CN107649483B - A kind of method that low temperature thermal desorption amalgamation stablizes the mercurous dangerous waste residue of improvement - Google Patents
A kind of method that low temperature thermal desorption amalgamation stablizes the mercurous dangerous waste residue of improvement Download PDFInfo
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- CN107649483B CN107649483B CN201710736348.0A CN201710736348A CN107649483B CN 107649483 B CN107649483 B CN 107649483B CN 201710736348 A CN201710736348 A CN 201710736348A CN 107649483 B CN107649483 B CN 107649483B
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- waste residue
- mercury
- dangerous waste
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- 239000002699 waste material Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 100
- 238000003795 desorption Methods 0.000 title claims abstract description 25
- 238000005267 amalgamation Methods 0.000 title claims abstract description 14
- 230000006872 improvement Effects 0.000 title description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 102
- 239000003864 humus Substances 0.000 claims abstract description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims abstract description 13
- 239000002734 clay mineral Substances 0.000 claims abstract description 8
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 238000004073 vulcanization Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000009938 salting Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 16
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052900 illite Inorganic materials 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 5
- 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 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 abstract description 25
- 238000011105 stabilization Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 13
- 238000012545 processing Methods 0.000 abstract description 11
- 238000009835 boiling Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 239000002689 soil Substances 0.000 description 36
- 230000008569 process Effects 0.000 description 25
- 238000002386 leaching Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 9
- 239000002910 solid waste Substances 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 240000007124 Brassica oleracea Species 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- -1 alkyl mercury Chemical compound 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- CDEIGFNQWMSEKG-UHFFFAOYSA-M chloro-[4-[(2-hydroxynaphthalen-1-yl)diazenyl]phenyl]mercury Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C([Hg]Cl)C=C1 CDEIGFNQWMSEKG-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FAYYUXPSKDFLEC-UHFFFAOYSA-L calcium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Ca+2].[O-]S([O-])(=O)=S FAYYUXPSKDFLEC-UHFFFAOYSA-L 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000783 metal toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940091258 selenium supplement Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011655 sodium selenate Substances 0.000 description 1
- 229960001881 sodium selenate Drugs 0.000 description 1
- 235000018716 sodium selenate Nutrition 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of low temperature thermal desorption amalgamations to stablize the method for administering mercurous dangerous waste residue, mercurous dangerous waste residue is first passed through the low-boiling inorganic reference state mercury of organically combine state mercury and part in the mercurous dangerous waste residue of low temperature thermal desorption processing removal by this method, then vulcanization salting liquid is added and carries out vulcanization reaction, adds ferrous salt precipitating excess S2‑, it adds clay mineral and humus is adsorbed, add pH adjusting agent and adjust mercurous danger waste residue pH to 6~7, conserve 3 days or more.The removal of low boiling point form mercury in mercurous dangerous waste residue may be implemented in this method, the stabilisation of higher boiling form mercury, substantially reduce the migration of mercury in mercurous dangerous waste residue, this method effectively can be removed and be stabilized solidification to variform mercury in waste slag containing mercury, and stabilization effect is good, low energy consumption, the period is short, the medicament stock source that this method uses is wide, at low cost, is conducive to be widely applied.
Description
Technical field
It is the present invention relates to mercurous dangerous controlling waste residue method, in particular to a kind of to be stablized by low temperature thermal desorption amalgamation
The method for administering mercurous dangerous waste residue, belongs to solid waste treatment technical field.
Background technique
In recent years, with the rapid development of industrial or agricultural, mercury is largely discharged in the production and use process, " national waste
Register " mercurous waste has been classified as HW29 class waste.Mercurous danger waste residue is primarily referred to as mercury ore exploitation smelting, chlorine industry, electricity
The mercurous solid waste that the industries such as pond and the thermometer manufacturing generate.These mercurous waste mercury contents are high, if improper conduct oneself well
It sets, it will pollute atmosphere, Soil Surrounding, surface water and underground water, the mercury and mercuric compounds in soil can be entered by food chain
Human body generates greatly harm to human body.Therefore, suitable method is selected to carry out the safe disposal of mercurous dangerous waste residue, to me
State's environmental improvement, protection human health are of great significance.
