CN104556342A - Medicament for restoring hexavalent chromium contaminated soil and underground water and preparation method of medicament - Google Patents
Medicament for restoring hexavalent chromium contaminated soil and underground water and preparation method of medicament Download PDFInfo
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- CN104556342A CN104556342A CN201510036060.3A CN201510036060A CN104556342A CN 104556342 A CN104556342 A CN 104556342A CN 201510036060 A CN201510036060 A CN 201510036060A CN 104556342 A CN104556342 A CN 104556342A
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- wilkinite
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002689 soil Substances 0.000 title claims abstract description 77
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003814 drug Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 143
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000002002 slurry Substances 0.000 claims abstract description 69
- 239000002699 waste material Substances 0.000 claims abstract description 67
- 239000000440 bentonite Substances 0.000 claims abstract description 65
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 65
- 239000003513 alkali Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 123
- 239000002253 acid Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 239000000428 dust Substances 0.000 claims description 35
- 210000002966 serum Anatomy 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000007689 inspection Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 67
- 239000011651 chromium Substances 0.000 abstract description 54
- 229910052804 chromium Inorganic materials 0.000 abstract description 46
- 230000009467 reduction Effects 0.000 abstract description 21
- 230000001988 toxicity Effects 0.000 abstract description 6
- 231100000419 toxicity Toxicity 0.000 abstract description 6
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- 230000000052 comparative effect Effects 0.000 description 17
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- 230000000694 effects Effects 0.000 description 11
- 238000012423 maintenance Methods 0.000 description 11
- 239000004033 plastic Substances 0.000 description 9
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- 238000005516 engineering process Methods 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
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- 238000001556 precipitation Methods 0.000 description 5
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- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 229940038773 trisodium citrate Drugs 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
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- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
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- 239000003365 glass fiber Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 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
- 239000011425 bamboo Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- -1 harmless to organism Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 229910021647 smectite Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
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- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a medicament for restoring hexavalent chromium contaminated soil and underground water. The restoring medicament consists of the following ingredients in percentage by mass: 35-45 percent of active carbon powder loaded acidified bentonite slurry, 35-45 percent of zero-valent iron powder loaded bentonite slurry and 10-30 percent of mixed slurry of bentonite and industrial waste alkali. The medicament is relatively high in hexavalent chromium reduction capability and can be used for effectively reducing the toxicity of the hexavalent chromium contaminated soil and underground water, efficiently reducing hexavalent chromium, curing trivalent chromium and also balancing the pH value of the soil and the underground water; meanwhile, the invention also provides a preparation method of the medicament, and thus the medicament can be used for treating wastes by using wastes and is low in cost and simple to prepare.
Description
Technical field
The invention belongs to civil engineering work, environmental geotechnical technical field, specifically, relate to reparation medicament and the preparation method of a kind of hexavalent chromium polluted soil and underground water, this reparation medicament can be used for afforesting, in the recovery project on the hexavalent chromium polluted stratum of construction land, be particularly useful for that the pollution of chromium of low-permeability sexavalent chrome is glutinous, silt.
Background technology
Chromium and compound plays a significant role in modern industrial society, continuing along with process of industrialization, the modern industrial enterprises such as plating, process hides, metallurgy, medicine are built in a large number and are developed, normal containing plurality of heavy metal chromium in the three wastes of its discharge, be discharged in surrounding environment and cause Soil Surrounding and groundwater pollution.Chromium exists with the form of sexavalent chrome Cr (VI) and trivalent chromium Cr (III) in soil and groundwater environment, wherein trivalent chromium is that people and animal carry out the trace element required for metabolism to glucose and grease, but Excess free enthalpy can work the mischief to human body; And sexavalent chrome has the solubleness higher far beyond trivalent chromium and transport property, large 100 times of its toxicity ratio trivalent chromium, has strong carcinogenesis, is classified as one of 17 kinds of highly dangerous toxicants by USEPA (EPA).China " integrated wastewater discharge standard (GB 8978-1996) " is classified as first kind pollutent.Sexavalent chrome in soil and trivalent chromium can transform under certain condition mutually, and therefore hexavalent chromium polluted soil not only answers reduction of hexavalent chromium to be hypotoxicity trivalent chromium when repairing, and also need to reduce active chromic content in soil.
