CN102247685B - Harmless treatment process for mercury-containing waste dangerous chemicals - Google Patents
Harmless treatment process for mercury-containing waste dangerous chemicals Download PDFInfo
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- CN102247685B CN102247685B CN201010177788.5A CN201010177788A CN102247685B CN 102247685 B CN102247685 B CN 102247685B CN 201010177788 A CN201010177788 A CN 201010177788A CN 102247685 B CN102247685 B CN 102247685B
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- mercury
- reaction system
- hydrogen peroxide
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- waste
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 36
- 239000000126 substance Substances 0.000 title claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000004568 cement Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 15
- -1 compound sulfide Chemical class 0.000 claims abstract description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000005864 Sulphur Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 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 claims description 16
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 229910021538 borax Inorganic materials 0.000 claims description 7
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 7
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000004328 sodium tetraborate Substances 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- 239000001119 stannous chloride Substances 0.000 claims description 7
- 235000011150 stannous chloride Nutrition 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000002386 leaching Methods 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 description 12
- 230000002588 toxic effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000000383 hazardous chemical Substances 0.000 description 9
- 239000002920 hazardous waste Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 229910000975 Carbon steel Inorganic materials 0.000 description 6
- 239000010962 carbon steel Substances 0.000 description 6
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229940074994 mercuric sulfate Drugs 0.000 description 4
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- LJBWEZVYRBKOCI-UHFFFAOYSA-N 2,4,6-triaminoquinazoline Chemical compound N1=C(N)N=C(N)C2=CC(N)=CC=C21 LJBWEZVYRBKOCI-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JCIIKRHCWVHVFF-UHFFFAOYSA-N 1,2,4-thiadiazol-5-amine;hydrochloride Chemical compound Cl.NC1=NC=NS1 JCIIKRHCWVHVFF-UHFFFAOYSA-N 0.000 description 2
- AGJBKFAPBKOEGA-UHFFFAOYSA-M 2-methoxyethylmercury(1+);acetate Chemical compound COCC[Hg]OC(C)=O AGJBKFAPBKOEGA-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- LPLYANIKARFGNI-UHFFFAOYSA-N azanium ethanol 2-hydroxypropanoate phenylmercury Chemical compound C(C(O)C)(=O)[O-].[NH4+].C(C)O.C(C)O.C(C)O.C1(=CC=CC=C1)[Hg] LPLYANIKARFGNI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- VJTAZCKMHINUKO-UHFFFAOYSA-M chloro(2-methoxyethyl)mercury Chemical compound [Cl-].COCC[Hg+] VJTAZCKMHINUKO-UHFFFAOYSA-M 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- ATZBPOVXVPIOMR-UHFFFAOYSA-N dimethylmercury Chemical compound C[Hg]C ATZBPOVXVPIOMR-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 2
- FQGYCXFLEQVDJQ-UHFFFAOYSA-N mercury dicyanide Chemical compound N#C[Hg]C#N FQGYCXFLEQVDJQ-UHFFFAOYSA-N 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- JVJUWCMBRUMDDQ-UHFFFAOYSA-N methylmercuric dicyanamide Chemical compound C[Hg]N=C(N)NC#N JVJUWCMBRUMDDQ-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 2
