BIIWP-B 37 Bimolecular association 152 Bimolecular reaction 143

INDEX A Absorption of C 0 laser lines 139,140 Absorption coefficients, C O laser-DBr 141 Acids, mineral 156 Addition reactions, deuterium isotope separation via vibrationally enhanced deuterium halide olefin 134 Adduct production, classification of .. 156 Adsorption 5 AECL—Sulzer amine process 53 Algae, presence of mud and organic .. 168 Alumina, catalyst pellets of platinum on 95 Alumina particles, presence of 169 Amine-hydrogen exchange 8, 40 bithermal enrichment using 54 Amine-hydrogen process 11, 17, 40, 53, 63 Amine, steam hydrogen 19 Amino groups of methylamine 47 Ammonia advantages of methylamine over .... 40 catalyst 90 cracking 78 exchange, hydrogen8-10, 40, 77 and hydrogen, isotopic exchange between liquid 71 hydrogen process 15,53,58,80 plant 63,67,89 deuterium concentrations in an .. 64 link-up with the 62 synthesis 88 system 43 Argentina 77 Arrhenius parameters for H X addition 136 Atmosphere, H S emissions to 34

Downloaded by KAOHSIUNG MEDICAL UNIV on June 9, 2018 | https://pubs.acs.org Publication Date: June 1, 1978 | doi: 10.1021/bk-1978-0068.ix001

1 2

1 6

2

Β Back-end of the separation cycle Bed contactor, packed Bed reactor, trickle BHWP aerial view II,S incidents reliability safety performance training section BHWP-A deuterium production reliability of

145 61 99 32 32 36 33 37 38 29 35

BIIWP-B 37 Bimolecular association 152 Bimolecular reaction 143 Biological 5 Bithermal enrichment using amine-hydrogen exchange 54 enrichment fluids 60 enrichment process 54—56 exchange processes 78 hydrogen-water— H W P 118 process 10-13,121 systems 57 Bruce heavy water plant 27, 28 "Bubbler," ethylene glycol 174

Canada 1, 2, 53, 77, 78, 93, 110 Canada Deuterium Uranium power reactor program ( C A N D U ) 2 C A N D U reactors 27-30, 122, 163 Capacity factors 35 Carbamate 42 Carbon monoxide absorption coefficients 141 Carbon-Teflon catalyst, platinum 121 Catalyst(s) 44 activity, effect of hydrogen gas flow rate and temperature on 102 ammonia 90 concentration 17 development 95 effect of platinum metal surface area on the activity of the 101 efficiency of 169 Engelhard 96 for isotopic exchange between hydrogen and liquid water, novel 93 metal hydrophobic 171 pellets of platinum on alumina 95 performance 98, 104, 105 platinum carbon-Teflon catalyst .... 121 solubility of the 72 thermal stability of the 72 Catalytic detritiation of water 171 Catalytic exchange 171-173 between heavy water vapor and deuterium gas 164

177

Rae; Separation of Hydrogen Isotopes ACS Symposium Series; American Chemical Society: Washington, DC, 1978.

SEPARATION O F HYDROGEN ISOTOPES


178 Catalytic exchange process, com bined electrolysis ( C E C E ) 110 Cesium methylamide 44 Chalk River 40 Chemical exchange 5—8 combined electrolysis and ( C E C E ) 2 processes 1, 14 China 2 Cold principle, hot— 78 Column efficiency 100 Combined electrolysis and chemical exchange ( C E C E ) 2, 110, 175 arrangement, monothermal 17 HWP 112 applications of the 121 block diagram of the 113 demonstration unit laboratory .... 115 synergistic effects of the 119, 120 process 22,171 T R P , applications of the 121 Commissioning progress report 37 Components, cost 127,128 Concentration in an ammonia plant, deuterium .... 64 catalyst 17 in the electrolysis cell water circuit, deuterium 116 Condensate and synthesis gas, deuterium recycle from 66 Conditions, determination of working 74 Coefficients, mass transfer 16 Contacting devices, cold 60 Contactons) development 40 ejector 61, 62 packed bed 61 sieve tray 61 special cold 59 Countercurrent crystallization systems 7 Crystallization 5 systems, countercurrent 7 water 20 Cycle, back-end of the separation 145 D D.O in C A N D U reactors, recovery of tritium from the and peak power production, simultaneous plant, small upgrading of Decomposition, thermal Design data Detritiation of water, catalytic Deuterium concentrations in an ammonia plant