The hexavalent chromium polluted soil remediation technology that present stage uses comprises original position and showering two kinds, all there is limitation in various degree, is unfavorable for that large-scale promotion uses.If showering is due to needs carrying soil, earth moving amount is more, large to Geotechnical Environment destructiveness, is only applicable to the reparation of a small amount of soil.In based technique for in-situ remediation, sexavalent chrome and trivalent chromium effective sealing can be wrapped in inert solid matrix to reduce the toxicity of contaminated soil by cement solidification/stabilization technology, but fundamentally do not change chromic form, there is pollution hidden trouble again, the high alkalinity of cement solidification simultaneously can change the acid base equilibrium of the soil body and water body, has a negative impact to periphery biology; Microorganism remediation technology is harsh to the requirement for environmental conditions such as temperature, pH, and not easily meet during site operation, its remediation efficiency is easily influenced; The medicament usage quantity of aqueous solution lavage is large, and acid or alkali environment single (simultaneously cannot ensure chromic reduction and chromic precipitation), is not suitable for the stratum that the permeability coefficients such as clay are less, in addition its ferrous sulfate (FeSO used
4), Sodium Pyrosulfite (Na
2s
2o
5), iron protochloride (FeCl
2) etc. in reduction medicament containing macro-corrosion negatively charged ion, secondary pollution can be caused to soil and underground water, jeopardously descend the structures such as engineered cementitious, reinforcing bar safety.For the above-mentioned defect that existing reparation means have, find a kind of sexavalent chrome that can reduce more up hill and dale in contaminated soil, underground water, effectively can reduce free state trivalent chromium content simultaneously, with low cost, applied widely, and the original position of non-secondary pollution hexavalent chromium polluted stratum recovery technique becomes the focus of insider's growing interest.
Summary of the invention
Technical problem: technical problem to be solved by this invention is: the reparation medicament that a kind of hexavalent chromium polluted soil and underground water are provided, this medicament has stronger reduction of hexavalent chromium ability, effectively can reduce the toxicity of chromium-polluted soil and underground water, while efficient reduction of hexavalent chromium, solidification trivalent chromium, and can the potential of hydrogen of balanced soil and underground water; The preparation method of this medicament is also provided simultaneously, makes this medicament realize the treatment of wastes with processes of wastes against one another, with low cost, make simple and easy.
Technical scheme: for solving the problems of the technologies described above, the technical solution used in the present invention is:
A reparation medicament for hexavalent chromium polluted soil and underground water, this reparation medicament, composed of the following components by mass percent:
The acid bentonite slurries of supported active carbon dust: 35%-45%;
The bentonite slurry of load zeroth order iron powder: 35%-45%;
Wilkinite and industrial alkali waste mixed serum: 10%-30%.
Further, the acid bentonite slurries of described supported active carbon dust, composed of the following components by mass percent:
And the pH value range of the acid bentonite slurries of this supported active carbon dust is 3.5-4.5.
Further, the bentonite slurry of described load zeroth order iron powder, composed of the following components by mass percent:
Wilkinite: 10%;
Zeroth order iron powder: 20%;
Water: 70%.
Further, described wilkinite and industrial alkali waste mixed serum, composed of the following components by mass percent:
Wilkinite: 5%;
Industrial alkali waste: 25%;
Water: 70%;
And the pH value range of wilkinite and industrial alkali waste mixed serum is 10.5-12.
A preparation method for above-mentioned hexavalent chromium polluted soil and the reparation medicament of underground water, this preparation method comprises the following steps:
The process preparing the acid bentonite slurries of supported active carbon dust is: activated carbon powder is crossed 200 mesh sieves, then activated carbon powder 20-40h is soaked, water logging there is not activated carbon powder, then activated carbon powder is mixed with Citric Acid, usp, Anhydrous Powder, Citric Acid, usp, Anhydrous Powder sodium, wilkinite, adding water and being adjusted to water ratio is 65%, stir 15-20min, wilkinite, activated carbon powder, Citric Acid, usp, Anhydrous Powder and Citric Acid, usp, Anhydrous Powder sodium are mixed, makes the acid bentonite slurries of supported active carbon dust; The acid bentonite slurries of this supported active carbon dust are according to mass percent, composed of the following components: wilkinite: 5%; Activated carbon powder: 10%; Citric Acid, usp, Anhydrous Powder: 18%; Citric Acid, usp, Anhydrous Powder sodium: 2%; Water: 65%;
The process of the bentonite slurry of preparation load zeroth order iron powder is: zeroth order iron powder is crossed 200 mesh sieves, then soaks zeroth order iron powder 30min-1h with the dilute hydrochloric acid solution that massfraction is 0.2%-0.5%, then rinse with water, until inspection does not measure Cl in the aqueous solution
-, remove iron powder surface oxide layer and grease, mix subsequently with wilkinite, and add water that to be adjusted to water ratio be 70%, stirring 10-15min, makes zeroth order iron powder mix with wilkinite, makes the bentonite slurry of load zeroth order iron powder; The bentonite slurry of this load zeroth order iron powder is according to mass percent, composed of the following components: wilkinite: 10%, zeroth order iron powder: 20%, water: 70%;
The process preparing wilkinite and industrial alkali waste mixed serum is: first dry industrial alkali waste, its water ratio is made to be less than 4%, and cross 2mm sieve, mix with wilkinite, adding water and being adjusted to water ratio is 70% again, stirs 10-15min, wilkinite is mixed with waste lye, make wilkinite and industrial alkali waste mixed serum, the pH value of this wilkinite and industrial alkali waste mixed serum is between 10.5-12, and this wilkinite and industrial alkali waste mixed serum sieve by 3mm; This wilkinite and industrial alkali waste mixed serum, composed of the following components by mass percent: wilkinite: 5%, industrial alkali waste: 25%, water: 70%.
