CN104475431B - A kind of stabilisation curing of high poison waste residue - Google Patents
A kind of stabilisation curing of high poison waste residue Download PDFInfo
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- CN104475431B CN104475431B CN201510000055.7A CN201510000055A CN104475431B CN 104475431 B CN104475431 B CN 104475431B CN 201510000055 A CN201510000055 A CN 201510000055A CN 104475431 B CN104475431 B CN 104475431B
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- waste residue
- high poison
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- solidification
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- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 239000002574 poison Substances 0.000 title claims abstract description 30
- 231100000614 poison Toxicity 0.000 title claims abstract description 30
- 230000006641 stabilisation Effects 0.000 title claims abstract description 25
- 238000005253 cladding Methods 0.000 claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 26
- 239000010440 gypsum Substances 0.000 claims abstract description 18
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 18
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 13
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011105 stabilization Methods 0.000 claims abstract description 10
- 239000012188 paraffin wax Substances 0.000 claims abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- 238000001723 curing Methods 0.000 claims description 28
- 238000007711 solidification Methods 0.000 claims description 28
- 230000008023 solidification Effects 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008187 granular material Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 12
- 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 claims description 12
- 239000011507 gypsum plaster Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 230000033228 biological regulation Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 239000010812 mixed waste Substances 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 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 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims 1
- 229940106691 bisphenol a Drugs 0.000 claims 1
- 238000005728 strengthening Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 231100000167 toxic agent Toxicity 0.000 abstract description 3
- 239000003440 toxic substance Substances 0.000 abstract description 3
- 239000002893 slag Substances 0.000 description 12
- 239000002920 hazardous waste Substances 0.000 description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000002386 leaching Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002910 solid waste Substances 0.000 description 8
- 240000006909 Tilia x europaea Species 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000004568 cement Substances 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
- 238000005516 engineering process Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010814 metallic waste Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000012850 discrimination method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000012852 risk material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NSVHDIYWJVLAGH-UHFFFAOYSA-M silver;n,n-diethylcarbamodithioate Chemical compound [Ag+].CCN(CC)C([S-])=S NSVHDIYWJVLAGH-UHFFFAOYSA-M 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to the stabilisation curing of one or more of high poison waste residue such as mercurous, arsenic, chromium, cadmium, cyanide.By chemical stabilization heavy metal, then coated, epoxy resin is coated, solidified through four claddings and twice with gypsum+paraffin successively, the highly toxic substance in waste residue is set to be fully cured in firming body, the firming body intensity of generation is big, with long-time stability, is easy to follow-up landfill stabilization.
Description
Technical field
The present invention relates to dangerous waste disposal technology, and in particular to a kind of stabilisation curing of the dangerous waste residue of high poison.
Background technology
According to《People's Republic of China's Solid Waste Pollution Harness method》Regulation, hazardous waste refers to be included in National Hazard
Waste register or the waste with hazard property assert according to the hazardous waste judging standard and discrimination method of national regulation.
With industrial expansion, the hazardous waste of industrial processes discharge is increasing.It is estimated that the whole world is annual
Hazardous waste yield is 3.3 hundred million tons.The severe contamination that is brought due to hazardous waste and potentially have a strong impact on, some company poles
Power is attempted to industrial undeveloped country and area transfer hazardous waste.
In China, the processing disposal situation of high poison hazardous waste allows of no optimist.Due to things such as mercury, arsenic, chromium, cadmium, cyanides
Matter toxicity is larger, and easily enters percolate, causes dangerous waste percolate to be difficult to processing even polluted underground water and surface water, seriously
Influence Environmental security.The stabilisation of dangerous waste containing this pollutant is solidified into a global problem.