Mercury can be divided by chemical form: mercury metal, inorganic reference state mercury, organically combine state mercury.The mercury of inorganic states mainly with
The Hg of free state2+And Hg+Form exists, wherein Hg+It can form slightly solubility mercury salt, and Hg2+It is mostly soluble mercury salt.It is organic
The mercury of chemical combination states of matter based on short-chain alkyl mercury, mercury with other small molecules or large biological molecule covalently to cooperate, with ligand to match
It is reference state that position or supermolecule form, which combine the state that is formed by, and organomercurial compound is more sensitive to light and heat, has higher
Volatility.
Currently, mercuric pollution treatment technology mainly has heat treating process, curing/stabilizing method, elution method, electro reclamation, life
Object repairing method etc..These methods have respective advantage and disadvantage, most study application at present it is most be still curing/stabilizing method with
Heat treating process.
Curing/stabilizing method is by physics and chemical action come the technical combinations of pollutant in immobilized waste.It stabilizes
It can occur chemically or physically react with the heavy metal contaminants in waste residue with solidified reagents, be allowed to be converted into and not readily dissolve, migrate
Ability is weak, the smaller form of toxicity.Currently, it is less specifically for the relevant report of mercurous dangerous waste residue stabilization processes, but needle
The technique study of stabilization agent and reparation to mercury contaminated soil is more, as Chinese patent (CN105414166A) discloses one
The liftoff topsoil plough of mercury contaminated soil is specifically turned over, air-dries, grinds, is sieved, obtain by the restorative procedure of kind mercury contaminated soil
To pretreated topsoil；The passivator that will be made of bentonite, hydroxyapatite, ATS (Ammonium thiosulphate) and calcium hydroxide,
It is mixed well with processed topsoil, places the passivation until mercury content 70% is fixed in topsoil 10-20 days
Agent reparation is completed；Topsoil is flattened to and is planted upper India cabbage mustard, it is in India cabbage mustard growth animated period that calcium thiosulfate is molten
It is simultaneously uniformly sprayed onto India's cabbage mustard root system surrounding soil by Yu Shuizhong, finally gathers in India cabbage mustard.Chinese patent (CN
105598145 A) a kind of in-situ remediation method of mercury contaminated soil is disclosed, this method selects charcoal, calcium polysulfide and Asia
Three kinds of passivator of sodium selenate can be effectively improved Soil Micro-environment after being applied in soil using charcoal mixing, in meta-alkali and
In the stronger soil of reproducibility, the migration of mercury is substantially reduced, organic official with powerful specific surface and porous structure, complexity
The mercury in a large amount of sticking soil of charcoal and energy that can be rolled into a ball；The mine of mercury can further be promoted by pouring calcium polysulfide solution in the soil
Change, its root soil microenvironment bioactivity is reinforced after planting crops, and selection applies sodium selenite solution, utilizes selenium and mercury
Antagonistic effect weakens its biological effectiveness.After adding three kinds of passivation processing, mercury content in crops is significantly reduced.In
State's patent (104998894 A of CN) discloses a kind of mercury contaminated soil solidification and stabilization method, including villaumite adds process, pH
Adjust process, mixed processes, addition activator process, digestion molding procedure and break process process.This method can be to difference
The mercury contaminated soil of pollution level carries out solidification and stabilization, can also cooperate with other huge sum of moneys in solidification and stabilization contaminated soil
Belong to.Product after solidification and stabilization can backfill or for other purposes.Although these methods of existing report are to a certain degree
On may be implemented the static stabilization of mercury in mercury contaminated soil, but the long processing period of these methods, and being difficult to adapt to a variety of
The stabilisation of form mercury, stabilization effect are poor.