Beneficial effect: compared with the hexavalent chromium polluted soil restoring technology of tradition, technical scheme of the present invention has following beneficial effect:
1. repair medicament and there is good reduction of hexavalent chromium and solidification trivalent chromium ability, and it is wide to be suitable for stratigraphic type.Medicament of the present invention is divided into the bentonite slurry of the acid bentonite slurries of supported active carbon dust, load zeroth order iron powder, wilkinite and industrial alkali waste mixed serum by Sequence of fertilizer application.Add wilkinite and ensure that the mobility and workability of injecting medicament, avoid a large amount of infiltration of medicament in underground using the aqueous solution easily to cause to run off, and the characteristic of its very difficult adsorbing hexavalent chromium also ensure that medicament is to chromic repair ability, in addition bentonite slurry provides the water surrounding required for the chemical reaction processes such as reduction of hexavalent chromium, is particularly useful for the pollution stratum that water content is lower.Numerous Fe-C galvanic cell can be formed in the water surrounding that iron powder in component and activated carbon powder provide at bentonite slurry, under the corrosive nature of electrochemical reaction, generate a large amount of Fe
2+, and then efficiently go back the sexavalent chrome in native soil, underground water.Whole process reaction is rapid, can complete chromic reduction in one day.In addition the citric acid in acid bentonite supported active carbon dust slurries then can keep the sour environment (pH 3.5-4.5) of reduction of hexavalent chromium needs, provides electrochemical reaction and Fe
2+a large amount of H consumed in reduction of hexavalent chromium process
+, and the interpolation of Citrate trianion enhances the surge capability of acid slurries, can maintain the appropriate acid environment required for repairing within considerable time.Soil can adsorb and fix the sexavalent chrome of 8.5% ~ 36.2%, and as a kind of tricarboxylic weak organic acid, the H that citric acid is more
+the sexavalent chrome of energy dissolving acid solvent, its carboxyl can by the sexavalent chrome complexing of non-aqueous state out simultaneously, the sexavalent chrome that therefore not only can reduce in the above soil pore water of ground water table and underground water, the sexavalent chrome also in reducible soil.Citric acid also can remove the iron powder surface zone of oxidation that may exist and grease etc., promotes largely the corrosion speed of zeroth order iron powder to improve chromic remediation efficiency.Under this external sour environment (pH<5), activated carbon powder has good reduction of hexavalent chromium ability equally, and this also further enhancing it and removes chromic ability.
At the acid bentonite slurries of supported active carbon dust and the bentonite slurry of load zeroth order iron powder, sexavalent chrome is thoroughly reduced on chromic basis, then utilizes basic agent-wilkinite and industrial alkali waste mixed serum and contaminated soil, underground water mix even further.In wilkinite and industrial alkali waste mixed serum, Industry Waste alkali lye is from Industry Waste rejected material, comprises used lime, spent caustic, useless carbide slag.As carbide slag comes from the waste produced in industrial acetylene process, its particle comparatively unslaked lime is thinner, and specific surface area is about 5 times of unslaked lime, and calcium hydroxide content is a little more than unslaked lime simultaneously.The OH that used lime, spent caustic, useless carbide slag produce
-all can react with trivalent chromium and generate Cr (OH)
3precipitation, and and Fe
3+reaction generates Fe (OH)
3colloid, and ironic hydroxide inherently a kind of flocculation agent efficiently, can promote Cr (OH) further
3the generation of precipitation; And the potential of hydrogen on energy active balance stratum, and generate nontoxic citrate of lime insolubles with citric acid reactions, make formation water present neutrality or weakly alkaline (pH is 7-9), Cr (OH) under this pH environment
3solubleness minimum, be conducive to eliminate trivalent chromium.Utilize in calcium carbide waste slag, used lime, spent caustic etc. and neutrality that citric acid provides or weakly alkaline environment, be conducive to periphery plant-growth, and significantly can reduce processing costs, the treatment of wastes with processes of wastes against one another simultaneously, realizes utilization of waste material, avoids secondary pollution.In addition the colloidalmaterial in the activated carbon powder in medicament, wilkinite and soil all can active adsorption Cr (OH)
3, strengthen for chromic removal effect.
