CN106947487A - A kind of modifying agent and preparation and application for Compound Heavy Metals soil - Google Patents
A kind of modifying agent and preparation and application for Compound Heavy Metals soil Download PDFInfo
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- CN106947487A CN106947487A CN201710243108.7A CN201710243108A CN106947487A CN 106947487 A CN106947487 A CN 106947487A CN 201710243108 A CN201710243108 A CN 201710243108A CN 106947487 A CN106947487 A CN 106947487A
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- modifying agent
- soil
- heavy metal
- charcoal
- heavy metals
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- 239000002689 soil Substances 0.000 title claims abstract description 142
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 118
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 90
- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 92
- 239000000843 powder Substances 0.000 claims abstract description 82
- 239000003610 charcoal Substances 0.000 claims abstract description 62
- 238000009628 steelmaking Methods 0.000 claims abstract description 36
- 239000011575 calcium Substances 0.000 claims abstract description 34
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 32
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 229910000831 Steel Inorganic materials 0.000 claims description 14
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000010959 steel Substances 0.000 claims description 14
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 13
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 150000001722 carbon compounds Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- 238000007885 magnetic separation Methods 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 241001122767 Theaceae Species 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 238000007711 solidification Methods 0.000 abstract description 19
- 230000008023 solidification Effects 0.000 abstract description 19
- 238000002386 leaching Methods 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 230000006641 stabilisation Effects 0.000 abstract description 8
- 238000011105 stabilization Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000011591 potassium Substances 0.000 description 13
- 229910052700 potassium Inorganic materials 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000011133 lead Substances 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- 230000035784 germination Effects 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 244000269722 Thea sinensis Species 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000007226 seed germination Effects 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 4
- SDRZXZKXVBHREH-UHFFFAOYSA-M potassium;dihydrogen phosphate;phosphoric acid Chemical compound [K+].OP(O)(O)=O.OP(O)([O-])=O SDRZXZKXVBHREH-UHFFFAOYSA-M 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 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 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003802 soil pollutant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- 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
-
- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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 discloses a kind of modifying agent and preparation and application for Compound Heavy Metals soil, the modifying agent is made up of the material of following mass percent：Steel-making slag powder 30 55%；Peroxophosphoric acid calcium powder 20 50%；Load phosphatic charcoal 5 30%.It is an advantage of the invention that：First, the modifying agent can significantly reduce heavy metals mobilization and toxicity leaching content in heavy metal polluted soil, be particularly suitable for use in content of beary metal height and the more acid pollution place of pollutant kind, Polluted Soil can significantly reduce the environmental risk in the second development and utilization of contaminated site after repairing as environmentally friendly material recycling；Meanwhile, the modifying agent raw material are easily obtained, it is with low cost, prepare simple, easy to use, effect stability, can be in large-scale application in the solidification and stabilization in combined pollution place is repaired.
Description
Technical field
The present invention relates to environmental geotechnical field, more particularly to a kind of modifying agent for Compound Heavy Metals soil and
Preparation and application.
Background technology
With the adjustment of China's city function and city layout, original position is in the enterprise of downtown area, suburb, such as chemical industry
Factory, metallurgical works, Electroplate Factory etc. all progressively close down or Tui Chengjin gardens, but industry, the production process of enterprise for many years, are removed at it
A large amount of pollutants are have accumulated in the soil left after moving, is not only that efficient utilize for leaving soil brings resistance, is also surrounding
Environment brings serious potential safety hazard.In recent years, government promulgates《Soil Pollution Control action plan》(ten, soil) is also by dirt
Dye soil remediation work is considered as one of current important people's livelihood engineering, carries out the work of associated contamination repairing and treating extremely urgent.
The features such as industrial pollution place heavy metal pollution of soil is rendered as many heavy metal species, high content and big acidity.
In the reparation in heavy metal pollution place, solidification stabilization technique is widely adopted.Conventional modifying agent mainly includes cement, lime
And the material such as phosphate, heavy metal solidification and stabilization has good effect, but there is also substantial amounts of shortcoming, for example, produces water
Mud energy consumption is big, greenhouse gas emission is more etc.；Lime, phosphate are non-renewable natural minerals, cost height etc.；And it is phosphatic
It is a large amount of to apply, it can seriously change soil texture and further trigger the phosphorus pollution of underground water, surface water.
In summary, there is many defects in traditional modifying agent, it is desirable to reduce the use of cement and phosphate material, find one
Stabilizing heavy metal can be solidified by planting, while solidifying, stabilization efficiency is high, with low cost, performance is stable, material source is extensive and environment is friendly
Good new and improved dose turns into environmentally friendly scientific worker's focus of attention.
The content of the invention
Goal of the invention：The first object of the present invention is to provide a kind of heavy metal that can be significantly reduced in heavy metal polluted soil
The modifying agent of the Compound Heavy Metals soil of migration and toxicity leaching content；It is heavy metal-polluted that the second object of the present invention is to provide this
The preparation method of the native modifying agent of dye；The third object of the present invention is to provide the application method of the heavy metal polluted soil modifying agent.
Technical scheme：Modifying agent of the present invention for Compound Heavy Metals soil, by the material group of following mass percent
Into：Steel-making slag powder 30-55%；Peroxophosphoric acid calcium powder 20-50%；Load phosphatic charcoal 5-30%.
