CN105754610A - Heavy metal cadmium, lead and arsenic compound contaminated soil restorative agent and preparation method thereof - Google Patents
Heavy metal cadmium, lead and arsenic compound contaminated soil restorative agent and preparation method thereof Download PDFInfo
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- CN105754610A CN105754610A CN201610079927.8A CN201610079927A CN105754610A CN 105754610 A CN105754610 A CN 105754610A CN 201610079927 A CN201610079927 A CN 201610079927A CN 105754610 A CN105754610 A CN 105754610A
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- heavy metal
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- metal cadmium
- bamate
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- 239000002689 soil Substances 0.000 title claims abstract description 105
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 33
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 24
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001495 arsenic compounds Chemical class 0.000 title abstract 5
- 150000002611 lead compounds Chemical class 0.000 title abstract 5
- 239000002028 Biomass Substances 0.000 claims abstract description 31
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims abstract description 27
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 26
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940080314 sodium bentonite Drugs 0.000 claims abstract description 26
- 229910000280 sodium bentonite Inorganic materials 0.000 claims abstract description 26
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 26
- 239000011975 tartaric acid Substances 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 25
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 19
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 229910052785 arsenic Inorganic materials 0.000 claims description 17
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 238000009418 renovation Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 238000011109 contamination Methods 0.000 claims description 12
- 239000010902 straw Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 238000007158 vacuum pyrolysis Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 229910021647 smectite Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000003610 charcoal Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 31
- 238000002386 leaching Methods 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 12
- 239000003814 drug Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 6
- 239000002910 solid waste Substances 0.000 description 6
- 230000007306 turnover Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 238000005067 remediation Methods 0.000 description 4
- 238000003900 soil pollution Methods 0.000 description 4
- 238000010668 complexation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 1
- 206010033307 Overweight Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229960002643 clofenotane Drugs 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 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
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 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 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005186 environmental transport Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000020825 overweight Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a heavy metal cadmium, lead and arsenic compound contaminated soil restorative agent. The heavy metal cadmium, lead and arsenic compound contaminated soil restorative agent is prepared from the following components in percentage by weight: 30-50 percent of biomass charcoal, 5-10 percent of diatomite, 5-10 percent of sodium bentonite, 5-10 percent of activated aluminum oxide, 10-20 percent of dithiocar-bamate, 5-10 percent of ethylenediaminetetraacetic acid, 5-10 percent of tartaric acid, 5-10 percent of polyacrylamide and 5-10 percent of sodium dodecyl sulfate. A preparation method for the heavy metal cadmium, lead and arsenic compound contaminated soil restorative agent comprises the following steps: mixing the biomass charcoal, diatomite, sodium bentonite, activated aluminum oxide, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide and sodium dodecyl sulfate in mass proportion to obtain a mixture; and adding the dithiocar-bamate into the mixture in corresponding mass proportion to sufficiently mix uniformly, thereby obtaining the prepared soil restorative agent. The prepared soil restorative agent has good effect in restoring the cadmium, lead and arsenic compound contaminated soil.
Description
Technical field:
The invention belongs to soil pollution recovery technique field, be specifically related to a kind of heavy metal cadmium, lead, arsenic combined contamination soil renovation agent and preparation method thereof.
Background technology:
" whole nation Soil Pollution Investigation publication " display within 2014, is announced: whole nation soil environment situation totally allows of no optimist according to Environmental Protection Department and Ministry of Land and Resources; some areas soil pollution is heavier; arable soil environmental quality causes anxiety, industry and mining discarded ground soil environment outstanding problem.The human activity such as industry and mining, agricultural and Environmental Background Values of Soils height are to cause soil pollution or the main cause exceeded standard.The whole nation total exceeding standard rate of soil is 16.1%, the most slightly, slightly, moderate and serious pollution point position ratio be respectively 11.2%, 2.3%, 1.5% and 1.1%.Pollution type is based on inorganic type, and organic type takes second place, and compound pollution proportion is less, and an inorganic pollution figure place that exceeds standard accounts for the 82.8% of all super punctuation bits.
