CN107715838A - It can remove vertical barrier material of contaminated site organic pollution and preparation method thereof - Google Patents
It can remove vertical barrier material of contaminated site organic pollution and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 230000004888 barrier function Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000440 bentonite Substances 0.000 claims abstract description 90
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 90
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002689 soil Substances 0.000 claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 239000010457 zeolite Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 65
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 56
- 239000002002 slurry Substances 0.000 claims description 48
- 239000007790 solid phase Substances 0.000 claims description 42
- -1 sodium hexametaphosphate modified bentonite Chemical class 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 13
- 239000002957 persistent organic pollutant Substances 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 230000035699 permeability Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 238000002955 isolation Methods 0.000 description 11
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 239000004576 sand Substances 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 229910000281 calcium bentonite Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D31/00—Protective arrangements for foundations or foundation structures; Ground foundation measures for protecting the soil or the subsoil water, e.g. preventing or counteracting oil pollution
- E02D31/002—Ground foundation measures for protecting the soil or subsoil water, e.g. preventing or counteracting oil pollution
- E02D31/004—Sealing liners
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D2300/00—Materials
- E02D2300/0045—Composites
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Abstract
The invention discloses vertical barrier in the original position of a kind of removable contaminated site organic pollution and preparation method thereof.The material includes calgon modified alta-mud, sorbing material and in-situ soil.Sorbing material is the composite of the composition of zeroth order micron iron powder, graphene and zeolite, and its quality is the 1~20% of calgon modified alta-mud quality.The material not only remains the hypotonicity of calgon modified alta-mud and good chemical compatibility, the organic pollution in underground water can also be removed, improve the barrier performance that bentonite vertically obstructs engineering barrier, extend service life, engineering cost is reduced, can be widely applied to the reparation in heavy metal and organic compound contaminated place.
Description
Technical Field
The invention relates to an in-situ vertical isolation barrier technology for controlling polluted underground water, and belongs to the technical field of isolation control of polluted sites.
Background
In recent years, with the economic development and the adjustment of industrial layout, a large number of industrial enterprises are gradually shut down or moved away from urban areas, wherein pollutants generated by high-pollution enterprises such as chemical plants, electroplating plants and the like during the production and operation for many years are still left in original plant places and spread to peripheral areas along with the flow of underground water, thus causing serious threats to public health and surrounding environment.
Because soil and underground water pollution has the characteristics of concealment, hysteresis and accumulation, and self-purification restoration is difficult to achieve, and manual treatment is often difficult to achieve the expected restoration effect due to the limitation of conditions such as geological conditions, environmental factors and economic factors. Although the vertical isolation barrier can not directly eliminate the pollution source, the vertical isolation barrier is used as a pollution site control isolation technology with simple construction, low manufacturing cost and excellent anti-seepage effect, can effectively limit the migration of pollutants and eliminate the adverse effect of the pollution site on the surrounding environment. In addition, vertical isolation barrier technology can provide sufficient time for humans to seek thorough, efficient and economical pollution remediation technologies.
Due to high expansibility and low permeability, the bentonite is widely applied to various antifouling isolation facilities, and a soil-bentonite vertical isolation engineering barrier is a common isolation control method at present. However, natural high-quality bentonite has limited resources and high price, and the permeability coefficient of bentonite is greatly increased under the erosion of chemical solution, so that the barrier effect on a polluted site is difficult to maintain. In many domestic polluted sites, the pollutants are various in types and high in concentration, and the composite polluted sites containing heavy metals and organic matters are not lacked, so that the seepage-proofing performance of the soil-bentonite isolation barrier is seriously tested.
Disclosure of Invention
The technical problem is as follows: the technical problem to be solved by the invention is as follows: the in-situ vertical barrier material capable of adsorbing organic matters has good chemical compatibility, can still maintain low permeability under the action of high-concentration heavy metal and organic matter pollution liquid, has certain pollutant interception capability on organic matter pollution, greatly improves the barrier seepage-proofing performance of bentonite, prolongs the service life, reduces the engineering cost, and can be widely applied to restoration of heavy metal and organic matter composite pollution sites.
The technical scheme is as follows: in order to solve the technical problems, the in-situ vertical barrier material capable of removing organic pollutants and the preparation method thereof adopt the following technical scheme:
the barrier material comprises 1-20% of sodium hexametaphosphate modified bentonite, 8-12% of sodium hexametaphosphate modified bentonite and 70-90% of in-situ soil by mass ratio, wherein the adsorption material is a composite material consisting of zeolite, zero-valent micron iron powder and graphene, and the mass ratio of the zeolite to the zero-valent micron iron powder to the graphene of the adsorption material is 6:1: 1-10: 1:1.