Heat treating process is that the mercury in soil is heated to enough temperature, makes mercury with gas by direct or indirect heat exchange
The form of state is volatilized from soil or isolated process.Heat treating process demercuration is the method that can effectively remove mercury in soils, root
It, can be using high temperature thermal desorption (600 DEG C~1000 DEG C) and low temperature thermal desorption according to the existence of mercury in soils and the content of mercury
Two kinds of (200 DEG C~600 DEG C).There are many kinds of forms in the soil for mercury, comprising: Hg, HgCl2、Hg2Cl2, HgO, HgS and with soil
Mercury, organically combine state mercury of the inorganic combination of earth etc., Hg, HgCl2、Hg2Cl2Etc. forms mercury boiling point it is lower, Low Temperature Thermal can be used
Desorption method is handled and is easier to remove, and the mercury boiling point of the forms such as HgO, HgS is very high, it is necessary to be heated to 700~800
DEG C even higher temperature, and heat treatment time can just be effectively removed commonly greater than 1 hour, therefore, needed for high temperature rehabilitating soil
Energy consumption is higher, and especially a large number of studies show that, heat treatment temperature is higher than 350 DEG C, destroys to the structure of soil serious.Currently, needle
It is very more to the research of mercury contaminated soil thermal desorption reparation, but most of is high temperature thermal desorption method, the research of low temperature thermal desorption compared with
Few, Chinese patent (CN103056157A) discloses a kind of low temperature pyrogenation processing method and device of mercury contaminated soil.It should
Patent is by mercury contaminated soil investment pyrolysis installation of the moisture content lower than 10%, and the initial temperature of pyrolysis installation is 250 DEG C, 30
400 DEG C are heated in minute, mercury in soils content is still higher after this method is repaired, and is much higher than " soil environment quality mark
It is quasi- " (GB15618-1995) grade III Standard, repairing effect is undesirable.Chinese patent (CN103785682A) discloses a kind of utilization
The method that organic acid promotes mercury contaminated soil heat treatment to repair, this method first by organic acid and mercury contaminated soil after mixing again
It puts into pyrolysis installation, is arranged 400~500 DEG C of pyrolysis temperature, handle the time 20~60 minutes, after this method is repaired in soil
Mercury content can be lower than " standard of soil environment quality " (GB15618-1995) grade III Standard, although this method passes through addition organic acid
Etc. can suitably reduce pyrolysis temperature, the removal efficiency of mercury is improved, but this method pyrolysis temperature is still at 400 DEG C or more.
Due to the enrichment slag that mercurous dangerous waste residue is mercury, mercury content is significantly larger than general mercury contaminated soil, existing place
The method of reason mercury contaminated soil is difficult to adapt in the processing of mercurous dangerous waste residue, also and is had no in the prior art using low temperature pyrogenation
Technology and medicament stabilization technique combine the relevant report of mercury in efficient stable waste residue.The present invention is steady by low temperature pyrogenation and medicament
Surely want to combine the mercury in the mercurous dangerous waste residue of efficient stable, substantially reduce its Leaching, meeting it, " hazard waste landfill is dirty
Dye control standard " the concentration limitation of landfill yard is allowed access into (GB18598-2001).
Summary of the invention
For defect existing for the methods of stabilization processes of mercurous dangerous waste residue in the prior art, the purpose of the present invention is
Be to provide it is a kind of pyrolysis technique and stabilization technology are combined, to realize having for variform mercury in mercurous dangerous waste residue
Effect removing and efficient stable, and low energy consumption, the lower-cost method for administering mercurous dangerous waste residue.
In order to achieve the object of the present invention, stablize the present invention provides a kind of low temperature thermal desorption amalgamation and administer mercurous danger
The method of dangerous waste residue, method includes the following steps:
1) mercurous dangerous waste residue is carried out air-dried, is broken into fine grained；
2) fine grained is heat-treated at a temperature of being placed in 200~400 DEG C；
3) vulcanization salting liquid is added in heat treated fine grained and carries out vulcanization reaction；
4) ferrous salt precipitating excess S is added2-；
5) it adds clay mineral and humus is adsorbed；
6) it is eventually adding pH adjusting agent and adjusts waste residue pH to 6~7, conserve 3 days or more.
Preferred scheme, the mercurous dangerous waste residue are air-dried to moisture content lower than 10%, are crushed to partial size less than 3cm.It will
Mercurous danger waste residue is dry and is crushed to the rate of volatilization that appropriate granularity is conducive to improve mercury.
Preferred scheme, the time of the heat treatment are 20~60 minutes；Preferred heat treatment time is 25~
35min.Technical solution of the present invention handles the short period at low temperature, can reduce energy consumption.
Preferred scheme, the sulphurizing salt are measured with 1 times or more of mercury mole in mercurous dangerous waste residue.Preferred vulcanization
Salt includes at least one of vulcanized sodium, ammonium sulfide, potassium sulfide, more preferably vulcanized sodium.
Preferred scheme, ferrous salt is with 0.5%~2% metering of mercurous dangerous slag quality.Preferably ferrous salt includes
At least one of ferrous sulfate, frerrous chloride, ferrous nitrate, more preferably ferrous nitrate.