- 229940096826 phenylmercuric acetate Drugs 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- CHQQUQPTUDVREO-UHFFFAOYSA-N 2,3,4,5,6-pentachlorophenol;phenylmercury Chemical compound [Hg]C1=CC=CC=C1.OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CHQQUQPTUDVREO-UHFFFAOYSA-N 0.000 description 1
- BLFCXYJTVFTNRX-UHFFFAOYSA-N 2-chloro-4-(furan-2-yl)pyrimidine Chemical compound ClC1=NC=CC(C=2OC=CC=2)=N1 BLFCXYJTVFTNRX-UHFFFAOYSA-N 0.000 description 1
- ZELCNSAUMHNSSU-UHFFFAOYSA-N 3,5-diamino-2-[(4-sulfamoylphenyl)diazenyl]benzoic acid Chemical compound OC(=O)C1=CC(N)=CC(N)=C1N=NC1=CC=C(S(N)(=O)=O)C=C1 ZELCNSAUMHNSSU-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XBBAEVVIDHSGKC-UHFFFAOYSA-N [As].[Hg] Chemical compound [As].[Hg] XBBAEVVIDHSGKC-UHFFFAOYSA-N 0.000 description 1
- BLCPUIDWWMBQSR-UHFFFAOYSA-N [Hg].[Cl-].[NH4+] Chemical compound [Hg].[Cl-].[NH4+] BLCPUIDWWMBQSR-UHFFFAOYSA-N 0.000 description 1
- GPQUEUOSGZMUQE-UHFFFAOYSA-N [O-2].[Hg+].[Hg+] Chemical compound [O-2].[Hg+].[Hg+] GPQUEUOSGZMUQE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- IDARKLQOQUZQOL-UHFFFAOYSA-N arsoric acid;mercury Chemical compound [Hg].O[As](O)(O)=O IDARKLQOQUZQOL-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RVARJMCTILSHND-UHFFFAOYSA-L bromomercury Chemical compound [Hg]Br.[Hg]Br RVARJMCTILSHND-UHFFFAOYSA-L 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007728 cost analysis Methods 0.000 description 1
- PHMMATAWQLJFIQ-UHFFFAOYSA-N cyanomercury(1+);oxygen(2-) Chemical compound [O-2].[Hg+]C#N.[Hg+]C#N PHMMATAWQLJFIQ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- FMSYTQMJOCCCQS-UHFFFAOYSA-L difluoromercury Chemical compound F[Hg]F FMSYTQMJOCCCQS-UHFFFAOYSA-L 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- LTLCGIKWGSDBMN-UHFFFAOYSA-L dimercury diacetate Chemical compound CC(=O)O[Hg][Hg]OC(C)=O LTLCGIKWGSDBMN-UHFFFAOYSA-L 0.000 description 1
- HWXOCCNUUYRBKP-UHFFFAOYSA-J dipotassium;mercury(2+);tetrathiocyanate Chemical compound [K+].[K+].[Hg+2].[S-]C#N.[S-]C#N.[S-]C#N.[S-]C#N HWXOCCNUUYRBKP-UHFFFAOYSA-J 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- YHASLHJYXUVQFW-UHFFFAOYSA-N hydroxymethylmercury Chemical compound OC[Hg] YHASLHJYXUVQFW-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- OMMDBGHLAZUINT-UHFFFAOYSA-N mercury 1,2,3,4,5-pentachlorobenzene phenol Chemical compound [Hg].C1(=CC=CC=C1)O.ClC=1C(=C(C(=C(C1)Cl)Cl)Cl)Cl OMMDBGHLAZUINT-UHFFFAOYSA-N 0.000 description 1
- FMWLBFIGGYUVQB-UHFFFAOYSA-N mercury phenol Chemical compound [Hg].C1(=CC=CC=C1)O.C1(=CC=CC=C1)O FMWLBFIGGYUVQB-UHFFFAOYSA-N 0.000 description 1
- PCWIWQHAGMGLFA-CVBJKYQLSA-L mercury(2+);(z)-octadec-9-enoate Chemical compound [Hg+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O PCWIWQHAGMGLFA-CVBJKYQLSA-L 0.000 description 1
- IOQKJDCMPKUNQN-UHFFFAOYSA-L mercury(2+);2-oxidobenzoate Chemical compound C1=CC=C2C(=O)O[Hg]OC2=C1 IOQKJDCMPKUNQN-UHFFFAOYSA-L 0.000 description 1
- BXDUJMLIUYJHNH-UHFFFAOYSA-L mercury(2+);oxalate Chemical compound [Hg+2].[O-]C(=O)C([O-])=O BXDUJMLIUYJHNH-UHFFFAOYSA-L 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N mercury(I) nitrate Inorganic materials [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(I) oxide Inorganic materials O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- BABMCXWQNSQAOC-UHFFFAOYSA-M methylmercury chloride Chemical compound C[Hg]Cl BABMCXWQNSQAOC-UHFFFAOYSA-M 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- KDNVJBRRDKAHDA-UHFFFAOYSA-L phenyl-[3-[[3-(phenylmercuriooxysulfonyl)naphthalen-2-yl]methyl]naphthalen-2-yl]sulfonyloxymercury Chemical compound C=1C2=CC=CC=C2C=C(CC=2C(=CC3=CC=CC=C3C=2)S(=O)(=O)O[Hg]C=2C=CC=CC=2)C=1S(=O)(=O)O[Hg]C1=CC=CC=C1 KDNVJBRRDKAHDA-UHFFFAOYSA-L 0.000 description 1