Wherein,
the mixing amount of sodium hexametaphosphate in the sodium hexametaphosphate modified bentonite is 2-4% of the mass of the bentonite, and the particle size of the modified bentonite is less than or equal to 0.15 mm.
The zero-valent micron iron powder is 170-200 meshes, and the mass ratio of the iron content is more than 99%.
The median particle size of the zeolite was 150 μm.
The graphene particles have a median particle size of 10 μm.
The preparation method of the in-situ vertical barrier capable of removing the organic pollutants comprises the following steps:
step 1), adding zero-valent micron iron powder, graphene and zeolite into ultra-clean water, and fully stirring to prepare mixed slurry;
step 2) carrying out vacuum filtration on the mixed slurry liquid, washing the obtained solid phase with ultra-clean water and absolute ethyl alcohol, then placing the solid phase in a vacuum drying oven for drying, taking out the solid phase and storing the solid phase in a vacuum dryer to obtain an adsorbing material;
step 3) dissolving crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite, fully stirring to obtain bentonite slurry, standing until the crystalline sodium hexametaphosphate is completely hydrated, stirring again, drying in an oven, grinding and sieving to obtain sodium hexametaphosphate modified bentonite;
step 4), mixing the sodium hexametaphosphate modified bentonite with water, adding an adsorbing material, and stirring to obtain bentonite slurry;
and 5) fully mixing the bentonite slurry with the in-situ soil to obtain the engineering barrier material.
Wherein,
in the step 1), the mass ratio of the added zeolite to the zero-valent micron iron powder to the added graphene is 6:1: 1-10: 1: 1; the rotating speed of the stirring apparatus is 1000-3000 r/min, and the stirring time is 1 h.
In the step 2), washing the solid phase obtained by vacuum filtration with ultra-clean water for 3-5 times, and then washing with absolute ethyl alcohol for 1-2 times; and (3) drying the solid phase by using a vacuum drying oven, wherein the temperature in the drying oven is 80-85 ℃, and the drying time is 12-18 h.
In the step 3), the mass ratio of the bentonite dry soil added into the sodium hexametaphosphate solution to the sodium hexametaphosphate solution is 1: 1.5-1: 3; stirring the bentonite and the sodium hexametaphosphate solution by using a stirrer, wherein the rotating speed of the stirrer is 500-3000 r/min, and the stirring time of the stirrer is 5-15 min; the bentonite slurry is kept stand at room temperature for 24-48 h; and (3) drying the bentonite slurry in an oven at 105-115 ℃ to constant weight, grinding and sieving the bentonite slurry to obtain a particle size smaller than 0.075mm after drying, and removing impurities.
In the step 4), sodium hexametaphosphate modified bentonite and water are prepared according to the mass ratio of 0.08: 1-0.12: 1; sieving the bentonite to obtain powder with particle size less than 0.075mm before mixing with water to remove impurities; and stirring the bentonite and the water by using a stirrer, wherein the rotating speed of the stirrer is 500-3000 r/min, and the stirring time of the stirrer is 5-15 min.
Has the advantages that: compared with the prior art, the embodiment of the invention has the following beneficial effects:
the in-situ vertical barrier material capable of removing organic pollutants provided by the embodiment of the invention keeps the low permeability and high chemical compatibility of the sodium hexametaphosphate modified bentonite material, can still keep a lower permeability coefficient under the action of high-concentration heavy metal and organic matter solution, has good pollutant interception capability on organic pollutants, and greatly improves the anti-seepage effect and the effective service life of bentonite isolation facilities.
The preparation method provided by the embodiment of the invention is simple and easy to operate, has simple requirements on production equipment, is easy to popularize and use, and has lower engineering cost.
The main components of the adsorbing material in the barrier material provided by the embodiment of the invention are zero-valent micron iron, graphene and zeolite, so that the source of nontoxic and harmless production raw materials is wide, the adsorbing material is widely applied to water purification treatment, and the adsorbing material belongs to an environment-friendly material. The bentonite is also used as a water purification and antifouling facility material, is nontoxic and harmless, can adsorb harmful substances, and belongs to an environment-friendly material.
The in-situ vertical barrier material capable of removing organic pollutants disclosed by the embodiment of the invention accords with ten national policies of our country, and has wide application prospect and environmental protection significance.
