EP0006329A1 - Encapsulating wastes - Google Patents
Encapsulating wastes Download PDFInfo
- Publication number
- EP0006329A1 EP0006329A1 EP79301080A EP79301080A EP0006329A1 EP 0006329 A1 EP0006329 A1 EP 0006329A1 EP 79301080 A EP79301080 A EP 79301080A EP 79301080 A EP79301080 A EP 79301080A EP 0006329 A1 EP0006329 A1 EP 0006329A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- waste
- process according
- mixture
- initiator
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 239000000945 filler Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000002901 radioactive waste Substances 0.000 claims abstract description 11
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 35
- 238000005538 encapsulation Methods 0.000 claims description 23
- 239000003456 ion exchange resin Substances 0.000 claims description 14
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 13
- 239000004568 cement Substances 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011398 Portland cement Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002920 hazardous waste Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000011396 hydraulic cement Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract 1
- 229920001225 polyester resin Polymers 0.000 description 13
- 239000004645 polyester resin Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000004160 Ammonium persulphate Substances 0.000 description 6
- 235000019395 ammonium persulphate Nutrition 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000010881 fly ash Substances 0.000 description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 description 5
- 239000000499 gel Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000004159 Potassium persulphate Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 231100001261 hazardous Toxicity 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000010812 mixed waste Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LFMQNMXVVXHZCC-UHFFFAOYSA-N 1,3-benzothiazol-2-yl n,n-diethylcarbamodithioate Chemical compound C1=CC=C2SC(SC(=S)N(CC)CC)=NC2=C1 LFMQNMXVVXHZCC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- TVFDJXOCXUVLDH-RNFDNDRNSA-N cesium-137 Chemical compound [137Cs] TVFDJXOCXUVLDH-RNFDNDRNSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- RMGVZKRVHHSUIM-UHFFFAOYSA-L dithionate(2-) Chemical compound [O-]S(=O)(=O)S([O-])(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
- G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
- G21F9/165—Cement or cement-like matrix
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
- G21F9/167—Processing by fixation in stable solid media in polymeric matrix, e.g. resins, tars
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
- G21F9/304—Cement or cement-like matrix
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/307—Processing by fixation in stable solid media in polymeric matrix, e.g. resins, tars
Definitions
- the present invention relates to a process for encapsulating hazardous wastes. It is known to encapsulate various hazardous wastes by incorporating the waste into a fluid material which is then allowed to set to a solid so as to bind the waste. This enables the waste to be handled more easily and prevents hazardous components of the waste escaping to the environment. Thus it is known from British patent specification 1 116 319 to incorporate radio active wastes in bitumen, cement or a polymerisable resin. If bitumen is used the waste must be subjected to the elevated temperatures used to melt the bitumen. This is not always desirable and the requirement for a heating step leads to additional complications. The use of bitumen is not very suitable for wet wastes because the elevated temperature will lead to the evolution of steam which may carry with it hazardous components of the waste and because bitumen is hydrophobic.
- cement as an encapsulating agent is not very satisfactory as the time required for the cement to set is usually undesirably long.
- the resulting product is friable and does not retain its structural integrity.
- British patent specification 938 211 discloses a process for solidifying or encapsulating an aqueous radio active waste by mixing the waste with a finely divided hydraulically setting absorption material e.g. Portland Cement.
- a self-hardening synthetic or casting resin e.g. "Palatal P6" sold by BASF.
- Palatal P6 a self-hardening synthetic or casting resin
- This is a mixture of unsaturated polyester and styrene and as is well known in the polyester art such resins are cured by the action of conventional organic peroxide curing agents.
- the process is an impregnation process and is clearly only applicable to a block which has set and is free from water as otherwise the resin will not penetrate the block. Pressure is required for the impregnation process and it will be difficult to obtain satisfactory penetration of the resin into the core of the block.
- the speed of the encapsulation process is dependent on the setting time of the hydraulic filler. The specification mentions setting times of 2 days. The process is thus not a very satisfactory method of encapsulating wastes.
- British patent specification 1 353 121 discloses the encapsulation of a radio active waste in the form of a dry powder using a mixture of (1) an unsaturated polyester prepared from maleic and phthalic anhydride reacted with propylene glycol and (2) a copolymerisable monomer e.g. styrene. Polymerisation is initiated by an initiator such as methyl ethyl ketone peroxide.
- British patent specification 1 479 150 also discloses the encapsulation of wet wastes (specifically radio active ion exchange resins) using an unsaturated polyester resin.