- MSYUMXXVCSLXMR-UHFFFAOYSA-N phenylmercury;hydrate Chemical compound O.[Hg]C1=CC=CC=C1 MSYUMXXVCSLXMR-UHFFFAOYSA-N 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a harmless treatment process of mercury-containing waste dangerous chemicals, which comprises the following steps: 1) adding mercury-containing waste into water, and adjusting the pH value to be less than 2; then adding hydrogen peroxide to convert organic mercury and univalent mercury in the reaction system into Hg2+(ii) a 2) Adjusting the pH value of the reaction system to 11-12, and heating to remove excessive hydrogen peroxide; 3) adding compound sulfide to lead Hg in a reaction system to be2+Completely converted into HgS precipitate; adding ferrous salt to make excess S2-A precipitate is formed; 4) adding a curing material into the precipitate and the waste liquid generated in the step 3) for curing treatment to obtain a cement cured body. The process provided by the invention organically integrates chemical treatment and cement curing technology, and the mercury leaching toxicity concentration of the obtained cement cured body is less than 0.1mg/L, thereby reaching the relevant national harmless standard.
Description
Technical field
The invention belongs to waste treatment processes technical field, relate in particular to a kind of harmless treatment process of waste dangerous chemical containing mercury.
Background technology
Curing technology is the important means of process heavy metal waste and other nonmetal hazardous waste.By solidification, harmful waste is fixed in a kind of fluid-tight matrix of inertia, hazardous contaminant can be changed into the stable material of low-solubility, low migration and hypotoxic physics and chemistry Property comparison by refuse after overcuring process.
The mechanism that curing technology stablizes waste component be Chemical bonding between refuse and coagulating agent, coagulating agent to the physical inclusion of refuse, coagulating agent hydrated product to the acting in conjunction of the absorption of refuse etc., make refuse change not charge of flowable solids or form tight solid into, change the permeability of refuse, compressibility and intensity.Hazardous waste can reach and alleviate or eliminate himself harmfulness after overcuring process, can transport safely, and can carry out final disposal easily.
Cement is the most frequently used hazardous waste stabilizing agent.Because cement is a kind of cement inorganic material, hard solidified cement body can be generated after hydration reaction, thus reach the object reducing hazard component leaching in refuse.Cement adding rate is different according to process type of waste difference, and its excursion can reach 5% ~ 60%.
The curing technology taking cement as base material for the treatment of containing the electroplating sludge of different heavy metal (as cadmium, chromium, copper, lead, zinc etc.), also for the treatment of containing organic complex waste, as PCBs, grease, resin, asbestos etc.
At home, cement solidification technology is never successfully applied to waste dangerous chemical containing mercury process, main cause is the mercurous rate of mercurous hazardous chemical high (usually more than 50%), vulcanisation mercury all can not effectively solidify outward, in the sulfonitric digestion agent (" solid waste Leaching leaching method sulfonitric method " (HJ/T299-2007)) of its product in pH=3.20 ± 0.05, total mercury all significantly leaches, far above the innoxious standard of 0.1mg/L, its subsequent treatment cannot reach the requirement of safety-health-environmental protection.