Detailed Description
The calcium bentonite modified by the sodium hexametaphosphate has a dispersed and compact microstructure, and has stronger negative potential on the surface of a soil body and smaller interlayer spacing of the bentonite. The modification mechanism of the sodium hexametaphosphate is that the thickness of a double-electrode layer of the bentonite is increased, a bentonite agglomerate is stripped, and the size of a pore is reduced through the effects of ion exchange, chemical adsorption and steric hindrance stabilization, so that the expansibility and the impermeability of the bentonite are improved.
Owing to the lower permeability coefficient, the sodium hexametaphosphate modified bentonite barrier has good anti-seepage effect. During the service period of the engineering barrier, the adsorbing material in the barrier can effectively adsorb organic matters in the polluted liquid, so that the removing effect is achieved, the pollutant intercepting capability of the engineering barrier is greatly improved, breakdown is prevented, and the service life of the engineering barrier is prolonged.
The examples are as follows:
for safety reasons, sandy soil is uniformly adopted as in-situ soil in the indoor test, and the physical properties of the sandy soil are shown in table 1. The bentonite used in the test is calcium bentonite, and the properties of the bentonite are shown in table 2.
Example 1:
step 1) adding 170-mesh zero-valent micron iron powder, graphene and zeolite into ultra-clean water at a mass ratio of 1:1:6, and fully stirring at a speed of 1000r/min for 1h to prepare mixed slurry;
step 2) carrying out vacuum filtration on the mixed slurry liquid, washing a solid phase for 3 times by using ultra-clean water and washing the solid phase for 1 time by using absolute ethyl alcohol, then placing the solid phase in a vacuum drying oven at 80 ℃ for drying for 12 hours, taking out the solid phase and storing the dried solid phase in a vacuum drier to obtain an adsorbing material;
step 3) dissolving a certain mass of crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite according to the mass ratio of the solution to the bentonite dry soil of 2:1, stirring at the speed of 500r/min for 5min to obtain bentonite slurry, standing at room temperature for 24h until the bentonite slurry is completely hydrated, stirring at the speed of 500r/min for 5min again, sending the bentonite slurry into a 105 ℃ oven for drying, and grinding and sieving with a 200-mesh sieve to obtain sodium hexametaphosphate modified bentonite;
step 4) mixing the sodium hexametaphosphate modified bentonite and water in a ratio of 0.1:1, and stirring at a speed of 500r/min to obtain bentonite slurry;
and 5) adding an adsorption material into the bentonite slurry, and fully mixing the bentonite slurry with the sand to obtain the engineering barrier material, wherein the mass of the adsorption material accounts for 1% of the mass of the sodium hexametaphosphate modified bentonite.
Example 2:
step 1) adding 170-mesh zero-valent micron iron powder, graphene and zeolite into ultra-clean water at a mass ratio of 1:1:6, and fully stirring at a speed of 2000r/min for 1h to prepare mixed slurry;
step 2) carrying out vacuum filtration on the mixed slurry liquid, washing a solid phase for 3 times by using ultra-clean water and washing the solid phase for 1 time by using absolute ethyl alcohol, then placing the solid phase in a vacuum drying oven at 80 ℃ for drying for 12 hours, taking out the solid phase and storing the dried solid phase in a vacuum drier to obtain an adsorbing material;
step 3) dissolving a certain mass of crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite according to the mass ratio of the solution to the bentonite dry soil of 2:1, stirring at the speed of 500r/min for 5min to obtain bentonite slurry, standing at room temperature for 24h until the bentonite slurry is completely hydrated, stirring at the speed of 500r/min for 5min again, sending the bentonite slurry into a 105 ℃ oven for drying, and grinding and sieving with a 200-mesh sieve to obtain sodium hexametaphosphate modified bentonite;
step 4) mixing the sodium hexametaphosphate modified bentonite and water in a ratio of 0.1:1, adding an adsorbing material, and stirring at a speed of 1500r/min to obtain bentonite slurry;
and 5) fully mixing the bentonite slurry with the sand to obtain the engineering barrier material, wherein the mass of the adsorption material accounts for 5% of the mass of the sodium hexametaphosphate modified bentonite.