The component material of the modifying agent is preferably：Steel-making slag powder 35-50%；Peroxophosphoric acid calcium powder 25-45%；Load is phosphatic
Charcoal 10-25%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：
(1) by the one or more in the vessel slag after magnetic separation, open hearth slag and the contour active slag of lectric furnace slag
By broken sieving；
(2) drying materials to its moisture content for taking particle diameter to be less than 2mm in the product obtained is less than 2%, it is preferred to use 100-
105 DEG C of airflow drying；
(3) product obtained is ground and crosses after the sieve of 150-200 mesh and (can for example use ball milling), then through 500-
700 DEG C of calcining 1-2h (can for example be preferred to use electric furnace calcining, energy-saving practical), obtain activated steel slag powder.
The phosphatic charcoal of load is prepared from by following methods：
(1) prepare concentration for 0.01-0.05mol/L phosphate solution (phosphate is preferred to use potassium dihydrogen phosphate, its
The aqueous solution is acidity, more preferable to activity of steel slag effect), the ground 0.1-0.3mm of charcoal is sieved, biological powdered carbon is obtained；
(2) by biological powdered carbon and aluminum sulfate according to mass ratio 20-30:1 mixing, obtains biological powdered carbon compound；
(3) the biological powdered carbon compound of gained is impregnated into phosphate solution, 10~15min of stirring is (equal to mixture
It is even), 36-48h is stood after vibration stirring 10-15h at 20-30 DEG C, gelatinous precipitate is obtained, wherein the purpose stirred twice
Difference, stirring is to allow solid-liquid fully to contact for the first time, is quick generation gel precipitate for the second time；
(4) gelatinous precipitate is less than 2%, products therefrom mill using 100-250 DEG C airflow drying to its moisture content
It is thin to cross 150-200 mesh sieves, obtain loading phosphatic charcoal, wherein, quick using airflow drying, medicament is prevented from caking, side
Continue medicament production after an action of the bowels.
One or more in the coffee grounds, tea foam and Chinese medicine slag are dried at 100-105 DEG C to its constant mass
Afterwards, charcoal is made by 400-700 DEG C of cracking under anoxic conditions.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content uses 100- for 14-20% calcium superphosphate
250 DEG C of airflow drying to its moisture content is less than 2%, ground 150-200 mesh sieves.
The preparation method of the modifying agent suitable for Compound Heavy Metals soil comprises the following steps：By weight percentage
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic charcoal of load are mixed, it is equal to mixing using dry stirring 0.5-1h
150-200 mesh sieves are crossed after even, modifying agent is obtained.
The application method of modifying agent suitable for Compound Heavy Metals soil is：By the modifying agent with it is heavy metal-polluted
Dye soil is mixed, wherein, the modifying agent consumption is the 5-15% of heavy metal polluted soil dry weight, and the heavy metal polluted soil
Moisture content be 16-30%.
The granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 65-100%, and wherein heavy metal lead contains
Amount is more than 2000mg/kg, and heavy metal zinc content is more than 2000mg/kg, and heavy metal copper content is more than 2000mg/kg, heavy metal nickel
Content is more than 2000mg/kg.
Beneficial effect：Compared with prior art, significant advantage of the invention is：
(1) heavy metals immobilization effect is good.First, the absorption that the slag energy heavy metal ion being related in the present invention has
Effect；Secondly, part of sulfuric acid calcium is contained in agriculture level calcium superphosphate, slag is under the excitation of calcium sulfate, its potential glue
Solidifying characteristic is represented, and calcium phosphate precipitation and the hydroxide precipitation of heavy metal have carried out effective package action, increase
The strong simple solidification effect using phosphatic heavy metal；Again, the calcium oxide aquation generation Ca being dissolved out in slag
(OH)2, and the main component of calcium superphosphate is Ca (H2PO4)2, it is a large amount of that both occur acid-base reaction generation under aqueous environment
Hydroxyapatite crystal.Hydroxyapatite can the efficient absorption complexing heavy metal such as Pb, Zn, Cu and Ni, itself and heavy metal are generated
Hydroxyapatite heavy metallic salt solubility tens orders of magnitude low compared with heavy metal hydroxide, while it is in acid and alkaline bar
Dissolve relatively low under part, solidification effect is more preferably stablized.
(2) excellent in durability.Traditional modifying agent is easily corroded by carbon dioxide and acid-rain corrosion is influenceed, and produces solidification pollution
Native environmental safety and engineering characteristic deteriorate relaxation phenomenon.The modifying agent being related in the present invention can effectively overcome disadvantages mentioned above,
Because the heavy phosphates class precipitation of generation is reunited around charcoal, its solubility under a variety of pH environment is relatively low, and
And under the package action of the hydrated product C-S-H gels of slag, connecing for heavy metal precipitation and acid solution can be effectively reduced
Touch；Slag has the ability of extremely strong acid buffer capacity and absorbing carbon dioxide in itself simultaneously, under carbon dioxide corrosion function, raw
Into CaCO3Crystal further fills the hole of firming body, effectively reduction acid solution infiltration capacity, and further increase firming body is being disliked
Stability under bad environment；In addition, loading phosphatic charcoal also wants preferable cushioning effect, the phosphorus of load to acid-rain corrosion
Hydrochlorate can effectively suppress the desorption of Adsorption of Heavy Metals, further the durability of increase firming body.