Chinese patent literature CN102580979 describes a kind of curing/stabilizing method of mercurous hazardous waste, method profit
Natural zeolite is handled with a kind of chemical reagent, the zeolite handled well is had the effect of preferably enrichment mercury, recyclingization
Phosphate ceramics are learned as curing agent and solidify waste slag containing mercury, the method effect preferably but the technique that is handled natural zeolite compared with
For complexity；Chinese patent literature CN 102151690 discloses a kind of method for handling arsenic sulfide slag, it is proposed that one kind is stabilized
The method of chemicals treatment arsenic sulfide slag, i.e., add inorganic flocculating agent liquid into arsenic sulfide slag, stir, add solid powder
Adsorbent, stirs, and is eventually adding asbestos wool stirring, and is conserved in hermetic bag, the shortcoming of this method be need to add compared with
Substantial amounts of stabilization agent, complex operation is higher with respect to processing cost；Chinese patent literature CN102205340 describes one kind
Process for recycling incineration ash of hazardous wastes, this method has not only reclaimed metal, and also residue is carried out with cement, carbide slag
Solidification is stabilized, but the firming body that the method is produced easily is corroded by percolate, there is the risk of secondary pollution；Chinese patent
Document CN101824543 introduces the vulcanizing treatment and the wherein method of valuable metal recovery of heavy metal waste, and the method is using vulcanization
The techniques such as method combination high temperature, high pressure, flotation are reclaimed to metal, so as to realize at the harmless resource utilization of heavy metal waste slag
Put, but have that cost is too high, the incomplete problem of heavy metal recovery；Chinese patent literature CN 102560124 describes one kind
Rotary kiln reclaims the method for disposal of solid waste of heavy metal, and such method has a preferable social benefit, but during easily produce
Secondary pollution；The A of Chinese patent literature CN 1493537 disclose a kind of processing method of dicyandiamide sludge as material, by alkaline oxygenated
Method or oxidization by bleaching powder method remove the cyanide in waste residue, and the method broken cyanide thoroughly, but produces a large amount of salinity influence percolates
Processing.
It is contemplated that carrying out stabilizing admittedly to high poison hazardous waste using chemical stabilization and cladding, solidification etc.
Change, by effective coating function, prevent harmful substance from entering percolate and then pollute environment.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of multiple-effect stabilize mercury in solidification hazardous waste, arsenic, chromium,
The stabilisation curing of cadmium, cyanide.
Realizing the technical scheme of the object of the invention is：
The present invention comprises the following steps：
1）Adjust pH：Acid or alkali are added under stirring into container so that the water-leach liquor pH of mixed waste residue
It is worth for 7~12；
2）Stabilize heavy metal：Heavy metal stable pharmaceutical is added into the waste residue after regulation pH, and continues stirring, high poison is given up
Heavy metal and medicament to form the compound of indissoluble by fully reacting and stabilized in slag；
3）Bond：Toward 2）Binding agent is added in step, stirring forms spherical particle thing after terminating；
4）Cladding：To step 3 under stirring）Covering is added in material after once coating, spheric granules is wrapped by agent
Uniform cladding；
5）Repeat 3）-4）Step；
6）Step 5）Solidified afterwards, to step 5 under stirring）Middle addition curing agent, makes material completion of cure, realizes waste residue
Removal.
A kind of stabilisation curing of high poison waste residue, comprises the following steps：
1）Adjust and add acid or alkali under pH, stirring into container so that the water-leach liquor pH of mixed waste residue
It is worth for 7~12；
2）Heavy metal is stabilized, heavy metal stable pharmaceutical is added into the waste residue after regulation pH, and continues stirring, high poison is given up
Heavy metal and medicament to form the compound of indissoluble by fully reacting and stabilized in slag；
3）Once coat, to step 2 under stirring）Plaster of paris powder is added in material after stabilization processes and appropriate
Water, stirs the material shape glomeration particulate matter after terminating；
4）Secondary cladding, to step 3 under stirring）Atoleine is added in material after once coating, makes spheric granules quilt
Paraffin is uniformly coated；
5）Three claddings, to step 4 under stirring）Plaster of paris powder and appropriate water are added in the material of secondary cladding, is stirred
Mix the material after terminating and form larger spherical particle thing；；
6）One-step solidification, by step 5）The particle after finishing is granulated again to dry naturally 1 to 2 day, strengthens consolidating for granule materials
Change intensity；
7）Four claddings, to step 6 under stirring）Material after one-step solidification adds epoxy resin, makes spheric granules by ring
Oxygen tree fat is uniformly coated；
8）To step 7 under secondary solidification stirring）Epoxy curing agent is added in the material of four claddings, makes spherical
Grain surface epoxy resin cure；Firming body after shaping is placed, dries naturally 2-3 days, makes resin solidification complete.
Step 1）Described in high poison waste residue one or more than one kinds of the mercurous, arsenic after broken, chromium, cadmium, cyanide etc.