Example 3:
step 1) adding 200-mesh zero-valent micron iron powder, graphene and zeolite into ultra-clean water, and fully stirring for 1h at the speed of 1000r/min according to the mass ratio of 1:1:10 to prepare mixed slurry;
step 2) carrying out vacuum filtration on the mixed slurry liquid, washing a solid phase for 3 times by using ultra-clean water and washing the solid phase for 1 time by using absolute ethyl alcohol, then placing the solid phase in a vacuum drying oven at 80 ℃ for drying for 12 hours, taking out the solid phase and storing the dried solid phase in a vacuum drier to obtain an adsorbing material;
step 3) dissolving a certain mass of crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite according to the mass ratio of the solution to the bentonite dry soil of 2:1, stirring at the speed of 500r/min for 5min to obtain bentonite slurry, standing at room temperature for 24h until the bentonite slurry is completely hydrated, stirring at the speed of 500r/min for 5min again, sending the bentonite slurry into a 105 ℃ oven for drying, and grinding and sieving with a 200-mesh sieve to obtain sodium hexametaphosphate modified bentonite;
step 4) mixing the sodium hexametaphosphate modified bentonite and water in a ratio of 0.1:1, adding an adsorbing material, and stirring at a speed of 1500r/min to obtain bentonite slurry;
and 5) fully mixing the bentonite slurry with the sand to obtain the engineering barrier material, wherein the mass of the adsorption material accounts for 1% of the mass of the sodium hexametaphosphate modified bentonite.
Example 4:
step 1) adding 200-mesh zero-valent micron iron powder, graphene and zeolite into ultra-clean water at a mass ratio of 1:1:8, and fully stirring at a speed of 1500r/min for 1h to prepare mixed slurry;
step 2) carrying out vacuum filtration on the mixed slurry liquid, washing a solid phase for 3 times by using ultra-clean water and washing the solid phase for 1 time by using absolute ethyl alcohol, then placing the solid phase in a vacuum drying oven at 80 ℃ for drying for 12 hours, taking out the solid phase and storing the dried solid phase in a vacuum drier to obtain an adsorbing material;
step 3) dissolving a certain mass of crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite according to the mass ratio of the solution to the bentonite dry soil of 2:1, stirring at the speed of 500r/min for 5min to obtain bentonite slurry, standing at room temperature for 24h until the bentonite slurry is completely hydrated, stirring at the speed of 500r/min for 5min again, sending the bentonite slurry into a 105 ℃ oven for drying, and grinding and sieving with a 200-mesh sieve to obtain sodium hexametaphosphate modified bentonite;
step 4) mixing the sodium hexametaphosphate modified bentonite and water in a ratio of 0.1:1, adding an adsorbing material, and stirring at a speed of 1500r/min to obtain bentonite slurry;
and 5) fully mixing the bentonite slurry with the sand to obtain the engineering barrier material, wherein the mass of the adsorption material accounts for 5% of the mass of the sodium hexametaphosphate modified bentonite.
Example 5:
step 1) adding 200-mesh zero-valent micron iron powder, graphene and zeolite into ultra-clean water, wherein the mass ratio is 1:1: (10), and fully stirring at the speed of 2200r/min for 1h to prepare mixed slurry;
step 2) carrying out vacuum filtration on the mixed slurry liquid, washing a solid phase for 3 times by using ultra-clean water and washing the solid phase for 1 time by using absolute ethyl alcohol, then placing the solid phase in a vacuum drying oven at 80 ℃ for drying for 12 hours, taking out the solid phase and storing the dried solid phase in a vacuum drier to obtain an adsorbing material;
step 3) dissolving a certain mass of crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite according to the mass ratio of the solution to the bentonite dry soil of 2:1, stirring at the speed of 500r/min for 5min to obtain bentonite slurry, standing at room temperature for 24h until the bentonite slurry is completely hydrated, stirring at the speed of 500r/min for 5min again, sending the bentonite slurry into a 105 ℃ oven for drying, and grinding and sieving with a 200-mesh sieve to obtain sodium hexametaphosphate modified bentonite;
step 4) mixing the sodium hexametaphosphate modified bentonite and water in a ratio of 0.1:1, adding an adsorbing material, and stirring at a speed of 1500r/min to obtain bentonite slurry;
and 5) fully mixing the bentonite slurry with the sand to obtain the engineering barrier material, wherein the mass of the adsorption material accounts for 10% of the mass of the sodium hexametaphosphate modified bentonite.