From polluting in terms of distribution situation, soils in south china pollutes and overweights the north；The subregion soil contamination problem such as Yangtze River Delta, the Delta of the Pearl River, Northeastern rust belt are the most prominent, southwest, variable charge soil heavy metals exceeding standard scope bigger；Cadmium, hydrargyrum, arsenic, 4 kinds of level of inorganic contaminants distributions of lead present the situation gradually risen from northwest to the southeast, from northeast to southwestward.
Major pollutants are cadmium, nickel, copper, arsenic, hydrargyrum, lead, clofenotane and polycyclic aromatic hydrocarbon.If being as the criterion with second national land investigation result, China's arable land latest data is 2,030,770,000 mu and calculates, and the cultivated area of middle serious pollution accounts for 2.9%, has reached 58,890,000 mu.
Administering method currently for heavy metal pollution of soil mainly has immobilization/stabilisation, elution method, washes local method, electromotion repairing technique method, chemical reduction method, phytoremediation, microorganism remediation, totally there is the problems such as remediation efficiency is low, processing cost is high.The quantities such as traditional restorative procedure such as landfill, drip washing, electrochemistry are big, and cost is high and frequently results in Soil structure and destroys and some nutrient loss.Therefore, exploitation one low cost, soil remediation medicament simple, efficient, eco-friendly are significant.
Chemical passivation renovation agent is the controlling area-source pollution technology of a kind of high-efficiency and economic, and this technology also complies with the needs of China's sustainable development.
Summary of the invention
The technical problem to be solved is to provide a kind of heavy metal cadmium, lead, arsenic combined contamination soil renovation agent and preparation method thereof, the present invention uses biomass carbon, kieselguhr, sodium bentonite, activated alumina, dithiocar-bamate, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate is mixed in proportion, make soil-repairing agent, add to by a certain percentage in heavy-metal contaminated soil according to pollution level, by absorption, ion exchanges, the synergism such as chelating react with the heavy metal in soil, heavy metal is made to form stable chemical form, stop its environmental transport and transfer and diffusion, reduce heavy metal murder by poisoning degree in the environment.
For solving above-mentioned technical problem, the invention provides a kind of heavy metal cadmium, lead, arsenic combined contamination soil renovation agent, its raw material is made up of biomass carbon, kieselguhr, sodium bentonite, activated alumina, dithiocar-bamate, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate, and the percentage by weight of each raw material of described soil-repairing agent is:
Biomass carbon 30-50%；
Kieselguhr 5-10%；
Sodium bentonite 5-10%；
Activated alumina 5-10%；
Dithiocar-bamate 10-20%；
Ethylenediaminetetraacetic acid 5-10%；
Tartaric acid 5-10%；
Polyacrylamide 5-10%；
Dodecyl sodium sulfate 5-10%；
The mass percent sum of each raw material is 100%.
Further, in described renovation agent, the mass percent of each raw material is:
Biomass carbon 50%；
Kieselguhr 5%；
Sodium bentonite 5%；
Activated alumina 5%；
Dithiocar-bamate 15%；
Ethylenediaminetetraacetic acid 5%；
Tartaric acid 5%；
Polyacrylamide 5%；
Dodecyl sodium sulfate 5%；
One heavy-metal contaminated soil renovation agent of the present invention, described biomass carbon is with the mixture of straw and calcium oxide as raw material, the mass ratio of described straw and calcium oxide is 20:1, system pressure be 20kPa, pyrolysis temperature be 500 DEG C under conditions of vacuum pyrolysis 30min, the pressed powder that particle diameter is below 3mm obtained by milled processed；
Described kieselguhr, activated alumina are respectively the pressed powder of below 2mm；
Described sodium bentonite be alkalescence coefficient more than 1, smectite content be 60-88%, particle diameter be the pressed powder of below 2mm；
Described ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate are the pressed powder of below 2mm.
Described dithiocar-bamate is the ammonia saline solution of polymerization dithiocarbonic acid, and mass concentration is 500mg/L.