(3) waste material, environmentally friendly modifying agent are effectively utilized.First, slag is used as a kind of industrial residue, large area
Accumulation, has had resulted in serious environmental pollution, by the activation to slag, effectively increases the value of slag, becomes useless
For treasured.Secondly, slag is directly used in the solidification and stabilization of heavy metal polluted soil as a kind of overbased material, solidified earth pH
It is higher, it can be utilized to the later development in soil and bring many problems, by activation modification, effectively increase slag heavy metal
Solidification effect while, also effectively reduce the pH of solidified earth, and by the addition of calcium superphosphate, make its heavy metal
Solidification and stabilization effect reaches most preferably.Again, coffee grounds, tea foam and Chinese medicine slag are also life waste residue, are cracked by high temperature,
It is prepared into after charcoal, is further modified, can be effectively increased to the same of the solidification effect of metal after phosphate in load
When can also realize slag is excited, increase the hydration activity of slag and the solidification and stabilization effect of heavy metal.
Embodiment
Embodiment 1
The present invention is made up of suitable for the modifying agent of Compound Heavy Metals soil the material of following mass parts：Steel-making slag powder
45%；Peroxophosphoric acid calcium powder 35%；Load phosphatic charcoal 20%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：Vessel slag is carried out after magnetic separation to crush
Sieve；Taking particle diameter to be less than in 2mm material placement baking oven in obtained product uses temperature aqueous to its for 105 DEG C of airflow drying
Rate is 1%；Obtained product is ground and crossed after the sieve of 200 mesh, then is obtained through 700 DEG C of electric furnaces calcining 2h.The steel-making slag powder alkali
Angle value is 2.07.
The main component and content of the slag are shown in Table 1, what deserves to be explained is, it is adaptable to slag of the invention is not limited to
Data in table 1, it is only the slag that the present embodiment is used：
The slag main component of table 1 and content
| Main chemical compositions | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | P2O5 |
| Content (%) | 36.30 | 16.26 | 3.32 | 18.66 | 8.35 | 1.26 |
The phosphatic charcoal of load is prepared from by following methods：Prepare the di(2-ethylhexyl)phosphate that concentration is 0.05mol/L
Hydrogen potassium solution, and the ground 0.2mm of charcoal is sieved, obtain biological powdered carbon；By the ratio of biological powdered carbon and aluminum sulfate according to quality
30:1 is sufficiently mixed, and obtains biological powdered carbon compound；Gained compound is impregnated into potassium dihydrogen phosphate obtained above molten
In liquid, stirring 15min is to well mixed, at 25 DEG C, stands 48h after vibration stirring 15h, obtains gelatinous precipitate；Will be solidifying
Gelatinous precipitate uses 200 DEG C of airflow drying to its moisture content for 1%, ground 200 mesh sieve of products therefrom, obtains loading phosphorus
The charcoal of acid dihydride potassium.The charcoal is dried to its quality not after change, closed to choose coffee grounds at 105 DEG C
Under anoxia condition, it is made by cracking 6h under 600 DEG C of environment, its physicochemical characteristics and main chemical compositions are shown in Table 2.
The charcoal basic chemical property of table 2 and essential element content
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 20% calcium superphosphate uses 250 DEG C
Stream drying to its moisture content is 1%, ground 200 mesh sieve.
The modifying agent suitable for Compound Heavy Metals soil, which comprises the following steps, to be prepared from：By above-mentioned mass parts
Activated steel slag powder, peroxophosphoric acid calcium powder and load phosphatic charcoal and mixed, using dry stirring 1h to being well mixed
200 mesh sieves are crossed afterwards, obtain modifying agent.
The application method of modifying agent suitable for Compound Heavy Metals soil is specially：By modifying agent with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the modifying agent consumption (accounts for composition metal for the 5% of heavy metal polluted soil dry weight
Polluted Soil dry weight).Heavy metal contaminants have two kinds：Polluted Soil a, is derived from lead, the zinc combined pollution soil in a certain industrial pollution place；
Polluted Soil b, is derived from copper, the nickel combined pollution soil in certain two industrial pollution place.Other main physicochemical properties are as shown in table 3.
The Polluted Soil Main physical chemical property of table 3
Embodiment 2
It is identical with the preparation process and maintenance processes of embodiment 1, except that, the volume of modifying agent is 10% (improvement
Agent accounts for heavy metal and organic compound contaminated native dry weight).
Embodiment 3
It is identical with the preparation process and maintenance processes of embodiment 1, except that, the volume of modifying agent is 15% (improvement
Agent accounts for heavy metal and organic compound contaminated native dry weight).
Comparative example 1
Without any modifying agent, only the Compound Heavy Metals soil sample in Example 1.
Comparative example 2
Modifying agent is prepared without overactivation using the slag in embodiment 1, other preparation processes are constant, volume and embodiment
3 be all mutually 15%.