2. medicament preparation method is simple to operate, and medicament utilization ratio is high.This pharmaceutical production process is simple, do not need complex apparatus, only need when preparing the acid bentonite slurries of supported active carbon dust to mix by technical grade Citric Acid, usp, Anhydrous Powder with without hydration Trisodium Citrate crystal with activated carbon powder, wilkinite, then add water stirring and adjusting homogeneity and mobility.The bentonite slurry of load zeroth order iron powder also only needs when preparing to adopt wet-mixed wilkinite, wet iron powder, then add water allotment homogeneity and mobility.Wilkinite and industrial alkali waste mixed serum are prepared and are taked industrial alkali waste mixing wilkinite equally, then add suitable quantity of water stirring and adjusting homogeneity and mobility.
3. the technical program is applied widely, to periphery eco-friendly.The present invention requires low to place soil pH value, temperature etc., is applicable to the hexavalent chromium polluted place of multiple potential of hydrogen.Institute's with medicament that makes is not containing toxic component, ecotope around place can not be endangered, as citric acid and Trisodium Citrate are extensively present in occurring in nature, be commonly used for the foodstuff additive such as beverage, grape wine, seasonings, harmless to organism, citric acid can generate stable with calcium hydroxide generation neutralization reaction and be insoluble in the citrate of lime of water.Citric acid makes this medicament not be only applicable to chromic reparation in the above pore water of ground water table and underground water to good extracting effect chromic in soil, is also applicable to the hexavalent chromium polluted reparation in soil.This medicament avoids and uses ferrous sulfate etc. as reductive agent or the mineral acid acidified wilkinite such as sulfuric acid, hydrochloric acid to the impact of soil corrosivity, place soil and underground water can be made after using to keep neutral or weakly alkaline, be applicable to plant-growth, after repairing, place can be used as land use for greening and the construction land such as building, industry.
Accompanying drawing explanation
Fig. 1 represents that the present invention tests total chromium concn value bar graph in 1 each sample repairing polluted soil.
Fig. 2 represents that the present invention tests hexavalent chromium concentration value bar graph in 1 each sample repairing polluted soil.
Fig. 3 represents that the present invention tests the pH value bar graph of 1 each sample repairing polluted soil.
Fig. 4 represents that the present invention tests 2 each sample and repairs total chromium concn value bar graph in underground water.
Fig. 5 represents that the present invention tests 2 each sample and repairs hexavalent chromium concentration value bar graph in underground water.
Fig. 6 represents that the present invention tests the pH value bar graph that 2 each sample repair underground water.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described in detail.
The reparation medicament of a kind of hexavalent chromium polluted soil of the present invention and underground water, composed of the following components by mass percent:
The acid bentonite slurries of supported active carbon dust: 35%-45%;
The bentonite slurry of load zeroth order iron powder: 35%-45%;
Wilkinite and industrial alkali waste mixed serum: 10%-30%.
In above-mentioned reparation medicament, the acid bentonite slurries of supported active carbon dust, composed of the following components by mass percent:
And the pH value range of the acid bentonite slurries of this supported active carbon dust is 3.5-4.5.
In above-mentioned reparation medicament, the bentonite slurry of load zeroth order iron powder, composed of the following components by mass percent:
Wilkinite: 10%;
Zeroth order iron powder: 20%;
Water: 70%.
In above-mentioned reparation medicament, wilkinite and industrial alkali waste mixed serum, composed of the following components by mass percent:
Wilkinite: 5%;
Salkali waste: 25%;
Water: 70%.
And the pH scope of wilkinite and industrial alkali waste mixed serum is 10.5-12.When industrial alkali waste is liquid, the quality that the Solute mass of industrial alkali waste accounts for wilkinite and industrial alkali waste mixed serum is 25%.
The mechanism of above-mentioned reparation medicament and hexavalent chromium polluted soil and underground water is: first inject the acid bentonite slurries of supported active carbon dust to hexavalent chromium polluted place to provide the sour environment of pH scope between 3.5-4.5 and to repair the aqueous environment needed, and under the effect of citric acid, the sexavalent chrome be adsorbed in soil is extracted; Thereafter inject the bentonite slurry of load iron powder, utilize the electrode reaction of the activated carbon powder in the acid bentonite slurries of supported active carbon dust and the bentonite slurry of load iron powder and zeroth order iron powder to generate a large amount of Fe
2+, produce redox reaction with sexavalent chrome and generate Fe
3+and trivalent chromium, and then be hypotoxic trivalent chromium by the hexavalent chrome reduction in soil and underground water.After this wilkinite injected and industrial alkali waste mixed serum then with the citric acid of the acid bentonite slurries of supported active carbon dust, make soil and underground water present weakly alkaline (pH scope is 7-9), OH wherein
-with trivalent chromium and Fe
3+react, generate Cr (OH) respectively
3precipitation and Fe (OH)
3gel, reduces the chromic content of free state in soil and underground water, reduces trivalent chromium in underground environment, is oxidized to chromic possibility.