One heavy-metal contaminated soil renovation agent of the present invention, by formation mixture that biomass carbon, kieselguhr, sodium bentonite, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate are stirred according to the above ratio, again the dithiocar-bamate of aforementioned proportion is added in mixture and stir, i.e. can obtain repairing medicament.
One heavy-metal contaminated soil renovation agent of the present invention, is obtained after mixture by said process, adds in heavy-metal contaminated soil, the 1-10% that reparations pharmaceutical quantities is contaminated soil weight added, then sprays a small amount of water and make Soil conservation moistening.
This medicament may be used for the improvement of single heavy metal contaminated soil, is also applied for the improvement of Compound Heavy Metals, it is adaptable to large area heavy-metal contaminated soil is repaired, and the mine including heavy metal pollution is repaired and heavy metal uses the reparation of manufacturing enterprise contaminated site.Compared with prior art, the medicament of repairing of the present invention has the advantage that preparation method is simple, feasible, regulation effect is good.
Relative to prior art, the beneficial effects of the present invention is:
Biomass carbon in renovation agent is obtained by vacuum pyrolysis biomass, and the biomass carbon porosity prepared under vacuum is high, and adsorptive value is high；With biomass such as straws as raw material, make full use of resource, it is to avoid because its burning causes environmental pollution.The yield promoting straw charcoal during vacuum pyrolysis by adding calcium oxide increases, and the biomass carbon obtained by vacuum pyrolysis has specific surface area big, and duct is enriched, and easily adsorbs all kinds of heavy metal ion, reduces the concentration of animal migration heavy metal ion in soil；Calcium oxide self in the biomass carbon prepared can make soil pH value improve soil surface negative charge to be increased, thus the affinity of soil heavy metal increases；On the other hand pH value raises, and is also beneficial to the existence of MOH+ and improves the adsorbance of heavy metal ion, promotes heavy metal in soil to form hydroxide or combined state precipitation or co-precipitation simultaneously.
Sodium bentonite is the clay mineral based on montmorillonite, and primary chemical formula is Nax (H2O)4(AI2-xMg0.83)Si4O10)(OH)2, its structure is pressed from both sides, by two silicon-oxy tetrahedrons, the crystal structure that one layer of alumina octahedral form.The layer structure that sodium bentonite structure cell is formed is primarily present sodium ion, easily by other cation replacements, has preferable ion exchangeable, can carry out ion exchange with the heavy metal in soil, reduce the bio-toxicity of heavy metal-polluted soil.
Activated alumina has many capillary channels, and specific surface area is big, has stronger affinity to water, oxide etc..
The heavy metal ion that aminodithioformic acid can effectively remove each metal ion species and various forms coexists.Dithiocarbamate-based strong complexation power can Direct precipitation chemical combination or the heavy metal ion of complexation, the stiff stability of complex avoids secondary pollution.During dithiocar-bamate and ethylenediaminetetraacetic acid, tartaric acid use simultaneously, ethylenediaminetetraacetic acid, tartaric acid are as compounding ingredient, form hydroxide precipitation with heavy metal to vie each other, promote aminodithioformic acid and heavy metal ion generation chelatropic reaction；In addition ethylenediaminetetraacetic acid, tartaric acid can be with heavy metal ion generation complex reaction.
The ammonia saline solution of polymerization dithiocarbonic acid, active group is dithiocarbonic acid, because the sulphur atom electronegativity in active group is little, radius has lost electronics more greatly, and easily polarization deformation produces negative electric field, thus can trapping positive ions tend to bonding, generate the dithiocar-bamate being insoluble in water.When it is combined with a certain metal ion, all forming four-membered ring by 2 sulphur atoms in its structure, the compound of formation is chelate.Dithiocar-bamate forms covalency chelate as trapping agent with heavy metal ion, cloth angle is joined to what electronics group space around central ion joined that cloth is decided by metal ion bonding orbital, dithiocar-bamate forms plane square structure with the metal ion of valence link track dsp2 type, four front three-dimensional-structures are formed with the metal ion of valence link track sp3 type, octahedral three-dimensional-structure is formed with the metal ion of valence link track ds2p3 type, owing to trapping agent forms, with the metal ion of different price bond orbital, the steric configuration that tension force is less, therefore what thing of Austria that dithiocar-bamate and metal ion generate has higher stability.