Powdery waste residue, particle diameter be no more than 3mm.
Step 2）Described in stabilized metal medicament be vulcanized sodium, thiocarbamide, sodium thiosulfate, heavy metal chelant in one kind
Or it is several, dosage is determined according to content of beary metal.
Step 3）First under agitation to step 2）Stabilization agent reaction terminate after material in add plaster of paris powder and
Water is once coated, addition and the step 2 of gypsum）The mass ratio of pending high poison waste residue is 1~3~5, the addition of water
The mass ratio of amount and the gypsum of addition is 1: 3~6.
Step 4）First under agitation to step 3）Granulate and the secondary cladding of atoleine progress, stone are added in the material after terminating
The addition of wax and step 3）The mass ratio of pending high poison waste residue is 1~5: 100.
Step 5）First under agitation to step 4）Plaster of paris powder is added in material after secondary cladding and suitable quantity of water is carried out
Three claddings, the addition of gypsum is 1 with the mass ratio of high poison waste residue：6~10, addition and the step 5 of water）Middle gypsum adds
The mass ratio of dosage is 1: 3~6.
Step 7）First under agitation to step 6）Epoxy resin, which is added, in the material dried after three claddings through body carries out four
Secondary cladding, epoxy resin is bisphenol A-type trade mark E-44, addition and the step 6 of epoxy resin）The mass ratio of material after processing
For 1: 8~10.
Step 8）Epoxy curing agent in secondary solidification is its corresponding aromatic amine curing agent, and epoxy resin is solid
Agent addition and step 7）The mass ratio of epoxy resin is 1: 2~3.
The present invention has positive effect：
The present invention can by the noxious materials such as mercury, arsenic, chromium, cadmium, cyanide by a stable bewitching Ji, lime, gypsum, paraffin,
Epoxy resin is substantially stably solidificated in firming body, so as to follow-up landfill.
The high poison waste residue that the present invention is handled has the larger lower feature of toxicity：According to HJ/T 299-2007《Solid waste
Leaching leaching method sulfonitric method》With GB/T 15555.3-1995《The sulphur of measure diethyl two of solid waste arsenic
For the silver-colored AAS of carbamic acid》、HJ 484—2009《The measure volumetric method and AAS of water quality cyanide》、
GB/T 15555.2-1995《Solid waste copper, zinc, lead, Cadmium detrmination atomic absorption spectrophotometry》、GB/T
15555.6-1995《The measure of the total chromium of solid waste is directly sucked in atomic absorption spectrophotometry》、GB/T
15555.1-1995《The measure cold atomic absorbent spectrophotometry of solid waste total mercury》Determined etc. national standard, the display of its result is high
In malicious waste residue containing mercury, arsenic, chromium, cadmium, cyanide high-risk material, using such as cement solidification, lime of existing method of disposal
Solidification etc. is difficult to reach security landfill requirement.
According to the characteristics of above-mentioned high poison waste residue, the present invention considers alkali to metal and the static stabilization and GB of cyanide
18598-2001《Hazard waste landfill contamination control standard》In pH is 7-12 when being filled to dangerous waste requirement, the present invention it is sour or
Person's alkali adjusts the pH of waste residue, and it is 7~12 to make its leachate pH；Stablized again with heavy metal stable pharmaceutical heavy metal composition
Change, medicament mainly includes machine and inorganic sulphide, sodium thiosulfate, heavy metal chelant etc., stabilization can be formed with metal
The compound of indissoluble；Stabilize after terminating again by gypsum, paraffin, three layers of gypsum cladding, make to form hydrophobic protection outside particle
Layer, prevent firming body fill after in erosion and firming body of the percolate to firming body salinity and metal ooze out；In order that above-mentioned
Protective layer after material one-step solidification is more firm；The material after solidification is subjected to four claddings with epoxy resin, further resistance
Moisture is stopped into salinity enters external environment in firming body and in firming body, has made the stable curings such as heavy metal, cyanide in particle
In, and granular form causes firming body to have enough intensity, it can be ensured that the highly toxic substance after disposal is completely by closed
Reach the effect of long-time stability.