Embodiment 4
The present invention is made up of suitable for the modifying agent of Compound Heavy Metals soil the material of following mass parts：Steel-making slag powder
50%；Peroxophosphoric acid calcium powder 25%；Load phosphatic charcoal 25%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：Open hearth slag is carried out after magnetic separation to crush
Sieve；It is 1.5% for 100 DEG C airflow drying to its moisture content that the material for taking particle diameter to be less than 2mm in obtained product, which uses temperature,；
Obtained product is ground and crossed after the sieve of 150 mesh, then is obtained through 500 DEG C of electric furnaces calcining 1h.The steel-making slag powder basicity value is
1.8。
The phosphatic charcoal of load is prepared from by following methods：Prepare the di(2-ethylhexyl)phosphate that concentration is 0.01mol/L
Hydrogen potassium solution, and the ground 0.1mm of charcoal is sieved, obtain biological powdered carbon；By biological powdered carbon and aluminum sulfate according to 20:1 mass
Ratio be sufficiently mixed, obtain biological powdered carbon compound；Gained compound is impregnated into potassium dihydrogen phosphate obtained above molten
In liquid, stirring 10min is to well mixed, at 20 DEG C, stands 36h after vibration stirring 10h, obtains gelatinous precipitate；Will be solidifying
Gelatinous precipitate uses 100 DEG C of airflow drying to its moisture content for 1.5%, and ground 150 mesh sieve of products therefrom is loaded
The charcoal of potassium dihydrogen phosphate.
The charcoal is dried to its quality not after change to choose coffee grounds at 100 DEG C, under anoxic conditions, warp
Cross to crack under 400 DEG C of environment and be made.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 14% calcium superphosphate uses 100 DEG C
Stream drying to its moisture content is 1.5%, ground 150 mesh sieve.
The modifying agent suitable for Compound Heavy Metals soil, which comprises the following steps, to be prepared from：By above-mentioned mass parts
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic charcoal of load are mixed, using dry stirring 0.5h to after being well mixed
150 mesh sieves are crossed, modifying agent is obtained.
The application method of modifying agent suitable for Compound Heavy Metals soil is specially：By modifying agent with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the modifying agent consumption (accounts for composition metal for the 5% of heavy metal polluted soil dry weight
Polluted Soil dry weight), and the moisture content of the heavy metal polluted soil is 16%, heavy metal polluted soil and the pollution selected in embodiment 1
Soil is identical, and the granule content that particle diameter is less than 0.075mm wherein in the heavy metal polluted soil is 65%.
Embodiment 5
The present invention is made up of suitable for the modifying agent of Compound Heavy Metals soil the material of following mass parts：Steel-making slag powder
35%；Peroxophosphoric acid calcium powder 45%；Load phosphatic charcoal 20%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：Open hearth slag is carried out after magnetic separation to crush
Sieve；It is absolutely dry that the material for taking particle diameter to be less than 2mm in obtained product uses temperature to be dried to for 150 DEG C of air-flow；Obtained product enters
Row grinds and crossed after the sieve of 180 mesh, then is obtained through 600 DEG C of electric furnaces calcining 1.5h.The steel-making slag powder basicity value is 2.2.
The phosphatic charcoal of load is prepared from by following methods：It is 0.03mol/L to prepare concentration with phosphate
Potassium dihydrogen phosphate, and the ground 0.3mm of charcoal is sieved, obtains biological powdered carbon；By biological powdered carbon and aluminum sulfate according to
25:The ratio of 1 mass is sufficiently mixed, and obtains biological powdered carbon compound；Gained compound is impregnated into phosphoric acid obtained above
In dihydro potassium solution, stirring 13min is to well mixed, at 25 DEG C, stands 42h after vibration stirring 12.5h, obtains gel and sink
Starch；Gelatinous precipitate is dried to absolutely dry, ground 170 mesh sieve of products therefrom using 180 DEG C of air-flow, obtains loading phosphoric acid
The charcoal of potassium dihydrogen.
The charcoal is dried to its quality not after change to choose tea foam at 102.5 DEG C, under anoxic conditions,
It is made by being cracked under 550 DEG C of environment.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 17% calcium superphosphate uses 150 DEG C
Stream is dried to absolutely dry, ground 170 mesh sieve.
The modifying agent suitable for Compound Heavy Metals soil, which comprises the following steps, to be prepared from：By above-mentioned mass parts
Activated steel slag powder, peroxophosphoric acid calcium powder and the phosphatic charcoal of load are mixed, equal to mixing using dry stirring 0.75h
170 mesh sieves are crossed after even.
The application method of modifying agent suitable for Compound Heavy Metals soil is specially：By modifying agent with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the modifying agent consumption (accounts for composition metal for the 10% of heavy metal polluted soil dry weight
Polluted Soil dry weight), and the moisture content of the heavy metal polluted soil is 23%, heavy metal polluted soil and the pollution selected in embodiment 1
Soil is identical, wherein, the granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 82.5%.