Preferred scheme, clay mineral and humus are with 2%~10% metering of mercurous dangerous slag quality.It is preferred viscous
Native mineral substance includes at least one of bentonite, zeolite, sepiolite, illite, montmorillonite, concave convex rod, more preferably illite
And/or montmorillonite.The mass ratio of more preferably scheme, clay mineral and humus is 1~3:1.
Preferred scheme, pH adjusting agent is to adjust the pH of mercurous dangerous waste residue in 6~7 meterings.Preferred pH adjusting agent packet
Include at least one of calcium oxide, calcium hydroxide, calcium carbonate.
Preferred scheme, heat treatment temperature is more preferably 350~400 DEG C in step 2).
Preferred scheme, in step 6), curing time is 3~7 days.
Mercurous dangerous waste residue is pre-processed using low temperature thermal decomposition method first in technical solution of the present invention, In
Mercurous dangerous waste residue is heat-treated at a temperature of 200~400 DEG C, the big portion in the mercurous dangerous waste residue that can quickly, effectively volatilize
Divide volatile mercury, such as HgCl2、Hg2Cl2And the realizations such as organic mercury volatilization, while can also be by the mercurous compound of hardly possible volatilization
It is oxidized to bivalent mercury, and bivalent mercury is easier to respect to monovalence mercury and S2-Form stable HgS.
Sulphurizing salt of the invention is as the reagent for stablizing mercury, in order to guarantee the Hg in reaction system2+It is heavy to generate completely
It forms sediment, the additional amount of sulphurizing salt is at least 1:1 with respect to the mole ratio of mercury element in waste residue.
Effect there are three ferrous salt of the invention is main, first, it can be by excess S present in reaction system2-Precipitating is formed,
With prevent mercuric sulphide from returning molten, second, Fe2+Oxidation generate ferric hydrous oxide colloid, recycle its adsorb and co-precipitation into
The one step removal of mercury, third, excessive Fe2+Presence be in waste residue environment under reducing condition, in this way be more conducive to mercuric sulphide generation.
Clay mineral and humus of the invention has the function of synergistic sorption Trace Mercury.
PH adjusting agent of the invention to control waste residue pH 6~7, be conducive under conditions of pH is 6~7 entire
System and mercuric sulphide are stabilized.
Since under normal circumstances, mercury metal, monovalence mercury and organically combine state mercury are more difficult stabilized by chemical agent,
Technical solution of the present invention uses the mercury of low boiling point form in the mercurous dangerous waste residue of low temperature thermal desorption processing removal first, simultaneously will
The mercurous compound of hardly possible volatilization is oxidized to bivalent mercury, then stablizes remaining mercury by chemical agent, greatly improves stable effect
Rate.In stabilization process, sulphurizing salt and Hg are utilized2+Reaction generates stable mercuric sulphide precipitating, but one in actual process
As need to be added excessive S2-, to guarantee mercury whole immobilization, but if sulphur excessively the larger HgS that will lead to further generates one
The soluble HgS of kind2-, dissolve again.And excessive S can be made by adding ferrous salt2-Formation FeS precipitating, while Fe2+It can also
Oxidation generates ferric hydrous oxide, and ferric hydrous oxide can pass through adsorption and the co-precipitation removal of mercury；In addition, Fe2+'s
In the presence of waste residue environment is under reducing condition, it is more conducive to the generation of mercuric sulphide in this way, and is very stably present in for a long time useless
In slag.But excessive Fe2+New problem can be caused, hydrolysis is easy to happen and releases H+Ion makes waste residue souring: 4Fe2++O2+
6H2O→4FeOOH+8H+, waste residue pH is adjusted by the way that alkaline matter is added, keeps waste residue pH finally stable between 6~7, this is mercury
The best pH of stablizing effect.In addition, the addition of clay pit species and humus can the remaining mercury of synergistic sorption, further consolidate steady
Surely change effect.
Stabilizer of the invention includes the materials such as sulphurizing salt, ferrous salt, clay pit species and humus, is solid particle
Shape is powdered, and sulphurizing salt is first added in when use, stirs evenly and adds ferrous salt after reacting a period of time, is eventually adding viscous
The adsorbent materials such as native mineral substance, humus are made sure to keep in mind after can not mixing to be added together, and otherwise sulphurizing salt can react with ferrous salt
And it reduces effective component and stablizing effect is caused to decline.