- the specification does not specifically state that a WEP was used but this would be apparent to a person skilled in the art in view of the reference to a methyl ethyl ketone/cobalt naphthenate initiator/activator system.
- a WEP type polyester resin formulation which is suitable for use in small scale tests may be completely unsatisfactory when attempts are made to cast large blocks.
- a formulation which is suitable for use with a waste with a given water content may be unsatisfactory when used with a waste with a different water content.
- the process for encapsulating a hazardous waste by allowing to set an encapsulation mixture containing an unsaturated polyester an ethylenically unsaturated monomer copolymerisable with said polyester, and an initiator,which mixture incorporates the hazardous waste, is characterised in that the mixture contains a hydraulic filler, the initiator is an initiator which is activated by aqueous alkaline conditions and setting takes place under aqueous alkaline conditions.
- the process of the present invention may be applied to a variety of wastes providing that they do not interfere with setting reaction to any substantial extent.
- the process may be applied to wastes containing toxic heavy metals or mercury, or organochlorine compounds. It is particularly useful for the encapsulation of radioactive wastes.
- the wastes may be pieces of contaminated equipment or clothing, but the process is particularly suitable for the encapsulation of particulate wastes.
- the wastes may be dry in which case water must be added to the mixture to cause it to set.
- the process is particularly suitable for the treatment of wet particulate radio active wastes which are usually difficult to handle by alternative methods.
- the quantity of water present in the waste may, for example, be in the range 20% to 60% by weight of waste, preferably below 50% by weight.
- the process of the present invention is particularly suitable for the encapsulation of wet ion-exchange resins both anionic and cationic.
- Other wet solid wastes to which the process of the invention may be applied are molecular sieves, graphite, sand and aluminosilicates, Magnox sludges (sludges containing magnesium hydroxide mixed with magnesium carbonate) filtration sludges.
- the process of the present invention may also be used to encapsulate wastes in the form of aqueous solutions. It will be necessary to use sufficient hydraulic filler to bind all the water on setting.
- M.xtures gelling in the range 10 to 30 minutes can be used however and a standard polyester made from a mixture of an ether glycol and a non-ether glycol e.g. from diethylene glycol and ethylene glycol, may be used together with a metal accelerator e.g. copper naphthenate, a reducing agent e.g sodium metabisulphite and a soap emulsifier.
- a metal accelerator e.g. copper naphthenate
- a reducing agent e.g sodium metabisulphite
- soap emulsifier e.g. an unsaturated polyester may be used which is inherently more reactive e.g. an unsaturated polyester produced from one or more glycols which are substantially all ether glycol in which case metal accelerators and reducing agents are not required.
- the hydraulic filler may be any substance which on mixing with water at ambient temperature reacts to form a crystalline lattice structure exhibiting a degree of mechanical stability and/or physical strength.
- Examples of hydraulic fillers are gypsum, calcium sulphate hemihydrate (plaster of Paris),.and pulverised fuel ash.
- the alkaline conditions required to activate the initiator may be provided by the addition of a substance which is not a hydraulic filler. However in a preferred embodiment of the invention, the substance which produces the alkaline conditions also acts as a hydraulic filler, and it is preferred to use an alkaline reacting hydraulic cement.
- Examples of hydraulic cements are high alumina cements, blast furnace cements, lime-pozzolana cement. It is preferred however to use mixtures containing Portland cement.
- the Portland cement may be substantially the only hydraulic filler present in the mixture. Alternatively it may be desirable to use mixtures of Portland cement with other fillers e.g. pulverised fuel ash.
- the Portland cement content in such mixtures may be from 6 to 95% by weight of total hydraulic filler, but is more preferably greater than 10% by weight, in particularly greater than 20% by weight.
- the initiator used in the process of the present invention is one which is activated by aqueous alkaline conditions, which distinguishes it from the organic peroxides usually used in polyester moulding compositions. It is preferred to use a water soluble salt of a per acid, in particular salts of persulphuric acid, e.g. ammonium, sodium and potassium persulphate. It is particularly preferred to use ammonium persulphate.
- the quantity of initiator used will depend on the speed of gelling required. Examples of suitable amounts are those in the range 1% to 5% by weight of the encapsulation mixture.
- the quantity of waste incorporated in the encapsulation mixture may vary over a wide range. For economic reasons it is desirable to incorporate a large quantity of waste into the mixture. However an excessive amount of waste may lead to a reduction in the physical strength of the final product obtained. The man skilled in the art will be able to determine by simple tests the maximum amount of waste which can be incorporated consistent with his requirements for the physical strength and integrity of the final product. Thus the quantity of waste may be 30% to 60% of the total weight of encapsulation mixture and waste and is preferably more than 40% by weight of the total. It is preferred to use sufficient quantity of encapsulation mixture to prevent the appearance of excess water on the surface of the set product, when treating a wet waste.