The meaning of waste dangerous chemical containing mercury harmlessness disposing:
Waste dangerous chemical, refer to the hazardous chemical abandoned by everyone without use or abandon, superseded, of poor quality, expired, to lose efficacy hazardous chemical, the hazardous chemical that the hazardous chemical in accordance with the law taken in administration activities by authorities such as public security, customs, quality inspection, industry and commerce, agricultural, security control, environmental protection and the public of reception submit." National Hazard refuse register " (2008) list 498 kinds of preferential administrative class waste dangerous chemicals, and mercurous class has 53 kinds (to comprise mercuric benzoate, mercuric oxalate, mercuric iodixde, potassiomercuric iodide, mecrurous iodide, hexichol (base) mercury, dimethylmercury, mercuric fluoride, mercury, mercurol, methoxy ethyl mercury chloride, methoxy ethyl mercuric acetate, pyrosulfuric acid mercury, di(2-ethylhexyl)phosphate ethyl mercury, mercuric sulphide, mercuric thiocyanate, mercuric thiocyanate ammonium, potassium mercuric thiocyanate, mercuric sulfate, mereurous sulfate, 2-chlorine mercury phenol, 4-chloromercuri-benzoate, ammonium chloride mercury, mercury chloride, methyl-mercuric chloride, ethylmercuric chloride, conotrane, gluconic acid mercury, amalgam lead, phenylmercury hydroxide, hydroxymethyl mercury, morsodren, mercury cyanide, mercuric potassium cyanide, Phenylmercury Lactate triethanol ammonium, arsenic mercury, mercuric arsenate, mercuric salicylate, four chlorination mercuration potassium, pentachloro-(benzene) phenol mercury, pentachlorophenol phenyl mercury, mercuric nitrate, mercuric nitrate benzene, mercurous nitrate, mercuric bromide, mercurous bromide, mercury oxide, mercurous oxide, mercuric oxycyanide, phenylmercuric acetate, mercuric acetate, mercurous acetate, mercuric oleate etc.), account for 10% of kind sum.
Severe poisonous chemicals refers to the chemicals with very acute toxicity harm, chemicals comprising Prof. Du Yucang and composition thereof (containing agricultural chemicals) and natural toxin." severe poisonous chemicals register " (2002 editions) include 335 kinds altogether, and wherein mercurous class comprises mercuric iodixde, dimethylmercury, methoxy ethyl mercury chloride, methoxy ethyl mercuric acetate, di(2-ethylhexyl)phosphate ethyl mercury, mercuric thiocyanate, mercury chloride, ethylmercuric chloride, morsodren, mercury cyanide, Phenylmercury Lactate triethanol ammonium, mercuric nitrate, mercuric bromide, mercury oxide, phenylmercuric acetate, mercuric acetate etc. 16 kinds.
The frequency participating in International Operations along with China improves day by day, the importance of anti-terrorism work becomes increasingly conspicuous, in time, Safety destroy discards mercurous hazardous chemical particularly mercurous toxic articles ensure to eliminate respective environment hidden danger, becomes the vital task of the departments of government such as various places public security, environmental protection.But compared with developed countries, China lacks the technology that really can realize discarding mercurous hazardous chemical harmlessness disposing, up to now, domesticly not yet there is the destruction unit possessing corresponding disposal qualification and actual disposing capacity.Most regional mercurous toxic articles are deposited and are failed for many years obtain Safety destroy and there is great potential safety hazard.
Summary of the invention
The object of the present invention is to provide a kind of harmless treatment process of waste dangerous chemical containing mercury, to overcome the deficiencies in the prior art.
The present invention solves above-mentioned technical problem by the following technical solutions:
A harmless treatment process for waste dangerous chemical containing mercury, comprises the following steps:
1) in mercury-containing wastes, add water, and be less than 2 by nitric acid adjust ph; Then add hydrogen peroxide, make the organic mercury in reaction system and monovalence mercury all be converted into Hg
2+;
2) regulate the pH of reaction system to be adjusted to 11 ~ 12 with NaOH, then be heated to the excessive hydrogen peroxide of 90-100 DEG C of removing;
3) add compound sulfide, make the Hg in reaction system
2+be converted into HgS precipitation completely; Add ferrous salt again and make excessive S
2-form precipitation;
4) to step 3) in add curing materials and be cured process in the precipitation that produces and waste liquid, obtain solidified cement body.