PH conditioner of the invention is the alkaline matters such as calcium oxide, calcium hydroxide, calcium carbonate, is solid powdery.
The method of mercurous dangerous controlling waste residue of the invention, specifically includes step in detail below:
(1) the mercurous dangerous waste residue of mercury air-dried to moisture content lower than 10%, be crushed to partial size less than 3cm, removed biggish
The sundries such as stone；
(2) it will air-dry, in broken waste particle investment Equipment for Heating Processing, and be arranged 200~400 DEG C for the treatment of temperature, place
The reason time 20~60 minutes, is heated；
(3) the mercurous dangerous waste residue after being heat-treated is come out by discharge port, by the mercury condensing recovery in tail gas, then through active carbon
The remaining mercury of Adsorption；
(4) sulphurizing salt is added after being cooled to room temperature in the mercurous dangerous waste residue after being heat-treated, and sulphurizing salt can be with the shape of solid
Formula is added, and can also be added, be stirred evenly with wiring solution-forming, makes the Hg in mercurous dangerous waste residue2+It is fully converted to HgS precipitating；
(7) ferrous salt is added, stirs evenly, makes excessive S2-Form FeS precipitating, while extra Fe2+Oxidation generates water
Ferriferous oxide is closed, then passes through ferriferous oxide adsorption and the further removal of mercury of co-precipitation, and Fe2+Presence make waste residue ring
Border is under reducing condition, is more conducive to the generation of mercuric sulphide in this way, and highly stable is present in waste residue for a long time；
(8) clay pit species and humus is added, stirs evenly, further consolidates stabilization effect；
(9) alkaline matter is added to stir evenly, the pH to 6~7 of waste residue is adjusted, if the pH of waste residue is after above-mentioned steps
Through in 6~7 ranges, then this step can be exempted from, finally conserve 3~7 days.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) efficient removal and stabilisation of various forms mercury in mercurous dangerous waste residue may be implemented in administering method of the invention.
2) present invention administers mercurous dangerous waste residue using the stable method of low temperature thermal desorption amalgamation, in heat treatment item
Most of low boiling point mercury in mercurous dangerous waste residue can be removed under part, reduced the consumption of subsequent stabilization process Chinese medicine, improved
Stabilization efficiency can also avoid the disadvantage that general thermal desorption method temperature is high, energy consumption is high.Therefore, low temperature thermal desorption of the invention
Combining chemically stable method not only can make the mercury of various forms in mercurous dangerous waste residue obtain fast eliminating and stabilization processes,
Stabilization efficiency is greatly improved, and energy consumption can be reduced, reduces medicament use cost.
3) stable pharmaceutical raw material sources of the invention it is wide, it is at low cost, be conducive to promote the use of.
4) mercurous dangerous waste residue may be implemented by simple operations step in the method for mercurous dangerous controlling waste residue of the invention
The fast eliminating of middle variform mercury and efficiently fixation, general maintenance 3 days, can reach preferable stablizing effect, by " solid is useless
Object Leaching leaching method horizontal vibration method " (HJ557-2009) leached, and the concentration of mercury is lower than in leachate
0.25mg/L meets the concentration limit that landfill yard is allowed access into " hazard waste landfill contamination control standard " (GB18598-2001)
System.
5) stabilizer of the invention fixes the mercury in mercurous dangerous waste residue by chemical stabilization, independent of microorganism
Activity, thus insensitive to heavy metal toxicity, waste residue property, applicability is wide.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Embodiment 1
Tongren district Guizhou Province mercury ore is taken to smelt the waste residue left, mercury content is up to 1150mg/kg in waste residue, according to " solid is useless
Object Leaching leaching method sulfonitric method " (HJ/T299-2007) leach taken slag specimen, mercury in leachate
Concentration is 3.25mg/L, is more than the concentration limit of mercury in " hazardous waste judging standard leaching characteristic identification " (GB5085.3-2007)
Value 0.1mg/L, this waste slag containing mercury are hazardous waste.According to " solid waste Leaching leaching method horizontal vibration method "
(HJ557-2009) taken slag specimen is leached, the concentration of mercury is 1.68mg/L in leachate, is more than " hazard waste landfill
Contamination control standard " concentration limit 0.25mg/L that landfill yard is allowed access into (GB18598-2001), it need to carry out stabilizing solid
Change processing reaches admissions criteria.