Deuterium (continued) concentration in the electrolysis cell water circuit 116 enrichment system 65 exchange between hydrogen and liquid water Ill between the water vapor and liquid water Ill equilibria 56 properties 54, 58 rate 14,42 gas, catalytic exchange between heavy water vapor and 164 halide, vibrationally excited 142 -to-hydrogen ratio 3,10 isotope separation via vibrationally enhanced deuterium halide olefin addition reactions 134 plant 82 production, B H W P - A 29 recovery 117 recycle from condensate and synthesis gas 66 separation methods, hydrogen 1 uranium power reactor program, Canada ( C A N D U ) 2 Development, reliability and manpower 28 Diagram, enthalpy-temperature 85, 86 Diagram, McCabe-Thiele 11, 83, 84 Diffusion 5 hydrogen 20 D i e t h y l a m i d e , potassium 44 Dimethylformamidide, lithium 47 Dimethylformamidide ( P D M F A ) , potassium 42, 43 Distillation 5-9 component costs in heavy water .... 128 heavy water 126 system, elements of a 128 systems—physical 126 water 20 Draft of a factory, preliminary 72 Dunham isotope relations 138

Ε 122 122 122 122 43 164 171 64

Effects of the C E C E - H W P , synergistic 119, 120 Effects, synergistic 117 Ejector contactor 61, 62 Electrolysis 5, 172,173 catalytic exchange process, combined ( C E C E ) 2, 110 cell water circuit, deuterium concentration in the 116 Elimination of H X , unimolecular 136


179

INDEX

Emissions to atmosphere, IL.S 34 Emissions to water, H »S 34 Energy consumption 20 Energy diagram, potential 154 Engineering problems 87 Enrichment system 81 Enthalpy-temperature diagram 85, 86 Environment, care of the 28, 34 Environmental performance 36 Equilibrium constant, perturbed 153 isotope effect 110 perturbed 161 statistical 152 Ethylene 142 additions, H F 156 pairs, H F 195 Exchange amine-hydrogen 8,40 ammonia-hydrogen 8-10, 40 between heavy water vapor and deutrium gas, catalytic 164 between hydrogen and liquid water, deuterium Ill between hydrogen and liquid water, novel catalysts for isotopic 93 between hydrogen and methyl amine, isotopic 71 between liquid ammonia and hydrogen, isotopic 71 between water and hydrogen sulfide, isotopic 71 between the water vapor and liquid water, deuterium 111 bithermal enrichment using amine-hydrogen 54 catalytic 171-173 chemical 5-8 combined electrolysis and chemical (CECE) 2 efficiencies, isotopic 59 equilibria, deuterium 56 hydrogen-ammonia 77 of HC1 with natural water, isotopic 146 isotope 79 kinetics 71 process ( es) bithermal 78 chemical 1, 14 combined electrolysis catalytic (CECE) 110 design of the H C l - H . O 148 dual temperature 78 features of hydrogen-water 106 hydrogen sulfide-water 31 water 28 properties, deuterium 54, 58 rate, deuterium 14,42


L

Exchange (continued) rate, effect of lithium-potassium mole ratio on reaction, hydrogen halide-water ... reaction, mechanism of the water-hydrogen water-hydrogen sulfide water-vapor—hydrogen Excitation, effectiveness of vibrational Extraction plant, operating experience with the tritium hydrogen

46 146 104 2,8 8 2 144 163

F Factors, capacity 35 Factory, preliminary draft of a 72 Fissure phenomena 169 Flash evaporation 114 Fluoroethylenes 156 Fragmentation 152 France 1,2,10,40,53,163 G Gas catalytic exchange between heavy water vapor and deuterium .... 164 deuterium recycle from condensate and synthesis 66 fed bithermal process 11 flow rate and temperature on catalyst activity, effect of hydrogen 102 reactor cover 169 supplement, electrolytic H as natural 123 synthesis 62, 63, 85 Gaseous effluent streams, removal of tritium from 171 Germany 1, 163 Girdler-Sulfide ( G S ) plants, final enrichment stage for 122 GS process 1-10,14,17-22, 29, 55-58, 93 Glace Bay heavy water plant 3, 4 Glycol 'limbbler," ethylene 174 Gravitational 5 Great Britain 163 Gulf process 20 2