Described step 1) in, the addition of water should control to make mercury-containing wastes form the aqueous solution or suspension.
Step 1) in, the mass percent concentration of described hydrogen peroxide is 20% ~ 30%, for guaranteeing to make the organic mercury in reaction system and monovalence mercury all be converted into Hg
2+, the H in hydrogen peroxide
2o
2should 2.5: 1 be not less than with the mol ratio of the mercury element in mercury-containing wastes.
Step 3) in, described compound sulfide is vulcanized sodium and ammonium sulfide, and the ratio of the mole of the element sulphur wherein contained in vulcanized sodium and ammonium sulfide is (3.5 ~ 4.5): 1; The addition of described compound sulfide is the integral molar quantity of element sulphur with the ratio of the mole of Hg element in (1.1 ~ 1.3): 1, ensures that the Hg2+ in reaction system can generate precipitation completely.
Step 3) in, described ferrous salt can use ferrous sulfate, frerrous chloride or ferrous nitrate etc.The addition of described ferrous salt is with the excessive S that can will exist in reaction system
2-formation precipitates.
Step 4) in, the addition of described curing materials and the mass ratio of described mercury-containing wastes are (6 ~ 8): 1; Described curing materials comprises 800# cement, PVOH amine, sulphur, sodium tetraborate and stannous chloride, and the proportioning of each component is as follows:
800# cement 89.5%-93.7%;
PVOH amine 3%-5%;
Sulphur 2%-3%;
Sodium tetraborate 1%-2%;
Stannous chloride 0.3%-0.5%.
Chemical disposal technology and cement solidification technology are organically integrated by technique provided by the present invention, by selecting to add compound sulfide under specific pH condition, make Hg
2+be converted into mercuric sulphide precipitation quantitatively, then be cured process formation solidified cement body.Finally make the Leaching concentration of the mercury of obtained solidified cement body be less than 0.1mg/L, reach the relevant innoxious standard of country.
Compared with prior art, the present invention also has the following advantages:
1, whole industrial flow is safe and reliable, and except having carbon dioxide when disposing organic mercury and discharging, without waste gas, discharge of wastewater, waste residue toxicity can be ignored, and amount send professional landfill yard direct landfill at least, and amount can be concentrated greatly and send mercury refinement unit to recycle.
2, practical, site disposal can be realized in conjunction with portable chemical laboratory, avoid toxic articles sending uncertain security risk in disposal transportation outside, completely eliminating the social safety hidden danger of mercurous toxic articles.
Accompanying drawing explanation
Fig. 1 is the harmless treatment process schematic flow sheet of waste dangerous chemical containing mercury of the present invention.
Detailed description of the invention
The present invention selects the mixture of multiple mercurous toxic articles as handling object, and adopt chemical disposal-cement solidification technique respectively through pilot scale and through engineering approaches application, its implementation process is:
Embodiment 1 pilot process:
(1) handling object
The mercurous toxic articles of Suzhou Shang Mei international cosmetic Co., Ltd, mercuric iodixde 49.5g, mercury chloride 488.9g, mercuric sulfate 223.3g, mercuric acetate 1988.1g, original mixture leachate (sulfonitric method) total mercury is higher than 20000mg/L.
(2) treatment process process
Process flow diagram is as shown in Figure 1:
In portable reactor, above-mentioned mercurous toxic articles mixture is added 3000g water, and adds nitric acid hydrotropy, make the pH value of solution be less than 2; Then add hydrogen peroxide (mass percent concentration of hydrogen peroxide is 20%-30%) and carry out oxidation reaction, wherein control the H in hydrogen peroxide
2o
2be 2.5: 1 with the mol ratio of the mercury element in mercury-containing wastes.After reaction carries out 1 hour, the organic mercury in reaction system and monovalence mercury is made all to be converted into Hg
2+.