(1) mercurous dangerous waste residue air-dried to moisture content lower than 10%, be crushed to partial size less than 3cm；
(2) it weighs and is heated in pretreated waste residue 500g investment annealing device, treatment temperature 350 is set
DEG C, it handles the time 30 minutes.Waste residue after heat treatment is come out by discharge port, by the mercury condensing recovery in tail gas, then through active carbon
The remaining mercury of Adsorption, tail gas after processing mercury content meet " discharge standard of air pollutants " (GB16297-
1996) prescribed limits in.
(3) waste residue after being heat-treated is cooled to the sodium sulfide solution of addition 5% after room temperature, and the additional amount of vulcanized sodium is sulphur member
The mole ratio of element and mercury element in waste residue is 1:1, is stirred evenly, and reacts 30min, makes the Hg in waste residue2+It is fully converted to HgS
Precipitating；
(4) ferrous nitrate is added, additional amount is the 1% of slag quality, is stirred evenly, and 15min is reacted；
(5) illite, montmorillonite and humus is added, the mass ratio between three is 1:1:1, and total additional amount is waste residue matter
The 5% of amount, stirs evenly；
(6) calcium hydroxide is added to stir evenly, the pH to 6-7 of waste residue is adjusted, if the pH of waste residue is after above-mentioned steps
Through in 6-7 range, then this step can be exempted from；
(7) it is carried out after conserving 3 days according to " solid waste Leaching leaching method horizontal vibration method " (HJ557-2009)
It leaches, the concentration of mercury is 0.06mg/L in leachate, meets " hazard waste landfill contamination control standard " (GB18598-
2001) the concentration limitation 0.25mg/L of landfill yard is allowed access into.
Comparative example 1
Waste residue same as Example 1 is taken, and through identical air-dried, break process, without thermal desorption processing, next
Stabilization step it is same as Example 1, maintenance 3 days after according to " solid waste Leaching leaching method horizontal vibration method "
(HJ557-2009) it being leached, the concentration of mercury is 0.58mg/L in leachate, much higher than the value in embodiment 1, and cannot
Meet the concentration limitation 0.25mg/ that landfill yard is allowed access into " hazard waste landfill contamination control standard " (GB18598-2001)
L。
Comparative example 2
Waste residue same as Example 1 is taken, and through identical air-dried, break process.Weigh pretreated waste residue 500g
Heat treatment same as Example 1 is carried out in annealing device, waste residue after heat treatment is cooled to after room temperature while being added
Sodium sulfide solution, ferrous nitrate, illite, montmorillonite and humus, additional amount is same as Example 1, is stirring evenly and then adding into
Calcium hydroxide adjusts pH to 6-7, according to " solid waste Leaching leaching method horizontal vibration method " (HJ557- after maintenance 3 days
2009) it is leached, the concentration of mercury is 0.49mg/L in leachate, much higher than the value in embodiment 1, and is not able to satisfy " danger
Dangerous waste reclamation contamination control standard " the concentration limitation 0.25mg/L of landfill yard is allowed access into (GB18598-2001).
Embodiment 2
Waste residue same as Example 1 is taken, and through identical air-dried, break process.Weigh pretreated waste residue 500g
It puts into annealing device, is 350 DEG C in setting treatment temperature, the processing time is respectively 20,30,40,50,60 minutes conditions
Under heated.Waste residue after heat treatment carries out stabilization processes same as Example 1, maintenance 3 after being cooled to room temperature
It is leached after it according to " solid waste Leaching leaching method horizontal vibration method " (HJ557-2009), mercury in leachate
Concentration be respectively 0.17mg/L, 0.06mg/L, 0.01mg/L, 0.006mg/L, ND, be able to satisfy " hazard waste landfill pollution
Control standard " the concentration limitation 0.25mg/L of landfill yard is allowed access into (GB18598-2001).