H

H C l - Η . , Ο exchange process, design of the 148 H F addition 156, 157 HF-ethylene pairs 159 H S emissions 34 H S incidents 31 H X addition, Arrhenius parameters for 136, 137 H X , unimolecular elimination of 136 2 2



180


Halide-olefin addition reactions .134, 135 Halide, vibrationally excited deuterium 142 Heavy water plant applications of the C E C E 121 bithermal Η - , - Η , Ο 118 block diagram of the C E C E 113 Bruce 27,28 CECE 112 demonstration unit, laboratory CECE 115 design of 80 Glace Bay 3, 4 model of a 91 synergistic effects of the CECE 119,120 processes 1 production 2 from synthesis gas, U H D E process for the recovery of 77 Henry's Law 14, 15 Hot-cold principle 78 Hydrates of perfluoroacetone, gaseous 158 Hydrates of trifluoroacetaldehyde, gaseous 158 Hydrogen 7, 42, 43 amine process 40 amine, steam19 ammonia exchange 77 ammonia systems 15 -based processes 14, 18 deuterium separation methods 1 deuterium-tritium separations based on laser augmented A - f B = C reactions proposed 152 diffusion 20 exchange amine 8, 40 ammonia 8-10. 40 bithermal enrichment using amine54 water 2, 8 extraction plant, operating experi ence with the tritium and 163 gas flow rate and temperature on catalyst activity, effect of 102 halide-olefin addition reactions 135 halide-water exchange reactions .... 146 isotopic exchange between liquid ammonia and 71 and liquid water, deuterium exchange between Ill and liquid water, novel catalysts for isotopic exchange between 93 and methylamine, isotopic exchange between 71 monomethylamine system ( M M A ) 71

Hydrogen (continued) as natural gas supplement, electrolytic 123 on P L M A solutions, effect of 45 on P M A solutions, effect of 45 process amine 11, 17,18, 53-58, 63-67 ammonia 53, 58 methane 20,21 steam 18 water 1 ratio, deuterium-to3, 10 solubility of 72 sufide dual temperature 28 exchange, water 8 isotope exchange between water and 71 process, water 1 system 77 water 40 toxicologic^ properties of 31 water exchange process 31 water system 94 system, ammonia80 system, water14, 15, 80, 94 transfer, steam 20 water exchange 77 water-HWP, bithermal 118 water processes, advantages of 107 Hydrophobic catalyst, metal 171

Ice-water systems 7 Impurities, oxygen-bearing 90 Incidents, I L S 31 India 1, 2, 10, 40, 53, 77 IR photons 134 Institute, Laue-Langevin 163 Isotope effect, equilibrium 110 enrichment 66 exchange 79 of HC1 with natural water 146 between hydrogen and liquid water, novel catalysts for 93 between hydrogen and methylamine 71 between liquid ammonia and hydrogen 71 between water and hydrogen sulfide 71 relations, Dunham 138 separation, principles of 78 separation via vibrationally enhanced deuterium halide olefin addition reactions 134 Italy 1


181

INDEX

Κ Kinetics, exchange

71

Monothermal process M u d and organic algae, presence of .. Ν

L Laboratory unit, results from 114 Lake Huron 28 Laser augmented A + Β = C reactions, proposed H / D / T separation based on 152 lines, absorption of C O 139, 140 methods 134 photolysis 159 Laue-Langevin Institute 163 Law, Henry's 14,15 Cithium 47 dimethylformamidide 47 methylamide 44 potassium 44 solubility of potassium 49 potassium mole ratio on exchange rate, effect of 46


1 2

9-11 168

Natural gas supplement, electrolytic H as North America Norway 2

123 28 2,8

Ο

i e

M Manpower development, reliability and 28,35 McCabe-Thiele diagrams 11,12, 83, 84 Metal hydrophobic catalyst 171 surface area on the activity of the catalyst, effect of platinum 101 transfer rate constant dependence on platinum 103 Methane 7 -hydrogen process 20 Methyl groups of methylamine 47 Methylamide cesium 44 lithium 44 potassium-lithium 44 sodium 44 solubility of 48, 49 solution, potassium 42 Methylamine 42-44, 65 amino groups of 47 over ammonia, advantages of 40 isotopic exchange between hydrogen and 71 methyl groups of 47 Methylenimine 43 N-Methylformamide, potassium 42 Mineral acids 156 Molecular sieve, displacement of the 168 Monomethylamine system, hydrogen (MMA) 71 Monothermal C E C E arrangement .... 17