Add NaOH again and the pH of reaction system is adjusted to 11 ~ 12, be then heated to 90-100 DEG C to remove excessive hydrogen peroxide.Add vulcanized sodium and ammonium sulfide more afterwards, the ratio of the mole of the element sulphur contained in vulcanized sodium and ammonium sulfide is 4: 1; Controlling to contain the integral molar quantity of element sulphur in vulcanized sodium and ammonium sulfide is 1.1: 1 with the ratio of the mole of Hg element.Add appropriate ferrous sulfate again and make S excessive in reaction system
2-form precipitation.
Above-mentioned gained precipitation is together added in 200L carbon steel tank with waste liquid, then adds 800# cement 18400g, PVOH amine 800g, sulphur 400g, sodium tetraborate 300g and stannous chloride 100g, be cured process and form stable solidified cement body.
(3) experimental rig specification and size
Portable reactor: 50L, material is double-deck Pyrex (GG17 material), and configuration frequency control agitator 1 overlaps (250W), temperature-controlling system etc.
Solidification equipment: 200L carbon steel tank.
(4) test effect
Detect by " hazard waste landfill Environmental capacity standard GB18598-2001 ", it is 0.18mg/L that solidified cement body leaches total mercury concentration, meets the direct landfill requirement of hazardous waste landfill.
Embodiment 2 through engineering approaches is applied:
(1) handling object
The mercurous hazardous chemical of the green happy solid waste recycling disposal Co., Ltd in Wujiang, 218kg, mercury content (on average) 47.18%, leaches mercury 2378mg/L.
(2) each processing unit technological parameter
Reaction tank: reaction tank is PP structure, is of a size of ￠ 3.0m × 2.2m, dischargeable capacity 14m
3, configure 1 agitating device, power is 7.5kW, above sets exhaust system (air-introduced machine power as 5.5kW), divides into plate and frame filter press 1 and overlap (80m
2).
Curing: two shaft pugmill mixer, productivity ratio 25m
3/ h.
Process flow diagram is as shown in Figure 1:
Above-mentioned mercurous toxic articles mixture 100kg is added 100kg water, and adds nitric acid hydrotropy, make the pH value of solution be less than 2; Then add hydrogen peroxide (mass percent concentration of hydrogen peroxide is 30%) and carry out oxidation reaction, wherein control the H in hydrogen peroxide
2o
2be 2.5: 1 with the mol ratio of the mercury element in mercury-containing wastes.After reaction carries out 1 hour, the organic mercury in reaction system and monovalence mercury is made all to be converted into Hg
2+.
Add NaOH again and the pH of reaction system is adjusted to 11 ~ 12, be then heated to 95 DEG C to remove excessive hydrogen peroxide.Add vulcanized sodium and ammonium sulfide more afterwards, the ratio of the mole of the element sulphur contained in vulcanized sodium and ammonium sulfide is 4: 1; Controlling to contain the integral molar quantity of element sulphur in vulcanized sodium and ammonium sulfide is 1.2: 1 with the ratio of the mole of Hg element.Add appropriate ferrous sulfate again and make S excessive in reaction system
2-form precipitation.
Above-mentioned gained precipitation is together added in curing with waste liquid, then adds 800# cement 552kg, PVOH amine 24kg, sulphur 12kg, sodium tetraborate 9kg and stannous chloride 3kg, be cured process and form stable solidified cement body.
(3) through engineering approaches application treatment effect
Detect by " hazard waste landfill Environmental capacity standard GB18598-2001 ", it is 0.04mg/L that solidified cement body leaches total mercury concentration, meets the direct landfill requirement of hazardous waste landfill.
(4) technical economic analysis
By engineering operation cost analysis (primarily of labour cost, the electricity charge, medicament expense and laboratory fee four part composition), the mercurous hazardous chemical disposal cost of every 1kg is 97 yuan (criticizing scale by 100kg/).
Embodiment 3 pilot process:
(1) handling object
The mercurous toxic articles of Suzhou Shang Mei international cosmetic Co., Ltd, mercuric iodixde 49.5g, mercury chloride 488.9g, mercuric sulfate 223.3g, mercuric acetate 1988.1g, original mixture leachate (sulfonitric method) total mercury is higher than 20000mg/L.