Polyacrylamide is high molecular polymer, has a good water solublity, nontoxic, non-corrosiveness, can improve the physical property of soil, increase soil macro aggregate number, improve soil hydraulic and water content, slow down soil losses, soil can be allowed to be fully contacted with leacheate；Additionally, polyacrylamide has carboxyl and amide groups isoreactivity group, coordinate bond can be formed by the metal ion with soil particle surface, have the synergism making stable chromium ion；
Dodecyl sodium sulfate is a kind of efficient anion surfactant, and easily with various additive compounds, cost is relatively low, and synthesis technique is ripe, with the hydrophobicity in chelating agen complex treatment soil containing heavy metal substance, improves soil remediation effect.
Except the respective chelating of said components, complexation, flocculate, precipitate, in addition to adsorption, biomass carbon, kieselguhr, sodium bentonite, the addition of activated alumina can improve soil physico-chemical property well, are greatly enhanced the permeability of soil；Under the effect of dodecyl sodium sulfate, easily and biomass carbon, kieselguhr, sodium bentonite, activated alumina cooperate and heavy metal ion is reacted for dithiocar-bamate, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide has flocculation simultaneously, in the soil environment having water, promote that pollutant in soil matter is assembled and adsorb with biomass carbon, kieselguhr, sodium bentonite, activated alumina.
Play synergism by said components so that heavy metal leaching rate in soil is substantially reduced, reach and be better than the primary standard of country " standard of soil environment quality " (GB15618-1995).
Detailed description of the invention:
Embodiment 1
Test soil collecting content of beary metal in certain heavy metal pollution region, this regional soil top layer is higher than the grade III Standard of " standard of soil environment quality " (GB15618-1995).Practical situation according to polluting is repaired:
A (), sampling from soil, detect and use turnover oscillator that soil is carried out leaching test according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect preprosthetic heavy metal-polluted soil concentration；
B prepared by (), soil-repairing agent: with the mixture of straw and calcium oxide as raw material, the mass ratio of described straw and calcium oxide is 20:1, system pressure be 20kPa, pyrolysis temperature be 500 DEG C under conditions of vacuum pyrolysis 30min, the biomass carbon powder that particle diameter is below 3mm obtained by milled processed；Obtain alkalescence coefficient more than 1, smectite content be 80%, the particle diameter sodium bentonite less than 2mm；Obtain particle diameter less than the kieselguhr of powder of 2mm, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate；Obtain the ammonia saline solution of the polymerization dithiocarbonic acid that mass concentration is 500mg/L.
The mass percent of each raw material is:
Biomass carbon 50%；
Kieselguhr 5%；
Sodium bentonite 5%；
Activated alumina 5%；
Dithiocar-bamate 15%；
Ethylenediaminetetraacetic acid 5%；
Tartaric acid 5%；
Polyacrylamide 5%；
Dodecyl sodium sulfate 5%；
By formation mixture that biomass carbon, kieselguhr, sodium bentonite, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate are stirred according to the above ratio, again the dithiocar-bamate of aforementioned proportion is added in mixture and stir, i.e. can obtain repairing medicament.
(c), the heavy-metal contaminated soil of 10kg is dug out, send into crusher in crushing, it is delivered to blender through belt, reparation medicament for soil quality 10% is sufficiently mixed with contaminated soil, in mixed process, spraying a small amount of water makes Soil conservation moisten, and stands 10 days after mixing, i.e. completes to repair.
(d), effect detection: sample the soil after repairing, detect and use turnover oscillator that soil is carried out leaching test according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), heavy metal-polluted soil concentration after detection reparation, result is as shown in table 1:
Table 1
| Cadmium (Cd) | Lead (Pb) | Arsenic (As) | |
| Before process (mg/kg) | 33.3 | 976 | 892 |
| After process (mg/kg) | 0.009 | 0.06 | 0.5 |
Cadmium in Soil after reparation, lead, arsenic content meet the primary standard of " standard of soil environment quality " (GB15618-1995).