Olefin addition reactions, hydrogen halide 134,135 Olefins, Arrhenius parameters for H X addition to 137 Operating experience 167 Operation, difficulties encountered during 168 Operation, principle of 164 Oxygen-bearing impurities 90 Ρ

Packed bed contactor 61 Packing(s) earning power of two experimental 132 experimental 127 performance—experimental 130 Sulzer 164 Pakistan 77 Perfluoroacetone 160 Photochemical, selective 5 Photolysis, laser 159 Photons, ir 134 Pilot plant tests 72 Plant(s) ammonia 63-67, 89 Bruce heavy water 28 conception, 400 ton 127 design of heavy water 80 deuterium 82 concentration in an ammonia 64 final enrichment stage for GS 122 Glace Bay heavy water 3 heavy water 2 link-up with the ammonia 62 model of a heavy water 91 operating experience with the tritium and hydrogen extraction 163 operation of the 87 packing module, parallel 131 performance, Bruce heavy water .... 27 polyfluoroethylene production 158 safety precautions 164 small DX> 122 start-up of the 167 400-ton 129


182

SEPARATION O F HYDROGEN

Platinum on alumina, catalyst pellets of 95 carbon-Teflon catalyst 121 metal surface area on the activity of the catalyst, effect of 101 metal, transfer rate constant dependence on 103 PLMA 44-50 Polyfluoroethylene production plant.. 158 Potassium amide ( K N H ) 80 Potassium dimethylamide 44 Potassium dimethylformamidide (PDMFA) 42,43 Potassium hydride 43 Potassium-lithium methylamide 44, 49 Potassium methylamide ( P M A ) 40-47 Potassium N-methylformamide 42 Potassium mole ratio on exchange rate, effect of lithium 46 Potential energy diagram 154 Power of experimental packings 132 production, simultaneous D 0 and peak 122 reactor program, Canada deuterium uranium ( C A N D U ) 2 Principle, hot-cold 78 Problems, engineering 87 Process (es) advantages of hydrogen water 107 amine-hydrogen .11,17,18, 53-58, 63-67 basic description of the 112 bithermal 10-13, 121 enrichment 56 exchange 78 CECE 22, 171 characteristics, general 3 chemical exchange 1,14 chemistry 40-42 comparison 20-22 design 40,67 GS 3 of the H C 1 - H 0 exchange 148 development 41 dual temperature exchange 78 economy of the 74 evaluation 23,24 features of hydrogen-water exchange 106 gas-fed bithermal 11 Girdler-Sulfide ( GS ) 1, 5-10,17-22, 29, 55-59,93 gulf 20 heavy water 1 hydrogen-amine 40 hydrogen-based 14,18 hydrogen sulfide—water exchange 31 methane-hydrogen 20, 21


2

2

2

ISOTOPES

Process ( es ) ( continued ) monothermal 10,11 production 28 for the recovery of heavy water from synthesis gas, U H D E .. 77 steam-hydrogen 18 transfer 18 types of 5 water exchange 28 water—hydrogen 1 Production heavy water 2 process 28 rate 35 unit diagram 73 Program, Canada deuterium uranium power reactor ( C A N D U ) 2 Properties, deuterium exchange 54 Properties of hydrogen sulfide, toxicological 31 Purification system 80

Q Quenching, vibrational

142

R Rate(s) constant dependence on platinum metal, transfer 103 deuterium exchange 14, 42 effect of lithium—potassium mole ratio on exchange 46 expression, Arrhenius 136 of methylamide solutions, thermolysis 50 production 35 and temperature on catalyst activity, effect of hydrogen gas flow 102 Ratio, deuterium-to-hydrogen 3, 10 Reaction(s) bimolecular 143 deuterium isotope separation via vibrationally enhanced deuterium halide olefin addition .... 134 hydrogen halide—water exchange . . . 146 mechanism of the exchange 104 proposed H / D / T separations based on laser augmented A + B = C 152 Reactor C A N D U type 27-30, 163 cover gas 169 high flux 163 program ( C A N D U ) 2 trickle bed 99 Recovery of heavy water from synthesis gas, U H D E process for the .... 77


183

INDEX

Reliability of B H W P - A Reliability and manpower development Results, preliminary Russia