(2) treatment process process
Process flow diagram is as shown in Figure 1:
In portable reactor, above-mentioned mercurous toxic articles mixture is added 3000g water, and adds nitric acid hydrotropy, make the pH value of solution be less than 2; Then add hydrogen peroxide (mass percent concentration of hydrogen peroxide is 20%-30%) and carry out oxidation reaction, wherein control the H in hydrogen peroxide
2o
2be 2.5: 1 with the mol ratio of the mercury element in mercury-containing wastes.After reaction carries out 1 hour, the organic mercury in reaction system and monovalence mercury is made all to be converted into Hg
2+.
Add NaOH again and the pH of reaction system is adjusted to 11 ~ 12, be then heated to 90-100 DEG C to remove excessive hydrogen peroxide.Add vulcanized sodium and ammonium sulfide more afterwards, the ratio of the mole of the element sulphur contained in vulcanized sodium and ammonium sulfide is 4.5: 1; Controlling to contain the integral molar quantity of element sulphur in vulcanized sodium and ammonium sulfide is 1.3: 1 with the ratio of the mole of Hg element.Add appropriate ferrous sulfate again and make S excessive in reaction system
2-form precipitation.
Above-mentioned gained precipitation is together added in 200L carbon steel tank with waste liquid, then adds 800# cement 18740g, PVOH amine 600g, sulphur 400g, sodium tetraborate 200g and stannous chloride 60g, be cured process and form stable solidified cement body.
(3) experimental rig specification and size
Portable reactor: 50L, material is double-deck Pyrex (GG17 material), and configuration frequency control agitator 1 overlaps (250W), temperature-controlling system etc.
Solidification equipment: 200L carbon steel tank.
(4) test effect
Detect by " hazard waste landfill Environmental capacity standard GB18598-2001 ", it is 0.15mg/L that solidified cement body leaches total mercury concentration, meets the direct landfill requirement of hazardous waste landfill.
Embodiment 4 pilot process:
(1) handling object
The mercurous toxic articles of Suzhou Shang Mei international cosmetic Co., Ltd, mercuric iodixde 49.5g, mercury chloride 488.9g, mercuric sulfate 223.3g, mercuric acetate 1988.1g, original mixture leachate (sulfonitric method) total mercury is higher than 20000mg/L.
(2) treatment process process
Process flow diagram is as shown in Figure 1:
In portable reactor, above-mentioned mercurous toxic articles mixture is added 3000g water, and adds nitric acid hydrotropy, make the pH value of solution be less than 2; Then add hydrogen peroxide (mass percent concentration of hydrogen peroxide is 20%-30%) and carry out oxidation reaction, wherein control the H in hydrogen peroxide
2o
2be 2.5: 1 with the mol ratio of the mercury element in mercury-containing wastes.After reaction carries out 1 hour, the organic mercury in reaction system and monovalence mercury is made all to be converted into Hg
2+.
Add NaOH again and the pH of reaction system is adjusted to 11 ~ 12, be then heated to 90-100 DEG C to remove excessive hydrogen peroxide.Add vulcanized sodium and ammonium sulfide more afterwards, the ratio of the mole of the element sulphur contained in vulcanized sodium and ammonium sulfide is 3.5: 1; Controlling to contain the integral molar quantity of element sulphur in vulcanized sodium and ammonium sulfide is 1.1: 1 with the ratio of the mole of Hg element.Add appropriate ferrous sulfate again and make S excessive in reaction system
2-form precipitation.
Above-mentioned gained precipitation is together added in 200L carbon steel tank with waste liquid, then adds 800# cement 17900g, PVOH amine 1000g, sulphur 600g, sodium tetraborate 400g and stannous chloride 100g, be cured process and form stable solidified cement body.
(3) experimental rig specification and size
Portable reactor: 50L, material is double-deck Pyrex (GG17 material), and configuration frequency control agitator 1 overlaps (250W), temperature-controlling system etc.
Solidification equipment: 200L carbon steel tank.
(4) test effect
Detect by " hazard waste landfill Environmental capacity standard GB18598-2001 ", it is 0.12mg/L that solidified cement body leaches total mercury concentration, meets the direct landfill requirement of hazardous waste landfill.