Embodiment 2
Test soil collecting content of beary metal in certain heavy metal pollution region, this regional soil top layer is higher than the grade III Standard of " standard of soil environment quality " (GB15618-1995).Practical situation according to polluting is repaired:
A (), sampling from soil, detect and use turnover oscillator that soil is carried out leaching test according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect preprosthetic heavy metal-polluted soil concentration；
B prepared by (), soil-repairing agent: with the mixture of straw and calcium oxide as raw material, the mass ratio of described straw and calcium oxide is 20:1, system pressure be 20kPa, pyrolysis temperature be 500 DEG C under conditions of vacuum pyrolysis 30min, the biomass carbon powder that particle diameter is below 3mm obtained by milled processed；Obtain alkalescence coefficient more than 1, smectite content be 80%, the particle diameter sodium bentonite less than 2mm；Obtain particle diameter less than the kieselguhr of powder of 2mm, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate；Obtain the ammonia saline solution of the polymerization dithiocarbonic acid that mass concentration is 500mg/L.
The mass percent of each raw material is:
Biomass carbon 30%；
Kieselguhr 10%；
Sodium bentonite 10%；
Activated alumina 10%；
Dithiocar-bamate 10%；
Ethylenediaminetetraacetic acid 10%；
Tartaric acid 10%；
Polyacrylamide 5%；
Dodecyl sodium sulfate 5%；
By formation mixture that biomass carbon, kieselguhr, sodium bentonite, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate are stirred according to the above ratio, again the dithiocar-bamate of aforementioned proportion is added in mixture and stir, i.e. can obtain repairing medicament.
(c), the heavy-metal contaminated soil of 10kg is dug out, send into crusher in crushing, it is delivered to blender through belt, reparation medicament for soil quality 10% is sufficiently mixed with contaminated soil, in mixed process, spraying a small amount of water makes Soil conservation moisten, and stands 10 days after mixing, i.e. completes to repair.
(d), effect detection: sample the soil after repairing, detect and use turnover oscillator that soil is carried out leaching test according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), heavy metal-polluted soil concentration after detection reparation, result is as shown in table 2:
Table 2
| Cadmium (Cd) | Lead (Pb) | Arsenic (As) | |
| Before process (mg/kg) | 29.1 | 931 | 653 |
| After process (mg/kg) | 0.01 | 0.2 | 0.9 |
Cadmium in Soil after reparation, lead, zinc, mercury content meet the primary standard of " standard of soil environment quality " (GB15618-1995).
Embodiment 3
Test soil collecting content of beary metal in certain heavy metal pollution region, this regional soil top layer is higher than the grade III Standard of " standard of soil environment quality " (GB15618-1995).Practical situation according to polluting is repaired:
A (), sampling from soil, detect and use turnover oscillator that soil is carried out leaching test according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), detect preprosthetic heavy metal-polluted soil concentration；
B prepared by (), soil-repairing agent: with the mixture of straw and calcium oxide as raw material, the mass ratio of described straw and calcium oxide is 20:1, system pressure be 20kPa, pyrolysis temperature be 500 DEG C under conditions of vacuum pyrolysis 30min, the biomass carbon powder that particle diameter is below 3mm obtained by milled processed；Obtain alkalescence coefficient more than 1, smectite content be 80%, the particle diameter sodium bentonite less than 2mm；Obtain particle diameter less than the kieselguhr of powder of 2mm, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate；Obtain the ammonia saline solution of the polymerization dithiocarbonic acid that mass concentration is 500mg/L.
The mass percent of each raw material is:
Biomass carbon 5%；
Kieselguhr 5%；
Sodium bentonite 5%；
Activated alumina 5%；
Dithiocar-bamate 20%；
Ethylenediaminetetraacetic acid 5%；
Tartaric acid 5%；
Polyacrylamide 10%；
Dodecyl sodium sulfate 10%；
By formation mixture that biomass carbon, kieselguhr, sodium bentonite, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate are stirred according to the above ratio, again the dithiocar-bamate of aforementioned proportion is added in mixture and stir, i.e. can obtain repairing medicament.