35 28 172 2


S Safety, employee 28—31 Safety performance, B H W P 33 Safety precautions, plant 167 Selective photochemical 5 Separation(s) based on laser augmented A -f- Β = C reactions, proposed H/D/T 152 cycle, back-end of the 145 factors 7-13, 20, 57, 65, 71, 93 94 methods, hydrogen-deuterium 1 Sieve displacement of the molecular 168 tray(s) 87 contactor 61 operation 16 Silicone-treated pellets 95 Sodium methylamide 44 Solubility 44 of the catalyst 72 of hydrogen 72 Stability of the catalyst, thermal 72 Statistical equilibrium 152 Steady state 154 Steam-hydrogen-amine 19 Steam-hydrogen process 18 Steam-hydrogen transfer 20 Stripping system 81—83 Sulfide dual temperature hydrogen 28 process, Girdler-Sulfide (GS) 1 process, water-hydrogen 1 system, hydrogen 77 system, water-hydrogen 40 toxicological properties of hydrogen 31 water exchange process, hydrogen .. 31 Sulzer packings 164 Surfaoe area on the activity of the catalyst, effect of platinum metal 101 Sweden 1 Switzerland 1, 41, 163 Synergistic effects 117-120 Synthesis, ammonia 88 Synthesis gas 62r-67, 80, 85, 90 deuterium recycle from condensate and 66 U H D E process for the recovery of heavy water from 77 System ammonia hydrogen 80 deuterium enrichment 65

System (continued) elements of a distillation enrichment GS hydrogen—monomethylamine (MMA) hydrogen—sulfide hydrogen sulfide-water hydrogen-water physical, distillation purification stripping transfer water-hydrogen water-hydrogen sulfide

128 81 11 71 77 94 94 126 80 81-83 81 80 40

Τ

;

Teflon catalyst, platinum carbon 121 Temperature on catalyst activity, effect of hydrogen gas flow rate and .... 102 diagram, enthalpy 85, 86 dual 31 exchange processes, dual 78 hydrogen sulfide, dual 28 Tetrahydrofurane, addition of H F to 158 Thermal decomposition 43 Thermal stability of the catalyst 72 Thermodynamic and kinetic relations 152 Thermolysis rate of methylamide solutions 50 Thiele diagrams, M c C a b e 11, 83, 84 Thylene glycol "bubbler" 174 Toxicological properties of hydrogen sulfide 31 Training section, B H W P 37 Transfer coefficients, mass 16 column 83 processes 18 rate constant dependence on platinum metal 103 steam—hydrogen 20 system 81 Trays, sieve 16, 87 Trickle bed reactor 99 Trifluoroacetaldehyde 160 Trimethylamine ( T M A ) , adjuvant effect of 72 Tritium from the D 0 in C A N D U reactors, recovery of 122 from gaseous effluent streams, removal of 171 and hydrogen extraction plant, operating experience with the . 163 recovery from light water 122 T R P , applications of the C E C E 121 2


184


u U H D E process for the recovery of heavy water from synthesis gas .. 77 United Kingdom 1 Uranium power reactor program, Canada deuterium ( C A N D U ) .... 2 USA 2,77 USSR 2

Water (continued) exchange hydrogen— 77 process 28 design of the H C 1 148 features of hydrogen106 hydrogen sulfide31 reactions, hydrogen halide146 H W P , bithermal H 118 H S emissions to 34 hydrogen 14, 15 exchange 2, 8 process 1 sulfide exchange 1,8,71 sulfide system 40, 94 system 80, 94 isotopic exchange of HC1 with natural 146 novel catalysts for isotopic exchange between hydrogen and liquid .. 93 processes, advantages of hydrogen 107 system, ice 7 tritium recovery from light 122 vapor and deuterium gas, catalytic exchange between heavy 164 vapor-hydrogen exchange 2 vapor and liquid water, deuterium exchange between the Ill Working conditions, determination of 74 2


V Vapor-hydrogen exchange, water Vibrational excitation, effectiveness of Vibrational quenching Vibrationally enhanced deuterium halide olefin addition reactions, deuterium isotope separation via

2

2 144 142

134

W

Water catalytic detritiation of circuit, deuterium concentration in the electrolysis cell crystallization deuterium exchange between hydrogen and liquid distillation component costs in heavy heavy

171 116 20 Ill 20 128 126


BIIWP-B 37 Bimolecular association 152 Bimolecular reaction 143

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