Example 6:
step 1) adding 200-mesh zero-valent micron iron powder, graphene and zeolite into ultra-clean water at a mass ratio of 1:1:10, and fully stirring at a speed of 2900r/min for 1h to prepare mixed slurry;
step 2) carrying out vacuum filtration on the mixed slurry liquid, washing a solid phase for 3 times by using ultra-clean water and washing the solid phase for 1 time by using absolute ethyl alcohol, then placing the solid phase in a vacuum drying oven at 80 ℃ for drying for 12 hours, taking out the solid phase and storing the dried solid phase in a vacuum drier to obtain an adsorbing material;
step 3) dissolving a certain mass of crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite according to the mass ratio of the solution to the bentonite dry soil of 2:1, stirring at the speed of 500r/min for 5min to obtain bentonite slurry, standing at room temperature for 24h until the bentonite slurry is completely hydrated, stirring at the speed of 500r/min for 5min again, sending the bentonite slurry into a 105 ℃ oven for drying, and grinding and sieving with a 200-mesh sieve to obtain sodium hexametaphosphate modified bentonite;
step 4) mixing the sodium hexametaphosphate modified bentonite and water in a ratio of 0.1:1, adding an adsorbing material, and stirring at a speed of 1500r/min to obtain bentonite slurry;
and 5) fully mixing the bentonite slurry with the sand to obtain the engineering barrier material, wherein the mass of the adsorption material accounts for 20% of the mass of the sodium hexametaphosphate modified bentonite.
Comparative example:
the other steps are similar to the examples, without adding an adsorbent material to the engineered barrier material.
Step 1) dissolving a certain mass of crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite according to the mass ratio of the solution to the bentonite dry soil of 2:1, stirring at the speed of 500r/min for 5min to obtain bentonite slurry, standing at room temperature for 24h until the bentonite slurry is completely hydrated, stirring at the speed of 500r/min for 5min again, sending the bentonite slurry into a 105 ℃ oven for drying, and grinding and sieving with a 200-mesh sieve to obtain sodium hexametaphosphate modified bentonite;
step 2) mixing the sodium hexametaphosphate modified bentonite and water in a ratio of 0.1:1, and stirring at a speed of 500r/min to obtain bentonite slurry;
and 3) fully mixing the bentonite slurry with the sand to obtain the engineering barrier material.
TABLE 1 index of physical Properties of sandy soil
| Parameter(s) | Numerical value |
| Specific gravity Gs | 2.65 |
| Sand content/%) | 100 |
| Median particle diameter d30/mm | 0.25 |
| Median particle diameter d10/mm | 0.5 |
| Natural water content/%) | 0 |
TABLE 2 index of physical Properties of calcium-based bentonite
And (3) permeability coefficient testing:
the polluted liquid in the test is taken from a Ningbo certain industrial polluted site, the main pollutants are heavy metals and organic matters, wherein the main pollution factors are as follows: zn (1188mg/L), Cd (6.69mg/L), Cu (625.8mg/L), As (40.55mg/L), Hg (2.28mg/L), trichloroethylene (11.2 mg/L).
The materials prepared in the above examples and comparative examples were subjected to permeability coefficient test.
The permeability coefficient test adopts a T0130-2007 variable water head permeability test in the China's republic of people's republic of China industry standard JTG 40-2007 Highway soil engineering test regulation JTG, the variable water head permeability test is suitable for clay and cohesive soil, and the permeability coefficient of the cohesive soil can be accurately, simply and conveniently tested. The test results are shown in table 3 below.
TABLE 3 penetration test results
And (3) testing the organic matter removal effect:
and during the penetration test, collecting the liquid overflowing from the water outlet, testing the content of organic matters in the liquid, and comparing the content with the original liquid of the polluted liquid. The trichloroethylene removal rate is shown in Table 4.
Table 4 organic matter removal effect test
The test results show that the addition of the adsorbing material does not adversely affect the anti-seepage performance of the sodium hexametaphosphate modified bentonite engineering barrier. The engineering barrier material added with the adsorbing materials with different mixing amounts and different particle sizes can maintain a lower permeability coefficient under the action of the heavy metal and organic compound polluted liquid, and is lower than the specified limit value (1 multiplied by 10 < -9 > m/s) of anti-seepage facilities such as national landfill liners and the like. In addition, after the adsorbing material is added, the pollutant intercepting capability of the engineering barrier is greatly improved, compared with a comparative example without adding organic matters, the removal rate of trichloroethylene is obviously improved, and the good removal effect on the organic matters is achieved. The added adsorbing material not only can keep high anti-seepage performance of the engineering barrier, but also can effectively limit the migration of organic pollutants to the periphery, reduce environmental risks and serve multiple purposes.
It is to be understood that: the foregoing is only a preferred embodiment of the present invention, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and such modifications and improvements should be considered as the protection scope of the present invention.