The particles coat major advantage that the present invention is used is mainly manifested in：
1）Solidification effect is good.The multilayer coating structure method effect that the present invention is used is substantially better than common lime and solidified and water
Mud solidifies, especially in terms of the leaching performance of high salinity and heavy metal.Below be for certain simulation high salt (simulated with sodium chloride,
Determine chlorion calculate leaching rate), heavy metal（Simulated with nickel sulfate, determine nickel ion and calculate leaching rate）Waste residue is differently made
Firming body leaches 48h Experimental comparison's data：
| Curing agent | Salinity leaching rate | Leaching rate of heavy metals |
| Cement | 83% | 67% |
| Lime | 94% | 79% |
| Gypsum | 68% | 51% |
| The present invention | 3% | 0.3% |
Above-mentioned effect be once coated according to plaster of paris powder, the secondary cladding of atoleine, the bag of plaster of paris powder three times
Cover, the technique effect that the cladding of epoxy resin four times, epoxy resin cure are obtained；Certainly it is appropriate to change covering material and using bag
The different multiple coating technology of number of times is covered, good technique effect can be also obtained, just not enumerate herein.
2）Save covering material.By covering materials such as gypsum, paraffin, epoxy resin by this surface coated rather than
The method directly mixed not only greatly reduces the usage amount of reagent, and also improves covered effect, the formation resistance of water-repellent layer
Stop etchant in environment and, to the corrosion function of firming body and the loss of salinity, solve the unstable FAQs of firming body.
3）It is convenient and simple for operation.Particles coat only needs to sufficiently uniformly mix material by stirring, and adds successively
Covering, shapes rapidly in the presence of the plaster of paris and water, and forms particle of uniform size.Paraffin and epoxy resin are liquid
Material, is added very convenient.
4）Intensity is good, it is easy to which transport and holding firming body are stable.Due to shape after the completion of gypsum and cured epoxy resin solidification
Into spheric granules be respectively provided with larger intensity and environmental suitability, solve deformation, cracking, transport that block cladding often has
When it is broken the problems such as, it ensure that the stability of firming body, is also convenient for transporting and stores.
Therefore solidification effect of the present invention is good, passes through the four of stable pharmaceutical, double-deck gypsum cladding, paraffin, epoxy resin etc.
Secondary cladding and secondary solidification, highly toxic substance is fully cured in firming body, and the firming body intensity of generation is big, with long-term
Stability, is easy to follow-up landfill operation.
Embodiment
Embodiment 1
Mercuric chloride catalyst catalyst of the high poison waste residue of the present embodiment processing in a large amount of acetylene production polyethylene process,
Carrier is activated carbon, below grain diameter 3mm, by analysis, wherein Hg chloride content 1%.
The processing method of the waste slag containing mercury of the present embodiment comprises the following steps：
It is 11.89 that white lime powder regulation pH value is first added into the beaker equipped with the 100g containing mercury catalyst；It is subsequently added
Industrial thiourea solution（Content 30%）10g is fully mixed thoroughly；Then gesso 30g and 8g water is added, 10min is persistently stirred, stirs
Mix the material terminated in stirring container and form uniform spheric granules；Add 7ml atoleines cladding spheric granules；Continue to add
Enter the granulation of the plaster of paris powder 10g and 3ml water, particle diameter increase；Bisphenol A-type is used after spontaneously drying solidification 1 day（Trade mark E-44）Epoxy
Resin 25ml coats material；Epoxy curing agent 10ml is subsequently added, spheric granules surface epoxy resin is uniform curing；Solidification
Somaization was 0.1mg/L according to mercury content in waste residue leachate is measured after 2 days, met GB 18598-2001《Hazard waste landfill
Contamination control standard》The limit value requirement of middle mercury.
Embodiment 2
The high poison waste residue of the present embodiment processing carrys out the arsenic slag of food phosphoric acid dearsenification workshop, according to GB/T
15555.3-1995《The measure silver diethyl dithio carbamate AAS of solid waste arsenic》Measure waste residue leaching
The content of arsenide is 300ppm in liquid；Solubles content 72%.
