 600 ml/min CO 2 (Evapor) : 8.75 ml/min Conc., : 1815 ppm(co 2 ) N 2 (Carrier) : 600 ml/min CO 2 (Evapor) : 4.375 ml/min Conc., : 893 ppm(co 2 ) 0 60 120 180 240 300 360 420 480 540 Time, min
1.2 1.1 1.0 0.9 0.8 Variable of conc., Continue flow variable of Conc., Conc., : 13140 ~ 446 ppm(co 2 ) Soda lime continue flow N 2 (Carrier) : 600 ml/min CO 2 (Evapor) : 24.7 ml/min Conc., : 4216 ppm(co 2 ) 0.7 C/Co 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 100 200 300 400 500 600 700 800 Time, min
1 μm이하 1 μm이상
adsorbent X500 X1000 X3000
adsorbent X500 X1000 X3000
adsorbent 3-4-4X50 X1000 X3000
adsorbent X500 X1000 X3000
1.1 1 0.9 0.8 Ca(OH)2 soda lime bead PS Gauze LiOH C/C0 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 20 40 60 80 100 120 140 160 180 200 220 Time(min)
1.6 1.4 1.2 5000ppm-4.2cm-0610 5000ppm-4.2cm-0602 5000ppm-4.2cm-0603 10000ppm-4.2cm-0607 5000ppm-5.5cm-0616( 동결건조 ) 5000ppm-7.5cm-0623( 비동결-스틱 ) N 2 (Carrier) : 2000 ml/min CO 2 (Evapor) : 10 ml/min Conc., : 5503 ppm(co 2 ) Column length : 4 cm Weight : 20 g 1.0 C/Co 0.8 0.6 0.4 0.2 0.0 0 60 120 180 240 300 360 420 480 540 600 Time (min)
C/Co 1.0 0.9 0.8 0.7 0.6 0.5 0.4 : Soda lime(old)-0.25g : Ca(OH)2-0.25g :LiOH.H2O-0.25g New soda lime -0.25g PHS(P)-0.25g Old soda lime-0.25g C type C pellet - 0.25g M type D pellet - 0.2447g Original type P pellet - 0.25g M type M1 pellet - 0.25g M type M2 pellet - 0.2432g M type M3 pellet - 0.25g M type M4 pellet - 0.25g 0.3 0.2 0.1 0.0 0 30 60 90 120 150 180 210 240 Time(min)
CO2 SV MFC N2 SV Air SV MFC N2 Air 탈착용액 폐수지 / 활성탄 / 제올라이트폐액 가열공정 2-2 로 용액 공정 5 수분 trap VENT 폐수지 다단스크린 공정 1 탈착용액 수분 trap Gas Chromatograph 탈착용액 스크린 폐수지 폐액 폐수지 공정 2-1 폐수지 펌프 N2 기체 공정 3 공정 4 탈착용액 혼합용액 폐수지회수탱크 탈착용액회수탱크 탈착용액저장탱크 (3 개 ) 탈착용액 탈착용액회수탱크 산용액저장탱크 (2 개 ) 슬러지혼합용액회수탱크 NaOH+ Ca(OH)2 혼합저장탱크혼합용액 혼합용액회수탱크
soltion GAS SAMPLING V.T N2 GAS RESIN 기체순환용 PUMP 공정 1 공정 2-1 공정 2-2 공정 2-3 ( 공정 1) 공정 2-4 정량 PUMP GAS SAMPLING 습도조절기 HEATER 습도조절기 GAS 순환용 PUMP CLAMP UNION 한국원자력연구소
기체순환용펌프 Gas Sampling (NaOH scrubbing) Check Valve 공정 2 공정 2 N2 MFC 폐수지 습도조절탱크 공정 1 ( 컬럼형 ) 탈착용액 폐수지회수탱크탈착용액회수탱크
플랜지 4 플랜지 3 플랜지 3 홈삽입용 ( 홈에가스켓끼운후압착 - 기체 leak 방지용 ) 2 Pipe (OD=50.8mm) (ID =46.8mm) 내부바스켓 ( 흡착제충진용 ) 600 하단스크린 ( 바스켓하단에위치 ) 플랜지 2 플랜지 1 플랜지 2 홈삽입용 ( 홈에가스켓끼운후압착 - 기체 leak 방지용 )
1 0.8 0.6 C/Co 0.4 0.2 0 R.H=15% R.H=55% R.H=85% simulated 0 300 600 900 1200 Time, min
1 0.8 0.6 C/Co 0.4 550ppm 0.2 0 1000ppm 2000ppm simulated 0 300 600 900 1200 Time, min
C A
C A B B A C
A C B A B C
Ca phase B A C