Claims (10)
1. The utility model provides a vertical barrier material of normal position that can get rid of contaminated site organic pollutant which characterized in that: the barrier material comprises 1-20% of sodium hexametaphosphate modified bentonite, 8-12% of sodium hexametaphosphate modified bentonite and 70-90% of in-situ soil by mass ratio, wherein the adsorption material is a composite material consisting of zeolite, zero-valent micron iron powder and graphene, and the mass ratio of the zeolite to the zero-valent micron iron powder to the graphene of the adsorption material is 6:1: 1-10: 1:1.
2. The in-situ vertical barrier material for removing organic contaminants from a contaminated site according to claim 1, wherein: the mixing amount of sodium hexametaphosphate in the sodium hexametaphosphate modified bentonite is 2-4% of the mass of the bentonite, and the particle size of the modified bentonite is less than or equal to 0.15 mm.
3. The in-situ vertical barrier material for removal of organic contaminants of claim 1, wherein: the zero-valent micron iron powder is 170-200 meshes, and the mass ratio of the iron content is more than 99%.
4. The in-situ vertical barrier material for removal of organic contaminants of claim 1, wherein: the median particle size of the zeolite was 150 μm.
5. The in-situ vertical barrier material for removal of organic contaminants of claim 1, wherein: the graphene particles have a median particle size of 10 μm.
6. The method for preparing the in-situ vertical barrier for removal of organic contaminants according to claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
step 1), adding zero-valent micron iron powder, graphene and zeolite into ultra-clean water, and fully stirring to prepare mixed slurry;
step 2) carrying out vacuum filtration on the mixed slurry liquid, washing the obtained solid phase with ultra-clean water and absolute ethyl alcohol, then placing the solid phase in a vacuum drying oven for drying, taking out the solid phase and storing the solid phase in a vacuum dryer to obtain an adsorbing material;
step 3) dissolving crystalline sodium hexametaphosphate in deionized water, stirring until the crystalline sodium hexametaphosphate is completely dissolved, adding bentonite, fully stirring to obtain bentonite slurry, standing until the crystalline sodium hexametaphosphate is completely hydrated, stirring again, drying in an oven, grinding and sieving to obtain sodium hexametaphosphate modified bentonite;
step 4), mixing the sodium hexametaphosphate modified bentonite with water, adding an adsorbing material, and stirring to obtain bentonite slurry;
and 5) fully mixing the bentonite slurry with the in-situ soil to obtain the engineering barrier material.
7. The method for preparing an in-situ vertical barrier material for removing organic pollutants according to claim 6, wherein the method comprises the following steps: in the step 1), the mass ratio of the added zeolite to the zero-valent micron iron powder to the added graphene is 6:1: 1-10: 1: 1; the rotating speed of the stirring apparatus is 1000-3000 r/min, and the stirring time is 1 h.
8. The method for preparing an in-situ vertical barrier material for removing organic pollutants according to claim 6, wherein the method comprises the following steps: in the step 2), washing the solid phase obtained by vacuum filtration with ultra-clean water for 3-5 times, and then washing with absolute ethyl alcohol for 1-2 times; and (3) drying the solid phase by using a vacuum drying oven, wherein the temperature in the drying oven is 80-85 ℃, and the drying time is 12-18 h.
9. The method for preparing an in-situ vertical barrier material for removing organic pollutants according to claim 6, wherein the method comprises the following steps: in the step 3), the mass ratio of the bentonite dry soil added into the sodium hexametaphosphate solution to the sodium hexametaphosphate solution is 1: 1.5-1: 3; stirring the bentonite and the sodium hexametaphosphate solution by using a stirrer, wherein the rotating speed of the stirrer is 500-3000 r/min, and the stirring time of the stirrer is 5-15 min; the bentonite slurry is kept stand at room temperature for 24-48 h; and (3) drying the bentonite slurry in an oven at 105-115 ℃ to constant weight, grinding and sieving the bentonite slurry to obtain a particle size smaller than 0.075mm after drying, and removing impurities.
10. The method for preparing an in-situ vertical barrier material for removing organic pollutants according to claim 6, wherein the method comprises the following steps: in the step 4), sodium hexametaphosphate modified bentonite and water are prepared according to the mass ratio of 0.08: 1-0.12: 1; sieving the bentonite to obtain powder with particle size less than 0.075mm before mixing with water to remove impurities; and stirring the bentonite and the water by using a stirrer, wherein the rotating speed of the stirrer is 500-3000 r/min, and the stirring time of the stirrer is 5-15 min.
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