The acid bentonite slurries of supported active carbon dust are made up of wilkinite, activated carbon powder, Citric Acid, usp, Anhydrous Powder, Citric Acid, usp, Anhydrous Powder sodium and water.Wherein utilize wilkinite to ensure to inject mobility and the workability of medicament, and the water surrounding required for reduction of hexavalent chromium is provided, avoid the infiltration of medicament in underground to run off.Described activated carbon powder can be industrial wooden, shell or ature of coal carbon dust, and its particle diameter is less than or equal to 200 orders.The object adding activated carbon powder in a medicament utilizes the potential difference of carbon dust and iron powder to form electrode reaction, makes iron powder be the Fe with high reducing power by Quick Oxidation
2+and enter in the aqueous solution, at Fe
0and Fe
2+acting in conjunction under reduction of hexavalent chromium.Citric Acid, usp, Anhydrous Powder and Citric Acid, usp, Anhydrous Powder sodium are technical grade, wherein use the effect of citric acid to be to provide sour environment (pH=3.5 ~ 4.5) required for reduction of hexavalent chromium.In addition citric acid can be extracted into being adsorbed in soil the part sexavalent chrome being difficult to repair in the aqueous solution, and then strengthens chromic repairing effect.Add the acid buffer capacity that Trisodium Citrate then can improve acid bentonite slurries, the pH environment residing for the chemical process of reduction of hexavalent chromium is maintained within a certain range, thus ensures chromic reduction efficiency.
The bentonite slurry of load zeroth order iron powder is made up of wilkinite, zeroth order iron powder and water.Wherein bentonitic effect is the mobility and the workability that ensure to inject medicament, that improves zeroth order iron powder uses homogeneity, avoid the rapid precipitation of zeroth order iron powder in slurries, and the water surrounding required for reduction of hexavalent chromium is provided, avoid the infiltration of medicament in underground to run off.Zeroth order iron powder can be the reduced iron powder that waste iron filing etc. is made, and its particle diameter is less than or equal to 200 orders.Zeroth order iron powder enters after in soil and underground water, produces electrode reaction, generate Fe sexavalent chrome to high reducing power with the activated carbon powder in the acid bentonite slurries of supported active carbon dust
2+, and then efficiently remove sexavalent chrome.The bentonite slurry of the acid bentonite slurries of supported active carbon dust and load zeroth order iron powder is separately also successively used, be in order to avoid the zeroth order iron powder in the bentonite slurry of the citric acid in the acid bentonite slurries of supported active carbon dust, activated carbon powder and load zeroth order iron powder is in the contact reacts in advance on earth's surface, reduce the unhelpful loss of medicament effective constituent.
Wilkinite and industrial alkali waste mixed serum are then made up of wilkinite, industrial alkali waste and water.Wherein industrial alkali waste can be used lime, spent caustic or useless carbide slag slurry or dry powder.Industrial alkali waste to be mixed with wilkinite and the stirring that adds water is modulated into uniform flow slurries.The effect of industrial alkali waste be in and the acid bentonite slurries of supported active carbon dust use the sour environment of rear generation for neutral or weakly alkaline, and react with free trivalent chromium and generate insoluble throw out; Bentonitic effect is the mobility and the workability that ensure to inject medicament, and that improves salkali waste uses homogeneity.
The mixing water of medicament can be tap water, underground water or place underground pollution water, and its effect is the mobility ensureing injection and mix slurries, and provides the aqueous environment required for reaction.
The preparation method of above-mentioned hexavalent chromium polluted soil and the reparation medicament of underground water, comprises the following steps:
The process preparing the acid bentonite slurries of supported active carbon dust is: activated carbon powder is crossed 200 mesh sieves, then activated carbon powder 20-40h is soaked, water logging there is not activated carbon powder, then activated carbon powder is mixed with Citric Acid, usp, Anhydrous Powder, Citric Acid, usp, Anhydrous Powder sodium, wilkinite, adding water and being adjusted to water ratio is 65%, stir 15-20min, wilkinite, activated carbon powder, Citric Acid, usp, Anhydrous Powder and Citric Acid, usp, Anhydrous Powder sodium are mixed, makes the acid bentonite slurries of supported active carbon dust; The acid bentonite slurries of this supported active carbon dust are according to mass percent, composed of the following components: wilkinite: 5%; Activated carbon powder: 10%; Citric Acid, usp, Anhydrous Powder: 18%; Citric Acid, usp, Anhydrous Powder sodium: 2%; Water: 65%.
In the process of the above-mentioned acid bentonite slurries preparing supported active carbon dust, activated carbon powder is soaked 20-40h in water, the impact that activated carbon powder adsorptive power is repaired sexavalent chrome can be weakened.