Embodiment 6
The present invention is made up of suitable for the modifying agent of Compound Heavy Metals soil the material of following mass parts：Steel-making slag powder
40%；Peroxophosphoric acid calcium powder 50%；Load phosphatic charcoal 10%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：Open hearth slag is carried out after magnetic separation to crush
Sieve；It is 0.5% for 125 DEG C airflow drying to its moisture content that the material for taking particle diameter to be less than 2mm in obtained product, which uses temperature,；
Obtained product is ground and crossed after the sieve of 200 mesh, then is obtained through 700 DEG C of electric furnaces calcining 2h.The steel-making slag powder basicity value is
2.6。
The phosphatic charcoal of load is prepared from by following methods：Prepare the di(2-ethylhexyl)phosphate that concentration is 0.05mol/L
Hydrogen potassium solution, and the ground 0.2mm of charcoal is sieved, obtain biological powdered carbon；By biological powdered carbon and aluminum sulfate according to 30:1 mass
Ratio be sufficiently mixed, obtain biological powdered carbon compound；Gained compound is impregnated into phosphate solution obtained above,
15min is stirred to well mixed, at 30 DEG C, 48h is stood after vibration stirring 15h, obtains gelatinous precipitate；Gel is sunk
Starch uses 250 DEG C of airflow drying to its moisture content for 0.5%, ground 190 mesh sieve of products therefrom, obtains loading di(2-ethylhexyl)phosphate
The charcoal of hydrogen potassium.
After the charcoal is dried to its quality at 105 DEG C and no longer changed to choose Chinese medicine slag, under anoxic conditions, warp
Cross to crack under 700 DEG C of environment and be made.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 18% calcium superphosphate uses 180 DEG C
Stream drying to its moisture content is 0.5%, and ground 190 mesh sieve obtains peroxophosphoric acid calcium powder.
The modifying agent suitable for Compound Heavy Metals soil, which comprises the following steps, to be prepared from：By above-mentioned mass parts
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic charcoal of load are mixed, using dry stirring 0.75h to after being well mixed
190 mesh sieves are crossed, modifying agent is obtained.
The application method of modifying agent suitable for Compound Heavy Metals soil is specially：By modifying agent with it is heavy metal-polluted
Dye soil carries out original place mixing.Wherein, the modifying agent consumption (accounts for composition metal for the 15% of heavy metal polluted soil dry weight
Polluted Soil dry weight), and the moisture content of the heavy metal polluted soil is 30%.Particle diameter is less than 0.075mm in heavy metal polluted soil used
Granule content be 83%, heavy metal polluted soil is identical with the Polluted Soil selected in embodiment 1, wherein, the heavy metal pollution
The granule content that particle diameter is less than 0.075mm in soil is 100%.
Embodiment 7
The present invention is made up of suitable for the modifying agent of Compound Heavy Metals soil the material of following mass parts：Steel-making slag powder
30%；Peroxophosphoric acid calcium powder 40%；Load phosphatic charcoal 30%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：Lectric furnace slag is broken after magnetic separation
Broken sieving；It is absolutely dry that the material for taking particle diameter to be less than 2mm in obtained product uses temperature to be dried to for 150 DEG C of air-flow；Obtained production
Thing is ground and crossed after the sieve of 180 mesh, then is obtained through 600 DEG C of electric furnaces calcining 1.5h.The steel-making slag powder basicity value is 2.2.
The phosphatic charcoal of load is prepared from by following methods：It is 0.03mol/L to prepare concentration with phosphate
Potassium dihydrogen phosphate, and the ground 0.3mm of charcoal is sieved, obtains biological powdered carbon；By biological powdered carbon and aluminum sulfate according to
25:The ratio of 1 mass is sufficiently mixed, and obtains biological powdered carbon compound；Gained compound is impregnated into phosphoric acid obtained above
In dihydro potassium solution, stirring 13min is to well mixed, at 25 DEG C, stands 42h after vibration stirring 12.5h, obtains gel and sink
Starch；Gelatinous precipitate is dried to absolutely dry, ground 200 mesh sieve of products therefrom using 180 DEG C of air-flow, obtains loading phosphoric acid
The charcoal of potassium dihydrogen.
The charcoal is dried to its quality not in change to choose the mixture of tea foam and coffee grounds at 102.5 DEG C
Afterwards, under anoxic conditions, it is made by being cracked under 600 DEG C of environment.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 18% calcium superphosphate uses 150 DEG C
Stream drying to its moisture content is 1%, ground 200 mesh sieve.
The modifying agent suitable for Compound Heavy Metals soil, which comprises the following steps, to be prepared from：By above-mentioned mass parts
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic charcoal of load are mixed, using dry stirring 0.75h to after being well mixed
Cross 200 mesh sieves.
The application method of modifying agent suitable for Compound Heavy Metals soil is specially：By modifying agent with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the modifying agent consumption (accounts for composition metal for the 5% of heavy metal polluted soil dry weight
Polluted Soil dry weight), and the moisture content of the heavy metal polluted soil is 25%, heavy metal polluted soil and the pollution selected in embodiment 1
Soil is identical, wherein, the granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 90%.
Embodiment 8
The present invention is made up of suitable for the modifying agent of Compound Heavy Metals soil the material of following mass parts：Steel-making slag powder
55%；Peroxophosphoric acid calcium powder 20%；Load phosphatic charcoal 25%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：Lectric furnace slag is broken after magnetic separation
Broken sieving；It is absolutely dry that the material for taking particle diameter to be less than 2mm in obtained product uses temperature to be dried to for 150 DEG C of air-flow；Obtained production
Thing is ground and crossed after the sieve of 180 mesh, then is obtained through 600 DEG C of electric furnaces calcining 1.5h.The steel-making slag powder basicity value is 2.2.