Claims (2)
1. a harmless treatment process for waste dangerous chemical containing mercury, comprises the following steps:
1) in mercury-containing wastes, add water, and be less than 2 by nitric acid adjust ph; Then add hydrogen peroxide, make the organic mercury in reaction system and monovalence mercury all be converted into Hg
2+;
2) with NaOH, the pH of reaction system is adjusted to 11 ~ 12, then the hydrogen peroxide that heating removing is excessive;
3) add compound sulfide, make the Hg in reaction system
2+be converted into HgS precipitation completely; Add ferrous salt again and make excessive S
2-form precipitation;
4) to step 3) in add curing materials and be cured process in the precipitation that produces and waste liquid, obtain solidified cement body; Step 3) in, described compound sulfide is vulcanized sodium and ammonium sulfide, and the ratio of the mole of the element sulphur wherein contained in vulcanized sodium and ammonium sulfide is (3.5 ~ 4.5): 1; The addition of described compound sulfide is the integral molar quantity of element sulphur with the ratio of the mole of Hg element in (1.1 ~ 1.3): 1; Step 1) in, the H in described hydrogen peroxide
2o
2with the mol ratio of the mercury element in mercury-containing wastes for being not less than 2.5:1; Step 4) in, the addition of described curing materials and the mass ratio of described mercury-containing wastes are (6 ~ 8): 1.
2. the harmless treatment process of waste dangerous chemical containing mercury as claimed in claim 1, it is characterized in that, described curing materials comprises 800# cement, PVOH amine, sulphur, sodium tetraborate and stannous chloride, and the weight percentage of each component is as follows:
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| CN102633296B (en) * | 2012-05-04 | 2014-11-05 | 新疆大学 | Method for preparing mercuric sulfide (HgS) quantum dots by using mercury-containing wastewater |
| CN102942211A (en) * | 2012-11-19 | 2013-02-27 | 新疆天业（集团）有限公司 | Method for recycling mercury from mercury-containing solid wastes |
| CN104032139B (en) * | 2014-06-05 | 2016-03-30 | 东北大学 | The method reclaiming mercury from mercurous tailings is decomposed in a kind of complexation leaching-strengthening |
| FR3053257B1 (en) * | 2016-06-29 | 2018-08-10 | Institut Francais Des Sciences Et Technologies Des Transports, De L'amenagement Et Des Reseaux | METHOD FOR IMMOBILIZING A WASTE COMPRISING MERCURY |
| CN106621778B (en) * | 2016-12-29 | 2019-08-02 | 江苏新世纪江南环保股份有限公司 | The method and device of ammonia process of desulfurization slurries demercuration |
| CN107597787B (en) * | 2017-08-11 | 2020-11-10 | 航天凯天环保科技股份有限公司 | Method for efficiently stabilizing mercury-containing waste residues |
| CN108395020B (en) * | 2018-04-10 | 2021-02-19 | 北京科技大学 | Universal harmless disposal method for mercury overproof wastewater |
| CN108687114B (en) * | 2018-05-16 | 2021-05-11 | 扬州杰嘉工业固废处置有限公司 | Mercury-containing reagent waste stabilization and solidification treatment process |
| CN110217923B (en) * | 2019-06-20 | 2021-11-23 | 海南宝来工贸有限公司 | Treatment method of mixed heavy metal waste liquid |
| CN111020195A (en) * | 2019-11-30 | 2020-04-17 | 沈阳环境科学研究院 | Method for recovering waste mercuric bromide reagent |
| CN111672862B (en) * | 2020-06-12 | 2024-05-31 | 北控城市环境资源(宜昌)有限公司 | Disposal structure and disposal method of mercury-containing lamp tube |
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Denomination of invention: A harmless treatment process for hazardous chemicals containing mercury Granted publication date: 20150225 Pledgee: China Merchants Bank Co.,Ltd. Jiaxing Branch Pledgor: Zhejiang guizero Environmental Protection Technology Co.,Ltd. Registration number: Y2024330000441 |