The processing method of the arsenic slag of the present embodiment comprises the following steps：
It is 9.4 that white lime powder regulation pH value is first added into the beaker equipped with the arsenic slag 100g for being crushed to granularity 3mm；With
Sodium sulfide solution 7g, the heavy metal chelating agent solution 1g of concentration 10% of concentration 30% are added afterwards；Then gesso 20g and water are added
5ml, lasting stirring, stirs the material shape glomeration particulate matter after terminating；Add 6ml atoleines cladding spheric granules；After
It is continuous to add the granulation of the plaster of paris powder 15g and 5ml water, particle diameter increase；Bisphenol A-type is used after spontaneously drying solidification 1 day（Trade mark E-44）
Epoxy resin 25ml coats material；Epoxy curing agent 10ml is subsequently added, spheric granules surface epoxy resin is uniform curing；
Do not detected after desiccation 2 days according to measuring arsenic in waste residue leachate.Meet GB 18598-2001《Hazard waste landfill contamination control
Standard》It is required that.
Embodiment 3
The present embodiment processing containing cyanogen waste residue of the high poison waste residue from cyanate ester resin workshop, according to HJ 484-
2009《The measure volumetric method and AAS of water quality cyanide》The content for measuring cyanide in waste residue leachate is
59ppm；Solubles content 80%, leachate pH is 10.34.
The processing method of the waste residue containing cyanogen of the present embodiment comprises the following steps：
Gesso 30g and 8ml water are first added into the beaker equipped with the 100g of waste residue containing cyanogen after crushing, is persistently stirred
Mix, the material that stirring terminates in stirred autoclave forms uniform spheric granules；Add 3ml atoleines and coat spherical
Grain；Continuously add the granulation of the plaster of paris powder 15g and 5ml water, particle diameter increase；Bisphenol A-type is used after spontaneously drying solidification 1 day（The trade mark
E-44）Epoxy resin 20ml coats material；Epoxy curing agent 10ml is subsequently added, spheric granules surface epoxy resin is uniform
Solidification；According to the content of cyanide in waste residue leachate is measured it is 0.2ppm after desiccation 2 days, meets GB 18598-2001《It is dangerous
Waste reclamation contamination control standard》The limit value requirement of middle cyanide.
Claims (8)
1. a kind of stabilisation curing of high poison waste residue, it is characterised in that comprise the following steps：
1）Adjust and add acid or alkali under pH, stirring into container so that the water-leach liquor pH value of mixed waste residue is 7
~12；
2）Heavy metal is stabilized, heavy metal stable pharmaceutical is added into the waste residue after regulation pH, and continue in stirring, high poison waste residue
Heavy metal and medicament to form the compound of indissoluble by fully reacting and stabilized；
3）Once coat, to step 2 under stirring）Plaster of paris powder and appropriate water are added in material after stabilization processes, is stirred
Mix the material shape glomeration particulate matter after terminating；
4）Secondary cladding, to step 3 under stirring）Atoleine is added in material after once coating, makes spheric granules by paraffin
Uniform cladding；
5）Three claddings, to step 4 under stirring）Plaster of paris powder and appropriate water, stirring knot are added in the material of secondary cladding
Material after beam forms larger spherical particle thing；
6）One-step solidification, by step 5）Granulate the particle after finishing again to dry naturally 1 to 2 day, the solidification for strengthening granule materials is strong
Degree；
7）Four claddings, to step 6 under stirring）Material after one-step solidification adds epoxy resin, makes spheric granules by asphalt mixtures modified by epoxy resin
Fat is uniformly coated；
8）Secondary solidification, to step 7 under stirring）Epoxy curing agent is added in the material of four claddings, makes spheric granules table
Face epoxy resin cure；Firming body after shaping is placed, dries naturally 2-3 days, makes resin solidification complete.
2. the stabilisation curing of high poison waste residue according to claim 1, it is characterised in that：Step 1）Middle waste residue is broken
The powdery waste residue one or more than one kinds of mercurous, arsenic, chromium, cadmium, cyanide after broken, particle diameter is no more than 3mm.
3. the stabilisation curing of high poison waste residue according to claim 1, it is characterised in that step 2）Middle heavy metal is steady
It is the one or more in vulcanized sodium, thiocarbamide, sodium thiosulfate, heavy metal chelant to determine medicament, and dosage contains according to heavy metal
Amount is determined.
4. the stabilisation curing of high poison waste residue according to claim 1, it is characterised in that step 3）First under agitation
To step 2）Stabilization agent reacts addition gypsum powder and water in the material after terminating and once coated, the addition of gypsum
With step 2）The mass ratio of pending high poison waste residue is 1：3~5, the addition of water is 1: 3 with the mass ratio of the gypsum of addition
~6.