(c), the heavy-metal contaminated soil of 10kg is dug out, send into crusher in crushing, it is delivered to blender through belt, reparation medicament for soil quality 10% is sufficiently mixed with contaminated soil, in mixed process, spraying a small amount of water makes Soil conservation moisten, and stands 10 days after mixing, i.e. completes to repair.
(d), effect detection: sample the soil after repairing, detect and use turnover oscillator that soil is carried out leaching test according to solid waste " Leaching leaching method sulfonitric method " (HJ/T299-2007), heavy metal-polluted soil concentration after detection reparation, result is as shown in table 3:
Table 3
| Cadmium (Cd) | Lead (Pb) | Arsenic (As) | |
| Before process (mg/kg) | 32.1 | 965 | 757 |
| After process (mg/kg) | 0.008 | 0.1 | 0.8 |
Cadmium in Soil after reparation, lead, zinc, mercury content meet the primary standard of " standard of soil environment quality " (GB15618-1995).
Claims (7)
1. a heavy metal cadmium, lead, arsenic combined contamination soil renovation agent, it is characterized in that: its raw material is made up of biomass carbon, kieselguhr, sodium bentonite, activated alumina, dithiocar-bamate, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate, the percentage by weight of each raw material of described soil-repairing agent is:
Biomass carbon 30-50%；
Kieselguhr 5-10%；
Sodium bentonite 5-10%；
Activated alumina 5-10%；
Dithiocar-bamate 10-20%；
Ethylenediaminetetraacetic acid 5-10%；
Tartaric acid 5-10%；
Polyacrylamide 5-10%；
Dodecyl sodium sulfate 5-10%；
The mass percent sum of each raw material is 100%.
A kind of heavy metal cadmium, lead, arsenic combined contamination soil renovation agent the most according to claim 1, it is characterised in that: the mass percent of each raw material of described soil-repairing agent is:
Biomass carbon 50%；
Kieselguhr 5%；
Sodium bentonite 5%；
Activated alumina 5%；
Dithiocar-bamate 15%；
Ethylenediaminetetraacetic acid 5%；
Tartaric acid 5%；
Polyacrylamide 5%；
Dodecyl sodium sulfate 5%.
A kind of heavy metal cadmium, lead, arsenic combined contamination soil renovation agent the most according to claim 1 and 2, it is characterized in that: described biomass carbon is with the mixture of straw and calcium oxide as raw material, the mass ratio of described straw and calcium oxide is 20:1, system pressure be 20kPa, pyrolysis temperature be 500 DEG C under conditions of vacuum pyrolysis 30min, the pressed powder that particle diameter is below 3mm obtained by milled processed.
A kind of heavy metal cadmium, lead, arsenic combined contamination soil renovation agent the most according to claim 1 and 2, it is characterised in that: described sodium bentonite be alkalescence coefficient more than 1, smectite content be 60-88%, particle diameter be the pressed powder of below 2mm.
A kind of heavy metal cadmium, lead, arsenic combined contamination soil renovation agent the most according to claim 1 and 2, it is characterised in that: described kieselguhr, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate are the pressed powder of below 2mm.
A kind of heavy metal cadmium, lead, arsenic combined contamination soil renovation agent the most according to claim 1 and 2, it is characterised in that: described dithiocar-bamate be mass concentration be the ammonia saline solution of the polymerization dithiocarbonic acid of 500mg/L.
7. a kind of heavy metal cadmium described in claim 1 to 6 any one, lead, the preparation method of arsenic combined contamination soil renovation agent, it is characterised in that: comprise the following steps:
(1), biomass carbon, kieselguhr, sodium bentonite, activated alumina, ethylenediaminetetraacetic acid, tartaric acid, polyacrylamide, dodecyl sodium sulfate are stirred formation mixture by corresponding mass ratio；
(2), the dithiocar-bamate of respective quality ratio is added in the mixture described in step (1), stir, obtain the soil-repairing agent of preparation.
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