The process of the bentonite slurry of preparation load zeroth order iron powder is: zeroth order iron powder is crossed 200 mesh sieves, then soaks zeroth order iron powder 30min-1h with the dilute hydrochloric acid solution that massfraction is 0.2%-0.5%, then rinse with water, until inspection does not measure Cl in the aqueous solution
-, remove iron powder surface oxide layer and grease, it mixed with wilkinite subsequently, and add water that to be adjusted to water ratio be 70%, stirring 10-15min, makes zeroth order iron powder mix with wilkinite, makes the bentonite slurry of load zeroth order iron powder; The bentonite slurry of this load zeroth order iron powder is according to mass percent, composed of the following components: wilkinite: 10%, zeroth order iron powder: 20%, water: 70%.
In the process of the bentonite slurry of above-mentioned preparation load zeroth order iron powder, utilize dilute hydrochloric acid solution to soak zeroth order iron powder, to remove iron powder surface oxide layer and grease, iron powder fully can be contacted with activated carbon powder and the aqueous solution, improve the utilising efficiency of zeroth order iron powder.
The process preparing wilkinite and industrial alkali waste mixed serum is: first dry industrial alkali waste, its water ratio is made to be less than 4%, and cross 2mm sieve, mix with wilkinite again, adding water and being adjusted to water ratio is 70%, make it have good mobility and workability, stir 10-15min, wilkinite is mixed with waste lye, make wilkinite and industrial alkali waste mixed serum, the pH value of this wilkinite and industrial alkali waste mixed serum is between 10.5-12, and this wilkinite and industrial alkali waste mixed serum sieve by 3mm; This wilkinite and industrial alkali waste mixed serum, composed of the following components by mass percent: wilkinite: 5%, industrial alkali waste: 25%, water: 70%.
Prove reparation medicament of the present invention below by test there is good reduction of hexavalent chromium and solidify chromic ability, and heavy metal-polluted soil Leaching is lower.
The ingredient origin adopted in test and specification as follows:
Wilkinite: purchased from Shanghai Meng Mei Chemical Co., Ltd. is 600 order wilkinites, and its smectite content>=30%, density is 3g/cm
3, apparent viscosity is 2.8mPa.S, and expansion multiple is 2.
Activated carbon powder: purchased from Zhengzhou bamboo grove gac development corporation, Ltd., for crossing the industry/sanitary sewage decolouring Powdered Activated Carbon of 200 mesh sieves, its moisture content 10%, ash is 5%, and pH value is 6.3, and specific surface area is 1263.8m
2/ g.
Citric acid: purchased from Wujiang Tian Yi Chemical Co., Ltd. is technical grade Citric Acid, usp, Anhydrous Powder, purity 98%.
Trisodium Citrate: purchased from Wujiang Tian Yi Chemical Co., Ltd. is technical grade Citric Acid, usp, Anhydrous Powder sodium, purity 98%.
Zeroth order iron powder: purchased from Jin Sui powder metallurgy company limited of Suzhou City, iron powder particle diameter is 200 orders, and iron level is greater than 98.5%.
Industrial alkali waste: adopt carbide slag, purchased from Jiangsu Chang Fei acetylene manufacturing company, pH (Tu Shui ratio=1:1) is 12.84, and N2 adsorption analyser records its specific surface area 24.66m
2g
-1, main chemical compositions is CaO 68.99%, SiO
28.84%, Al
2o
32.16%, Fe
2o
30.15%, the particle that particle diameter is less than 75 μm accounts for 71.8%.
The sample be made up of said components is as shown in the table:
One, sexavalent chrome repairing effect test in soil
Test apparatus: rotating speed is the convertible oscillation device of 30 ± 2r/min.
Touchstone: national environmental protection industry standard " solid waste Leaching leaching method sulfonitric method " (HJ/T 299-2007).
Subjects: above-mentioned 4 samples, and a comparative sample.This comparative sample is conch board PC32.5 composite Portland cement, and Xray fluorescence spectrometer measures its principal element content and is: CaO 44.37%, SiO
227.41%, Al
2o
313.09%.
Test soil takes from Jiangsu Electroplate Factory, and pollution of chromium concentration is 7366mg/kg, and wherein content of 6-valence Cr ions is 2350mg/kg.
Process of the test: the process of the test of 4 samples is identical.The process of the test of a sample is: get pollution of chromium soil, at room temperature ventilate air-dry, mix with the acid bentonite slurries of the supported active carbon dust of sample and stir respectively after crossing 2mm sieve, then the bentonite slurry adding load zeroth order iron powder is stirred well to evenly.The Polluted Soil mixed and pharmaceutical mixture are positioned in plastic sealing bag, maintenance 3 days in standard curing room (temperature 20 DEG C, relative humidity 95%).Take out maintenance soil sample, to mix with industrial alkali waste mixed serum with wilkinite and stir, being again positioned in plastic sealing bag, then in the middle maintenance of standard curing room (temperature 20 DEG C, relative humidity 95%) 7 days.Take out maintenance soil sample, detect soil sample pH, and carry out sulfonitric method toxicity characteristic leaching procedure, detect trivalent chromium and hexavalent chromium concentration in leach liquor.