5. the stabilisation curing of high poison waste residue according to claim 1, it is characterised in that step 4）First under agitation
To step 3）Granulate and the secondary cladding of atoleine progress, addition and the step 3 of paraffin are added in the material after terminating）It is pending
High poison waste residue mass ratio be 1~5: 100.
6. the stabilisation curing of high poison waste residue according to claim 1, it is characterised in that step 5）First under agitation
To step 4）Gypsum powder is added in material after secondary cladding and suitable quantity of water carries out three claddings, the addition and high poison of gypsum
The mass ratio of waste residue is 1：6~10, addition and the step 5 of water）The mass ratio of the addition of middle gypsum is 1: 3~6.
7. the stabilisation curing of high poison waste residue according to claim 1, it is characterised in that step 7）First under agitation
To step 6）Epoxy resin is added after one-step solidification in material through drying naturally and carries out four claddings, epoxy resin is bisphenol-A
Type trade mark E-44, addition and the step 6 of epoxy resin）The mass ratio of material after processing is 1: 8~10.
8. the stabilisation curing of high poison waste residue according to claim 1, it is characterised in that step 8）In secondary solidification
Epoxy curing agent be its corresponding aromatic amine curing agent, epoxy curing agent addition and step 7）Middle epoxy
The mass ratio of resin is 1: 2~3.
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| CN104761113B (en) * | 2015-04-28 | 2017-06-13 | 江苏理工学院 | Stabilization and solidification method of electroplating sludge |
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| CN108529805B (en) * | 2015-07-10 | 2021-04-27 | 江苏理工学院 | Treatment method of hazardous waste landfill leachate |
| CN105537247B (en) * | 2016-01-27 | 2018-02-09 | 湖南有色金属研究院 | A kind of method for solidifying arsenic-containing waste residue using industrial residue |
| CN106862235B (en) * | 2017-02-14 | 2019-05-24 | 武汉深能环保新沟垃圾发电有限公司 | A kind of on-line checking heavy metal solid waste method for innocent treatment |
| CN106955888B (en) * | 2017-03-30 | 2019-10-29 | 北京高能时代环境技术股份有限公司 | The stabilization method of waste residue containing Cr, Cr contaminated soil or combinations thereof |
| CN108217896A (en) * | 2018-01-24 | 2018-06-29 | 东莞市升佳净水材料有限公司 | A kind of polymerization alkali and preparation method thereof |
| CN109013669B (en) * | 2018-09-28 | 2021-07-06 | 长春黄金研究院有限公司 | Method for treating tailings of cyanided tailing pond |
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| CN111228711B (en) * | 2020-01-15 | 2021-08-06 | 扬州杰嘉工业固废处置有限公司 | Method for stabilizing and curing mercury-containing waste salt slag by using petrochemical waste alkali slag |
| CN112458290B (en) * | 2020-11-06 | 2022-08-12 | 金川集团股份有限公司 | Harmless treatment method for solid waste of nickel-containing iron slag |
| CN113953305B (en) * | 2021-09-29 | 2023-06-23 | 云南驰宏锌锗股份有限公司 | Harmless treatment method for polyethylene plastic with arsenic sulfide slag |
| CN113996631A (en) * | 2021-09-29 | 2022-02-01 | 云南驰宏锌锗股份有限公司 | Method for solidifying calcium arsenate slag cement |
| CN114425555B (en) * | 2022-01-27 | 2023-03-14 | 山西丽浦创新科技有限公司 | Low-carbon environment-friendly resource utilization process and system for high-mercury cyanide-containing gold separation waste residues |
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| US5569811A (en) * | 1994-10-06 | 1996-10-29 | Dean; Miles W. | Method for isolating, immobilizing and rendering waste non-leachable |
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| CN1301929C (en) * | 2003-05-07 | 2007-02-28 | 河海大学 | Composite silt solidified material |
| FR2933099B1 (en) * | 2008-06-30 | 2011-11-25 | Spado Sa | COATING COMPOSITION FOR THE STORAGE OF TOXIC WASTES FOR HEALTH AND / OR ENVIRONMENT WITHOUT AROMATIC CURING AGENT |
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| CN106734071B (en) * | 2014-06-27 | 2019-05-28 | 江苏理工学院 | Method for treating cyanogen-containing waste residue by bleaching powder |
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