Embodiment 3
Waste residue same as Example 1 is taken, and through identical air-dried, break process.Weigh pretreated waste residue 500g
It puts into annealing device, is 30 minutes in the setting processing time, treatment temperature is respectively 200,250,300,350,400 DEG C
Under the conditions of heated.Waste residue after heat treatment carries out stabilization processes same as Example 1 after being cooled to room temperature, supports
Shield is leached after 3 days according to " solid waste Leaching leaching method horizontal vibration method " (HJ557-2009), leachate
The concentration of middle mercury is 0.23mg/L, 0.18mg/L, 0.11mg/L, 0.06mg/L, ND, is able to satisfy " hazard waste landfill pollution
Control standard " the concentration limitation 0.25mg/L of landfill yard is allowed access into (GB18598-2001).
Embodiment 4
Waste residue same as Example 1 is taken, and through identical air-dried, break process.Weigh pretreated waste residue 500g
Heat treatment same as Example 1 is carried out in annealing device, waste residue after heat treatment is added 5% after being cooled to room temperature
Potassium sulfide solution, the additional amount of potassium sulfide are that the mole ratio of mercury element in element sulphur and waste residue is 1:1, stir evenly, react
Frerrous chloride is added in 30min, and additional amount is the 1% of slag quality, stirs evenly, and reacts 15min；Be added bentonite, zeolite and
Humus, the mass ratio between three is 1:1:1, and total additional amount is the 5% of slag quality, is stirred evenly；Next adjust pH's
Step is same as Example 1, according to " solid waste Leaching leaching method horizontal vibration method " (HJ557- after maintenance 3 days
2009) it is leached, the concentration of mercury is 0.12mg/L in leachate, higher than the value in embodiment 1, but is able to satisfy " dangerous useless
Object fills contamination control standard " the concentration limitation 0.25mg/L of landfill yard is allowed access into (GB18598-2001).
Claims (8)
1. a kind of low temperature thermal desorption amalgamation stablizes the method for administering mercurous dangerous waste residue, it is characterised in that: including following step
It is rapid:
1) mercurous dangerous waste residue is carried out air-dried, is broken into fine grained；
2) fine grained is heat-treated at a temperature of being placed in 200~400 DEG C；
3) vulcanization salting liquid is added in heat treated fine grained and carries out vulcanization reaction；The sulphurizing salt is with mercurous dangerous waste residue
1 times or more of middle mercury mole measures；
4) ferrous salt precipitating excess S is added2-；The ferrous salt is with 0.5%~2% metering of mercurous dangerous slag quality；
5) it adds clay mineral and humus is adsorbed；
6) it is eventually adding pH adjusting agent and adjusts waste residue pH to 6~7, conserve 3 days or more.
2. a kind of low temperature thermal desorption amalgamation according to claim 1 stablizes the method for administering mercurous dangerous waste residue,
Be characterized in that: the mercurous dangerous waste residue is air-dried to moisture content lower than 10%, is crushed to partial size less than 3cm.
3. a kind of low temperature thermal desorption amalgamation according to claim 1 stablizes the method for administering mercurous dangerous waste residue,
Be characterized in that: the time of the heat treatment is 20~40 minutes.
4. a kind of low temperature thermal desorption amalgamation according to claim 1,2 or 3 stablizes the side for administering mercurous dangerous waste residue
Method, it is characterised in that: the sulphurizing salt includes at least one of vulcanized sodium, ammonium sulfide, potassium sulfide.
5. a kind of low temperature thermal desorption amalgamation according to claim 1,2 or 3 stablizes the side for administering mercurous dangerous waste residue
Method, it is characterised in that: the ferrous salt includes at least one of ferrous sulfate, frerrous chloride, ferrous nitrate.
6. a kind of low temperature thermal desorption amalgamation according to claim 1,2 or 3 stablizes the side for administering mercurous dangerous waste residue
Method, it is characterised in that: the clay mineral and humus are with 2%~10% metering of mercurous dangerous slag quality；The clay
Mineral include at least one of bentonite, zeolite, sepiolite, illite, montmorillonite, concave convex rod.
7. a kind of low temperature thermal desorption amalgamation according to claim 1,2 or 3 stablizes the side for administering mercurous dangerous waste residue
Method, it is characterised in that: the pH adjusting agent is to adjust the pH of mercurous dangerous waste residue in 6~7 meterings；The pH adjusting agent includes oxygen
Change at least one of calcium, calcium hydroxide, calcium carbonate.
8. a kind of low temperature thermal desorption amalgamation according to claim 1,2 or 3 stablizes the side for administering mercurous dangerous waste residue
Method, it is characterised in that: curing time is 3~7 days.
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