- the relative proportions of unsaturated polyester, ethylenically unsaturated monomer and hydraulic filler may vary over a wide range.
- suitable compositions may contain 50 to 70 parts of polyester resin, 25 to 65 parts of unsaturated monomer and 80 to 150 parts of hydraulic filler and 3 to 5 parts of initiator.
- the waste does not contain water it will be necessary to add it so as to cause the encapsulation mixture to set. Even if some water is present in the waste it may be desirable to add additional water.
- the quantity of water initially present may for example be at least 50% by weight of the hydraulic filler.
- the dry encapsulation mixture is prepared in advance of the encapsulation step it may be desirable to add fumaric acid to stabilise it. It may be desirable to add non-ionic surfactants.
- the addition of fatty acids to control pot life i.e. the time for which the mixture remains fluid after water is added) and give ease of dispersion of the encapsulation mixture after prolonged storage may be useful.
- the quantities of waste, hydraulic filler unsaturated polyester and copolymerisable monomer are preferably such as give a product which has a specific gravity of at least 1.2. This is important if the encapsulated material is to be disposed of by dumping in the ocean.
- the encapsulation mixtures of the present invention may be prepared by simple low speed mixing apparatus without the necessity • (see GB 1 098 132, GB 1 091 325, GB 1 092, 747). of using expensive high shear mixers such as are used in the production of WEPs (water extended polyesters). If the waste is particulate it may be introduced into the mixing apparatus with the other ingredients. The mixture is then discharged into a mould in which it is allowed to set. For non-particulate waste e.g. pieces of machinery, encapsulation mixture may be fed to the mould, the waste added and the mould may then be filled with additional encapsulation mixture.
- the mixture may be removed from the mould.
- the resulting moulded block may then be if required be inserted into a protective container and disposed of by dumping.
- the mould in which the block is formed may act also as a container.
- polyester resin A Similar to polyester resin A except this was processed to a higher viscosity and contained less inhibitors.
- Polyester resin A 60 parts by weight was mixed at ambient temperature with a hydraulic cement (40 parts by weight) (sold under the name Hydracrete) ammonium persulphate (2 parts by weight), sodium metabisulphate (0.5 parts by weight), copper naphthenate (equivalent to 5 ppm copper) and liquid soap (1.0 parts by weight).
- Ion exchange resin 50 parts by weight containing about 47% by weight of water was then mixed in and the mixture was allowed to set in a mould. The mixture gelled in 11 minutes and had set sufficiently to allow the block of encapsulated ion exchange resin to be removed from the mould in 2 to 3 hours.
- a composition was made by mixing together at ambient temperature polyester resin C, Portland cement and ammonium persulphate in the proportions shown in Table 1.
- Waste in the form of wet ion exchange resin (75 grams) containing 47% by weight of water was added to the mixture and cast in a mould.
- the mixture in the mould gelled in 30 minutes and readily demoulded in 2 to 3 hours showing no signs of separated water.
- Example 2 These were comparative tests not according to the invention and were carried out as Example 2 except that cumene hydroperoxide paramenthane hydroperoxide and methyl ethyl ketone peroxide respectively were used in place of ammonium persulphate.
- the mixture in the mould thickened over a period of 4 to 6 hours without properly gelling. Overnight a sticky uncured soft mass was produced showing large quantities of free water and liquid polyester resin.
- Example 2 This was carried out in a similar way to Example 2 but using polyester resin B in place of polyester resin C.
- the quantities used are shown in Table 2 and the same quantity (75 grams) of the wet ion exchange resin was added as in Example 2.
- the mixture was poured into a mould. It gelled after 11 minutes and could be readily demoulded in 1-12 hours showing no signs of separated water.
- the mixture in the mould gelled in 25 minutes and could be readily demoulded in 3 to 4 hours showing no signs of separated water.
- the ingredients set out in Table 3 were mixed together at an ambient temperature of 20°C and allowed to set in a mould.
- the pot life of the mixtures i.e. the time required for gelling to take place was measured and is given in Table 3. All the mixtures were readily demoulded in 1-2 hours and exhibited no separated water.
- the white cement, high early strength cement, and oil well cement are all different types of cement well known to those skilled in the cement art.