The phosphatic charcoal of load is prepared from by following methods：It is 0.03mol/L to prepare concentration with phosphate
Potassium dihydrogen phosphate, and the ground 0.3mm of charcoal is sieved, obtains biological powdered carbon；By biological powdered carbon and aluminum sulfate according to
25:The ratio of 1 mass is sufficiently mixed, and obtains biological powdered carbon compound；Gained compound is impregnated into phosphoric acid obtained above
In dihydro potassium solution, stirring 13min is to well mixed, at 25 DEG C, stands 42h after vibration stirring 12.5h, obtains gel and sink
Starch；Gelatinous precipitate is dried to absolutely dry, ground 200 mesh sieve of products therefrom using 180 DEG C of air-flow, obtains loading phosphoric acid
The charcoal of potassium dihydrogen.
The charcoal is dried to its quality not in change to choose the mixture of coffee grounds and Chinese medicine slag at 102.5 DEG C
Afterwards, under anoxic conditions, it is made by being cracked under 450 DEG C of environment.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 18% calcium superphosphate uses 150 DEG C
Stream drying to its moisture content is 1%, and ground 200 mesh sieve obtains peroxophosphoric acid calcium powder.
The modifying agent suitable for Compound Heavy Metals soil, which comprises the following steps, to be prepared from：By above-mentioned mass parts
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic charcoal of load are mixed, using dry stirring 0.75h to after being well mixed
Cross 200 mesh sieves.
The application method of modifying agent suitable for Compound Heavy Metals soil is specially：By modifying agent with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the modifying agent consumption (accounts for composition metal for the 10% of heavy metal polluted soil dry weight
Polluted Soil dry weight), and the moisture content of the heavy metal polluted soil is 23%, heavy metal polluted soil and the pollution selected in embodiment 1
Soil is identical, wherein, the granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 75%.
Embodiment 9
The present invention is made up of suitable for the modifying agent of Compound Heavy Metals soil the material of following mass parts：Steel-making slag powder
55%；Peroxophosphoric acid calcium powder 40%；Load phosphatic charcoal 5%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：Lectric furnace slag is broken after magnetic separation
Broken sieving；It is absolutely dry that the material for taking particle diameter to be less than 2mm in obtained product uses temperature to be dried to for 150 DEG C of air-flow；Obtained production
Thing is ground and crossed after the sieve of 180 mesh, then is obtained through 600 DEG C of electric furnaces calcining 1.5h.The steel-making slag powder basicity value is 2.2.
The phosphatic charcoal of load is prepared from by following methods：It is 0.03mol/L to prepare concentration with phosphate
Potassium dihydrogen phosphate, and the ground 0.3mm of charcoal is sieved, obtains biological powdered carbon；By biological powdered carbon and aluminum sulfate according to
25:The ratio of 1 mass is sufficiently mixed, and obtains biological powdered carbon compound；Gained compound is impregnated into phosphoric acid obtained above
In dihydro potassium solution, stirring 13min is to well mixed, at 25 DEG C, stands 42h after vibration stirring 12.5h, obtains gel and sink
Starch；Gelatinous precipitate is dried to absolutely dry, ground 200 mesh sieve of products therefrom using 180 DEG C of air-flow, obtains loading phosphoric acid
The charcoal of potassium dihydrogen.
The charcoal is dried to its quality not in change to choose the mixture of tea foam and Chinese medicine slag at 102.5 DEG C
Afterwards, under anoxic conditions, it is made by being cracked under 550 DEG C of environment.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 18% calcium superphosphate uses 150 DEG C
Stream drying to its moisture content is 1%, and ground 200 mesh sieve obtains peroxophosphoric acid calcium powder.
The modifying agent suitable for Compound Heavy Metals soil, which comprises the following steps, to be prepared from：By above-mentioned mass parts
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic charcoal of load are mixed, using dry stirring 0.75h to after being well mixed
Cross 200 mesh sieves.
The application method of modifying agent suitable for Compound Heavy Metals soil is specially：By modifying agent with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the modifying agent consumption (accounts for composition metal for the 15% of heavy metal polluted soil dry weight
Polluted Soil dry weight), and the moisture content of the heavy metal polluted soil is 23%, heavy metal polluted soil and the pollution selected in embodiment 1
Soil is identical, wherein, the granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 82.5%
Embodiment 10
To embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, embodiment 4, embodiment 5, embodiment 6, reality
Apply the soil of the sample after implementing in example 7, embodiment 8 and embodiment 9 and sealing is wrapped with freshness protection package, be more than 95% condition in 20 DEG C, humidity
It is lower maintenance 28 days after solidification Polluted Soil do toxicity characteristic leaching procedure：
Testing standard：National environmental protection professional standard《Solid waste Leaching leaching method sulfonitric method》(HJ/
T 299-2007)。
Process of the test：By the solidification Polluted Soil after maintenance, weigh wherein 50g samples and be placed in drying, constant weight to two at 105 DEG C
The error of secondary weighing value is less than ± 1%, and calculating obtains sample moisture content.Calculated according to moisture content and repair native dry weight, weigh butt
Quality is 10g reparation soil sample, and according to《Solid waste Leaching leaching method sulfonitric method》(HJ/T 299-2007)
Defined method and step are tested.Result of the test is as shown in table 4.