The process of the test of comparative sample is: get pollution of chromium soil, at room temperature ventilates air-dry and crosses 2mm sieve, adding comparative sample and fully mix, then add the water being equivalent to Polluted Soil mass percent 40%, and be stirred well to evenly.The Polluted Soil mixed and comparative sample mixture are positioned in plastic sealing bag, maintenance 10 days in standard curing room (temperature 20 DEG C, relative humidity 95%), take out maintenance soil sample, detect soil sample pH, and carry out sulfonitric method toxicity characteristic leaching procedure, detect trivalent chromium and hexavalent chromium concentration in leach liquor.
In test, 4 samples and Polluted Soil mass ratio are 1:10.Comparative sample and Polluted Soil mass ratio are 1:10.
Test-results is as follows:
What Fig. 1 represented is repair total chromium concn value in soil sample sulfonitric method leach liquor, and Fig. 2 represents hexavalent chromium concentration value in reparation soil sample sulfonitric method leach liquor, and Fig. 3 represents reparation soil sample pH value.Can find out that the total chromium concn of leach liquor of 4 sample reparation soil is all less than 15mg/L from Fig. 1 and Fig. 2, and hexavalent chromium concentration is all less than 5mg/L, meets limit value requirement.Wherein minimum with the concentration value of sample 3 in the total chromium concn of leach liquor, be only 3.83mg/L; Leach liquor trivalent chromium concentration is minimum with sample 1, be 2.67mg/L, and leach liquor hexavalent chromium concentration value is minimum with sample 4, is 0.28mg/L.On the contrary, the leach liquor hexavalent chromium concentration of comparative sample reparation soil is 21.56mg/L, and much larger than the limit value of 5mg/L, and its total chrome content is 66.22mg/L, have also exceeded total chromium concn limit value of 15mg/L.4 samples repair native pH value substantially all between 6-9, and in neutral or weakly alkaline, and comparative sample repairs the pH value of soil up to 12.93, is strong basicity.As apparent from Fig. 1 and Fig. 2 can: adopt 4 its sexavalent chromes of the repairing hexavalent chromium polluted soil of sample of the present invention and total chromium Steep cencentration value all remarkable in comparative sample, it has stronger reduction of hexavalent chromium and solidifies chromic ability, in addition 4 samples repair the pH value of soil substantially between 5.5-9, and the soil acidity or alkalinity after its reparation is more suitable for biological growth.
Two, trivalent chromium repairing effect test in underground water.
Test apparatus: 500mL sealed plastic bottle, precision is the pH meter of 0.01.
Subjects: above-mentioned 4 samples, and a comparative sample.This comparative sample is conch board PC32.5 composite Portland cement, and Xray fluorescence spectrometer measures its principal element content and is: CaO 44.37%, SiO
227.41%, Al
2o
313.09%.
Pollution of chromium underground water takes from 2m place, below this earth's surface, sewage draining exit place of Electroplate Factory, and its total chrome content is 18.3mg/L, and wherein hexavalent chromium concentration is 7.6mg/L.
Process of the test: the process of the test of 4 samples is identical.The process of the test of a sample is: get pollution of chromium underground water and be positioned in 500mL sealed plastic bottle, pour the acid bentonite slurries of sample supported active carbon dust into and stir 15min to even, then the bentonite slurry adding load zeroth order iron powder fully stirs 15min to even.The polluted underground water mixed and pharmaceutical mixture are sealed in Plastic Bottle, maintenance 3 days in standard curing room (temperature 20 DEG C, relative humidity 95%).Thereafter take out Plastic Bottle open and add wilkinite and industrial alkali waste mixed serum, mix and stir 15min to evenly, again to seal and in the middle maintenance of standard curing room (temperature 20 DEG C, relative humidity 95%) 7 days.With the water sample after the glass fiber filter maintenance of 0.45 μm, detect trivalent chromium, hexavalent chromium concentration and the pH value in water sample.
The process of the test of comparative sample is: get same pollution of chromium underground water and be positioned in 500mL sealed plastic bottle, adds comparative sample and stirs 15min to mixing.The polluted underground water mixed and comparative sample mixture are sealed in Plastic Bottle, maintenance 10 days in standard curing room (temperature 20 DEG C, relative humidity 95%).With the water sample after the glass fiber filter maintenance of 0.45 μm, detect trivalent chromium, hexavalent chromium concentration and the pH value in water sample.
In test, 4 samples and polluted underground water mass ratio are 1:5, and comparative sample and polluted underground water mass ratio are 1:5.