- compositions set out in Table 4 were prepared in the same way as in the previous examples at an ambient temperature of 20°C.
- Example 20 The mixture of Example 20 was demoulded in 6-8 hours and showed a slight surface wetness.
- the mixed waste was a mixture of ion-exchange resins.
- volume shrinkage was approximately 2.5% in all cases.
- Binder for encapsulation mixture as for Example 24 replacing the crushed Lewatit by 9 parts by weight of water.
- Cast specimens were submitted to varying dosages of gamma radiation and tested before and after exposure. Table 9 shows the results.
- Specimens were prepared using the formulation of Example 24 using radio active waste ion exchange resin contaminated with Caesium 137 isotope. These specimens were prepared and tested in accordance with "Leach Testing of Immobilised Radio active Waste Solids", A Proposal for a Standard Method, E. D. Hespe Atomic Energy Review Vol. 9 page 195 (1971).
- Peak exotherm measurements were made using thermocouples positioned at the centre points of the castings.
- the mixed waste resin used in Examples 1 to 22 inclusive was that described in Example 6.
- the water content in Examples 1 to 21 was 47% but in Example 22 was 42%.
- compositions were made up in the manner of the previous Examples: * Composition as given in Example 22.
- compositions were hand mixed and were readily pourable prior to gelation.
- Compositions of Examples 27 to 30 could be demoulded between 1 and 4 hours after mixing showing no signs of separated water and on demoulding they were homogeneous and free from cracks and voids other than minor air inclusions.
- the composition of Comparative Test G did not set within 24 hours.
- the composition of Example 31 was demouldable within 24 hours.
- Example 22 Compositions mixed by hand were readily pourable prior to gelation.
- the compositions of Examples 32 to 34 were demouldable within 1 to 4 hours after mixing showing no signs of separated water, and on demoulding were homogeneous and free from cracks and voids other than minor air inclusions.
- the composition of Comparative Test H did not set within 24 hours.
- the mixtures according to the present invention were pourable and easily handled before setting and were prepared using low shear paddle mixers in contrast to the high shear mixers used to make water extended polyester mixtures. It should be noted that the water-in- polyester emulsions used in making water extended polyesters are often very thick and difficult to pour.
- the mixtures of the present invention when set were uniform, free from major cracks and voids other than small air inclusions. They were mechanically strong and could be transported without crumbling or breaking.
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7826549 | 1978-06-08 | ||
GB2654978 | 1978-06-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0006329A1 true EP0006329A1 (en) | 1980-01-09 |
Family
ID=10497901
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP79301080A Ceased EP0006329A1 (en) | 1978-06-08 | 1979-06-07 | Encapsulating wastes |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0006329A1 (enrdf_load_stackoverflow) |
JP (1) | JPS55500406A (enrdf_load_stackoverflow) |
ES (1) | ES481367A1 (enrdf_load_stackoverflow) |
WO (1) | WO1980000047A1 (enrdf_load_stackoverflow) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2505539A1 (fr) * | 1981-05-11 | 1982-11-12 | Snial Resine Poliestere Spa | Procede de solidification des dechets radio-actifs contenus dans des resines echangeuses d'ions, articles solides ainsi obtenus et composition contenant une matiere radioactive a base de resines echangeuses d'ions |
FR2607957A1 (fr) * | 1986-12-05 | 1988-06-10 | Commissariat Energie Atomique | Bloc contenant des dechets en vue de leur stockage et procede de realisation d'un tel bloc |
US5900258A (en) * | 1996-02-01 | 1999-05-04 | Zeolitics Inc. | Anti-bacterial compositions |
FR2773504A1 (fr) * | 1998-01-12 | 1999-07-16 | Bouygues Sa | Procede pour conditionner des particules de resines echangeuses d'ions et application au traitement d'une eau radioactive |
US7445591B2 (en) | 2001-12-21 | 2008-11-04 | British Nuclear Fuels Plc | Treatment of waste products |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH654436A5 (fr) * | 1983-04-29 | 1986-02-14 | Syncrete Sa | Procede d'enrobage de dechets radioactifs. |