The toxicity characteristic leaching procedure result (mg/L) of table 4
Sulfonitric method leaching method be used to evaluate solid waste whether be hazardous waste standard, be also analysis solid
The common method of pollutant Leaching feature of the waste under acid precipitation effect.From the toxicity characteristic leaching procedure result of table 4, lead to
Comparing embodiment 1-3, embodiment 4-6 and embodiment 7-9 is crossed to can be seen that：Mixed with the reparation soil of modifying agent of the present invention, it is leached
Zn, Pb, Ni and Cu leaching concentration, by comparative example 1, are not located as the addition content of modifying agent increases and reduces in liquid
Heavy metals mobilization in the source Polluted Soil of reason is extremely strong, and heavy metal Zn, Pb, Ni and Cu leaching content are far above《Hazardous waste reflects
Other standard leaching characteristic identification》Boundary value in (GB 5085.3-2007), in conjunction with the embodiments 1-9 can be found that adding for modifying agent
Plus the stripping quantity of heavy metal can be significantly reduced, increase environmental safety.Knowable to embodiment 3 and comparative example 2 are contrasted, addition is originally
Modifying agent in invention and after conserving 28 days, the stability of heavy metal all increases, and the stablizing effect in embodiment 3 is more bright
Aobvious, its leaching content is far below《Hazardous waste judging standard leaching characteristic identification》Boundary value in (GB 5085.3-2007), and
The steel-making slag powder in modifying agent in comparative example 2 is not activated only by loading phosphatic charcoal preparation, and it can be on a ground
The migration characteristic of heavy metal Zn, Pb, Ni and Cu in soil is reduced in degree, the harm of its environmentally safe property is reduced, still may be used
To meet the basic demand of the present invention, it follows that carrying out activation modification processing to slag used, can effectively it strengthen to modifying agent
The solidification stablizing effect of heavy metal, if slag can also realize the skill of the present invention to a certain extent without activation process
Art effect.
Embodiment 11
To embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, embodiment 4, embodiment 5, embodiment 6, reality
Apply the solidification Polluted Soil after example 7, embodiment 8 and embodiment 9 are conserved as described in Example 10 and do reparation mud acid alkalinity test：
Testing standard：The method of testing 4972-01 of the pH value of soil.
Process of the test：By the solidification Polluted Soil after maintenance, weigh wherein 50g samples and be placed in drying, constant weight to two at 105 DEG C
The error of secondary weighing value is less than ± 1%, and calculating obtains sample moisture content.Calculated according to moisture content and repair native dry weight, cross 1mm sieves simultaneously
The reparation soil sample that butt quality is 10g is weighed, is mixed with the stirring of 10g distilled water, stands test solution pH value after 1h.Result of the test
As shown in table 5.
The acid-base value result of the test of table 5
The acid-base value of the solidification soil body is to evaluate an important indicator of modifying agent curing heavy metal effect, and it is to repairing place
The secondary development scheme and degree utilized influence it is great.By the acid-base value result of the test of table 5, pass through embodiment 1-3 and contrast
The comparison of example 1 is understood, after addition modifying agent, and the pH of the solidification soil body is significantly improved, and after conserving 28 days, the pH value for Polluted Soil is equal
Between 6~9, close to neutrality, be conducive to repairing the utilization in place, while the pH for solidifying the soil body in embodiment 4-9 is also significantly carried
After height, maintenance 28 days, for Polluted Soil pH value also between 6~9, close to neutral；Comparative example 2 relative to embodiment 3 by
In not carrying out activation process to slag, cause pH value slightly higher, but can also realize technical scheme substantially, if pH is held
High can be utilized to soil later development of continuing rising brings many problems.
Embodiment 12
To embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, embodiment 4, embodiment 5, embodiment 6, reality
Apply example 7, the Polluted Soil of the maintenance of embodiment 8 and embodiment 9 as described in Example 10 carries out phytotoxicity experiment (germination
Rate is tested)：
Process of the test：Percentage of seedgermination experiment uses the soya bean to heavy metal in soil pollutant load more sensitivity, with
Its germination percentage carries out oxicity analysis as ecological index heavy metal and organic compound contaminated soil, is more conventional from life
State toxicological point weighs the important method of soil environment quality and soil pollution.Element after should conserving 28 days first is native and repaiies
Earth backing, it is standby that natural wind dry doubling crosses 2mm sieves.Each sample takes 4kg soil (element soil or each repair soil) dress basin, and (back cut diameter is
25cm, base diameter is 20cm, a height of 20cm), ridging height is 18cm；Soil in basin is irrigated to specific retention with distilled water and is
60%, keep specific retention constant thereafter and infiltration indoors is placed 2 days；Soya bean is finally sowed, soya bean sowing is left in depth 0.3cm
The right side, 100 are sowed per basin；Suitable soil moisture is periodically after planting kept using spray pattern, make seed indoors area without shade,
Germinateed under the conditions of 18-22 DEG C of room temperature, natural lighting.Germination percentage=(seed number is planted experimentally in chitting piece grain number/confession) × 100%.Examination
Test result as shown in table 6.