Test-results is as follows:
Fig. 4 represents total chromium concn value in reparation underground water, and Fig. 5 represents hexavalent chromium concentration value in reparation underground water, and Fig. 6 represents the pH value of repairing underground water.As can be seen from the figure the total chromium concn of leach liquor of 4 sample reparation soil and hexavalent chromium concentration are all less than 0.1mg/L, meet limit value requirement.Wherein, total chromium concn value is minimum with sample 3, is only 0.026mg/L; Hexavalent chromium concentration value is minimum with sample 4, is 0.001mg/L; Trivalent chromium concentration value is minimum with sample 1, is only 0.016mg/L.On the contrary, the hexavalent chromium concentration that comparative sample is repaired in underground water is 6.21mg/L, and total chromium concn is 14.27mg/L, and far above the limit value of 0.1mg/L, the ability of its repairing hexavalent chromium polluted underground water is poor, is far weaker than 4 samples.In addition, 4 samples repair the pH value of underground water between 6.03-8.63, and the pH value that comparative sample repairs underground water is 12.26, presents strong basicity.4 samples repair the neutrality of underground water or weakly alkaline environment to around ecology advantageously.
Claims (5)
1. a reparation medicament for hexavalent chromium polluted soil and underground water, is characterized in that, this reparation medicament, composed of the following components by mass percent:
The acid bentonite slurries of supported active carbon dust: 35%-45%;
The bentonite slurry of load zeroth order iron powder: 35%-45%;
Wilkinite and industrial alkali waste mixed serum: 10%-30%.
2., according to the reparation medicament of hexavalent chromium polluted soil according to claim 1 and underground water, it is characterized in that, the acid bentonite slurries of described supported active carbon dust, composed of the following components by mass percent:
Wilkinite: 5%;
Activated carbon powder: 10%;
Citric Acid, usp, Anhydrous Powder: 18%;
Citric Acid, usp, Anhydrous Powder sodium: 2%;
Water: 65%;
And the pH value range of the acid bentonite slurries of this supported active carbon dust is 3.5-4.5.
3., according to the reparation medicament of hexavalent chromium polluted soil according to claim 1 and underground water, it is characterized in that, the bentonite slurry of described load zeroth order iron powder, composed of the following components by mass percent:
Wilkinite: 10%;
Zeroth order iron powder: 20%;
Water: 70%.
4., according to the reparation medicament of hexavalent chromium polluted soil according to claim 1 and underground water, it is characterized in that, described wilkinite and industrial alkali waste mixed serum, composed of the following components by mass percent:
Wilkinite: 5%;
Industrial alkali waste: 25%;
Water: 70%;
And the pH value range of wilkinite and industrial alkali waste mixed serum is 10.5-12.
5. a preparation method for the reparation medicament of hexavalent chromium polluted soil according to claim 1 and underground water, is characterized in that, this preparation method comprises the following steps:
The process preparing the acid bentonite slurries of supported active carbon dust is: activated carbon powder is crossed 200 mesh sieves, then activated carbon powder 20-40h is soaked, water logging there is not activated carbon powder, then activated carbon powder is mixed with Citric Acid, usp, Anhydrous Powder, Citric Acid, usp, Anhydrous Powder sodium, wilkinite, adding water and being adjusted to water ratio is 65%, stir 15-20 min, wilkinite, activated carbon powder, Citric Acid, usp, Anhydrous Powder and Citric Acid, usp, Anhydrous Powder sodium are mixed, makes the acid bentonite slurries of supported active carbon dust; The acid bentonite slurries of this supported active carbon dust are according to mass percent, composed of the following components: wilkinite: 5%; Activated carbon powder: 10%; Citric Acid, usp, Anhydrous Powder: 18%; Citric Acid, usp, Anhydrous Powder sodium: 2%; Water: 65%;
The process of the bentonite slurry of preparation load zeroth order iron powder is: zeroth order iron powder is crossed 200 mesh sieves, then soaks zeroth order iron powder 30min-1h with the dilute hydrochloric acid solution that massfraction is 0.2%-0.5%, then rinse with water, until inspection does not measure Cl in the aqueous solution
-, remove iron powder surface oxide layer and grease, mix subsequently with wilkinite, and add water that to be adjusted to water ratio be 70%, stirring 10-15min, makes zeroth order iron powder mix with wilkinite, makes the bentonite slurry of load zeroth order iron powder; The bentonite slurry of this load zeroth order iron powder is according to mass percent, composed of the following components: wilkinite: 10%, zeroth order iron powder: 20%, water: 70%;
The process preparing wilkinite and industrial alkali waste mixed serum is: first dry industrial alkali waste, its water ratio is made to be less than 4%, and cross 2mm sieve, mix with wilkinite, adding water and being adjusted to water ratio is 70% again, stirs 10-15min, wilkinite is mixed with waste lye, make wilkinite and industrial alkali waste mixed serum, the pH value of this wilkinite and industrial alkali waste mixed serum is between 10.5-12, and this wilkinite and industrial alkali waste mixed serum sieve by 3 mm; This wilkinite and industrial alkali waste mixed serum, composed of the following components by mass percent: wilkinite: 5%, industrial alkali waste: 25%, water: 70%.
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