CH656539A5 (fr) * | 1983-08-23 | 1986-07-15 | Syncrete Sa | Procede de traitement de dechets chimiques ou radioactifs. |
DE3802755A1 (de) * | 1988-01-30 | 1989-08-10 | Kernforschungsanlage Juelich | Verfahren zur einlagerung von radioaktiven abfallstoffen |
US4828761A (en) * | 1988-05-04 | 1989-05-09 | The United States Of America As Represented By The United States Department Of Energy | Process for impregnating a concrete or cement body with a polymeric material |
US5481064A (en) * | 1992-05-08 | 1996-01-02 | Sanko Motor Chemical Co., Ltd. | Waste fluid treatment process |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1246848A (fr) * | 1959-10-13 | 1960-11-25 | Commissariat Energie Atomique | Procédé d'élimination de déchets radioactifs et produits obtenus suivant ce procédé |
FR2273350A2 (en) * | 1974-05-27 | 1975-12-26 | Commissariat Energie Atomique | Radioactive waste storage using ion exchange resin - or filtration or flocculation adjuvants |
US4077901A (en) * | 1975-10-03 | 1978-03-07 | Arnold John L | Encapsulation of nuclear wastes |
FR2361724A1 (fr) * | 1976-08-12 | 1978-03-10 | Commissariat Energie Atomique | Procede de stockage de resines echangeuses d'ions contaminees |
FR2366234A1 (fr) * | 1976-04-27 | 1978-04-28 | Crouzet Pierre | Procede de fabrication d'un produit a base d'une emulsion et d'un agent de prise, et produit obtenu par application de ce procede |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2356253C2 (de) * | 1973-11-10 | 1982-06-09 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Verfahren zur Verfestigung einer organischen, radioaktive Stoffe enthaltenden Abfallflüssigkeit |
DE2549195A1 (de) * | 1974-11-05 | 1976-05-06 | Asea Atom Ab | Verfahren, um verbrauchte, kornfoermige, organische ionenaustauschmasse in zement einzubetten |
-
1979
- 1979-06-07 JP JP50086279A patent/JPS55500406A/ja active Pending
- 1979-06-07 ES ES481367A patent/ES481367A1/es not_active Expired
- 1979-06-07 EP EP79301080A patent/EP0006329A1/en not_active Ceased
- 1979-06-07 WO PCT/GB1979/000099 patent/WO1980000047A1/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1246848A (fr) * | 1959-10-13 | 1960-11-25 | Commissariat Energie Atomique | Procédé d'élimination de déchets radioactifs et produits obtenus suivant ce procédé |
FR2273350A2 (en) * | 1974-05-27 | 1975-12-26 | Commissariat Energie Atomique | Radioactive waste storage using ion exchange resin - or filtration or flocculation adjuvants |
US4077901A (en) * | 1975-10-03 | 1978-03-07 | Arnold John L | Encapsulation of nuclear wastes |
FR2366234A1 (fr) * | 1976-04-27 | 1978-04-28 | Crouzet Pierre | Procede de fabrication d'un produit a base d'une emulsion et d'un agent de prise, et produit obtenu par application de ce procede |
FR2361724A1 (fr) * | 1976-08-12 | 1978-03-10 | Commissariat Energie Atomique | Procede de stockage de resines echangeuses d'ions contaminees |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2505539A1 (fr) * | 1981-05-11 | 1982-11-12 | Snial Resine Poliestere Spa | Procede de solidification des dechets radio-actifs contenus dans des resines echangeuses d'ions, articles solides ainsi obtenus et composition contenant une matiere radioactive a base de resines echangeuses d'ions |
FR2607957A1 (fr) * | 1986-12-05 | 1988-06-10 | Commissariat Energie Atomique | Bloc contenant des dechets en vue de leur stockage et procede de realisation d'un tel bloc |
EP0274927A1 (fr) * | 1986-12-05 | 1988-07-20 | Commissariat à l'Energie Atomique | Bloc contenant des déchêts en vue de leur stockage et procédé de réalisation d'un tel bloc |
US4839102A (en) * | 1986-12-05 | 1989-06-13 | Commissariat A L'energie Atomique | Block for containing and storing radioactive waste and process for producing such a block |
US5900258A (en) * | 1996-02-01 | 1999-05-04 | Zeolitics Inc. | Anti-bacterial compositions |
FR2773504A1 (fr) * | 1998-01-12 | 1999-07-16 | Bouygues Sa | Procede pour conditionner des particules de resines echangeuses d'ions et application au traitement d'une eau radioactive |
US7445591B2 (en) | 2001-12-21 | 2008-11-04 | British Nuclear Fuels Plc | Treatment of waste products |
Also Published As
Publication number | Publication date |
---|---|
ES481367A1 (es) | 1980-02-01 |
JPS55500406A (enrdf_load_stackoverflow) | 1980-07-10 |
WO1980000047A1 (en) | 1980-01-10 |
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