The percentage of seedgermination of table 6 (%)
Percentage of seedgermination experiment can reflect toxic action of the soil to plant.As can be seen from Table 6：Plain soil (contrast
Example 1, that is, be not added with the Polluted Soil of modifying agent) in content of beary metal it is very high, have a strong impact on the Huang in the germination percentage of seed, Polluted Soil
Beans percentage of seedgermination is only 8% and 12%.And the modifying agent in comparative example 2 then improves germination percentage to a certain extent, but carry
Limited extent is risen, is only capable of reaching 49% and 52% germination percentage, illustrates that the present invention is used and changes made from not activated steel-making slag powder
There is certain stabilization in good dose to the heavy metal in Polluted Soil, act on limited at that time；On the contrary, in embodiment of the present invention 1-9
Modifying agent reparation soil percentage of seedgermination 85% is all higher than in the case of a variety of volumes, highest even can reach 99%.It is real
The difference for applying example 1,2,3 and comparative example 1 shows that modifying agent of the present invention repairs the autochthonal state close friend of Compound Heavy Metals, is conducive to
The activation process of the plant on place periphery and development of microorganisms growth after reparation, embodiment 3 and the comparative illustration of comparative example 2 to slag
Toxic action of the soil to plant can also be effectively reduced, the solidification stabilizing power of its heavy metal is reflected from side.
Claims (9)
1. a kind of modifying agent for Compound Heavy Metals soil, it is characterised in that：It is made up of the material of following mass percent：
Steel-making slag powder 30-55%；Peroxophosphoric acid calcium powder 20-50%；Load phosphatic charcoal 5-30%.
2. the modifying agent according to claim 1 for Compound Heavy Metals soil, it is characterised in that：The steel-making slag powder
35-50%；Peroxophosphoric acid calcium powder 25-45%；Load phosphatic charcoal 10-25%.
3. the modifying agent according to claim 1 or 2 for Compound Heavy Metals soil, it is characterised in that：The slag
Powder is activated steel slag powder, is prepared from by following methods：
(1) will be one or more by broken sieving in the vessel slag after magnetic separation, open hearth slag and lectric furnace slag；
(2) drying materials to its moisture content for taking particle diameter to be less than 2mm in the product obtained is less than 2%；
(3) product obtained is ground and crossed after the sieve of 150-200 mesh, then through 500-700 DEG C of calcining 1-2h, obtains activating steel
Ground-slag.
4. the modifying agent according to claim 1 for Compound Heavy Metals soil, it is characterised in that：The load phosphoric acid
The charcoal of salt is prepared from by following methods：
(1) phosphate solution that concentration is 0.01-0.05mol/L is prepared, the ground 0.1-0.3mm of charcoal is sieved, given birth to
Thing powdered carbon；
(2) by biological powdered carbon and aluminum sulfate according to mass ratio 20-30:1 mixing, obtains biological powdered carbon compound；
(3) the biological powdered carbon compound of gained is impregnated into phosphate solution, stirs 10-15min, vibrate and stir at 20-30 DEG C
Mix and 36-48h is stood after 10-15h, obtain gelatinous precipitate；
(4) gelatinous precipitate is less than 2%, mistake that products therefrom is levigate using 100-250 DEG C airflow drying to its moisture content
150-200 mesh sieves, obtain loading phosphatic charcoal.
5. it is used for the modifying agent of Compound Heavy Metals soil according to claim 1 or 4, it is characterised in that：The biology
Charcoal is dried to its constant mass by the one or more in coffee grounds, tea foam and Chinese medicine slag at 100-105 DEG C, in anoxic
Under the conditions of be made by 400-700 DEG C of cracking.
6. the modifying agent according to claim 1 for Compound Heavy Metals soil, it is characterised in that：The calcium superphosphate
Powder is prepared from by following methods：By P2O5Content is that 14-20% calcium superphosphate is contained to it using 100-250 DEG C of airflow drying
Water rate is less than 2%, ground 150-200 mesh sieves.
7. the preparation method of the modifying agent for being used for Compound Heavy Metals soil described in claim 1, it is characterised in that including such as
Lower step：Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic charcoal of load are mixed by weight percentage, using dry method
Stir 0.5-1h and cross 150-200 mesh sieves to after being well mixed, obtain modifying agent.
8. the application method of the modifying agent for being used for Compound Heavy Metals soil described in claim 1, it is characterised in that：Will be described
Modifying agent is mixed with heavy metal polluted soil, wherein, the modifying agent consumption is the 5-15% of heavy metal polluted soil dry weight,
And the moisture content of the heavy metal polluted soil is 16-30%.
9. the application method of the modifying agent according to claim 8 for Compound Heavy Metals soil, it is characterised in that：Institute
State particle diameter in heavy metal polluted soil and be less than 0.075mm granule content for 65-100%, wherein content of heavy metal lead is more than
2000mg/kg, heavy metal zinc content is more than 2000mg/kg, and heavy metal copper content is more than 2000mg/kg, and heavy metal nickel content is big
In 2000mg/kg.
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| CN115181574A (en) * | 2022-08-15 | 2022-10-14 | 施可丰化工股份有限公司 | Saline-alkali soil conditioner and preparation method thereof |
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