CN104803486A - Permeable reactive barrier material for groundwater chromium pollution remediation and preparation method thereof - Google Patents

Permeable reactive barrier material for groundwater chromium pollution remediation and preparation method thereof Download PDF

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Publication number
CN104803486A
CN104803486A CN201510191672.XA CN201510191672A CN104803486A CN 104803486 A CN104803486 A CN 104803486A CN 201510191672 A CN201510191672 A CN 201510191672A CN 104803486 A CN104803486 A CN 104803486A
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medium
mass ratio
permeable reactive
reactive barrier
barrier material
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CN104803486B (en
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李玲
唐晓声
邹权
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Guangda Environmental Restoration (Jiangsu) Co., Ltd.
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JIANGSU SUNTIME ENVIRONMENTAL REMEDIATION CO Ltd
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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Inorganic Chemistry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a permeable reactive barrier material for groundwater chromium pollution remediation and a preparation method thereof. The permeable reactive barrier material is a mixture of reaction mediums, quartz sand and soil, wherein the reaction mediums are particle materials and comprise reducing medium sodium bisulfite, sodium thiosulfate, sodium hydrosulfite, citric acid, adsorbing medium activated carbon, apatite, peat, diatomite, a biological medium humic acid, straw, saw dust, rice straw and cement. According to the preparation method further disclosed by the invention, the permeable reactive barrier material is prepared, and has the advantages of being slow in material release, long-time in sustained reaction and higher in medium utilization efficiency; due to various mediums, the precipitation possibility is effectively lowered, and the problems of single PRB (permeable reactive barrier) hardening and blockage are avoided; meanwhile, due to the chemical-microorganism combined reaction, secondary pollution is reduced.

Description

A kind of permeable reactive barrier material and preparation method repairing underground water pollution of chromium
Technical field
The invention belongs to polluted underground water and repair field, be specifically related to a kind of the permeable reactive barrier material and the preparation method that repair underground water pollution of chromium.
Background technology
Because past people environmental consciousness is weak, chromium slag huddles that to leave about phenomenon very general, and chrominm salt production technology environmental practice is inadequate, the a large amount of water soluble hexavalent chromium contained in chromium slag and chromic salts and carcinogens yellow ultramarine, store up in process for a long time and scrub through rainwater, permeate the ground with rainwater, cause groundwater pollution, serious threat is caused to the health of local resident.According to incompletely statistics, many places, China's existing underground water pollution of chromium region 100, be distributed in 24 provinces in the whole nation, the groundwater pollution in some pollution of chromium regions is very serious, concentration, up to hundreds of mg/L, exceedes the 0.05mg/L up to ten thousand times of groundwater quality standard (GB/T14848-93) 3 class water quality requirement.Thus treating groundwater pollution of chromium has become the current environmental problem needing to solve.
In recent years, permeable reactive barrier (permeablereactivebarrier, PRB) is as a kind of original position Remedy Technology of Contaminated Groundwater, can permanently effectively operate, not influence ecological environment, and cheap, safeguard simple, become domestic and international study hotspot.This technology has more application in developed countries such as North America and Europe, and according to U.S.'s super fund project statistics, 2005-2008 has 8 projects to employ this technology.Usual using ferrous material as reaction medium abroad at present, process underground water pollution of chromium by the chemical reduction reaction of iron.But the ferrous material Costco Wholesales such as Zero-valent Iron are higher, and after reaction for some time, ferrous material surface is easily corroded, and produces iron mineral precipitation (as FeO, Fe (OH) 2, Fe (OH) 3deng) cover material surface forming reactions protective membrane, along with the effect of Cumulate Sum microorganism of precipitation, produce reaction efficiency low, easily to harden the problems such as blocking.
Summary of the invention
The object of the present invention is to provide a kind of the permeable reactive barrier material and the preparation method that repair underground water pollution of chromium, solve the reaction efficiency existed in existing ferrous material PRB process underground water pollution of chromium process low, easily to harden the problems such as blocking.
Repair a permeable reactive barrier for underground water pollution of chromium, its material is primarily of reaction medium, quartz sand, mixing with soil composition, and its concrete mass ratio is 1:(0.2 ~ 0.4): (0.6 ~ 0.8).
Further, above-mentioned reaction medium is particulate state, comprises reducing medium, adsorption medium, Biomedia, cement, and its concrete mass ratio is 1:(0.5 ~ 0.7): (0.6 ~ 0.8): (0.5 ~ 0.7).
Further, above-mentioned particulate material, median size 3.5 ~ 5mm.
Further, above-mentioned reducing medium comprises sodium bisulfite, Sulfothiorine, V-Brite B, citric acid, and its concrete mass ratio is 1:(1.5 ~ 1.7): (0.3 ~ 0.5): (2.5 ~ 3.5);
Above-mentioned adsorption medium comprises gac, phosphatic rock, peat, diatomite, and its concrete mass ratio is 1:(0.4 ~ 0.6): (0.4 ~ 0.6): (0.8 ~ 1.2);
Above-mentioned Biomedia comprises humic acid, stalk, sawdust, straw, and its concrete mass ratio is 1:(1.0 ~ 1.2): (0.8 ~ 1.0): (0.8 ~ 1.0).
The permeable reactive barrier material preparation method of above-mentioned reparation underground water provided by the invention pollution of chromium is:
1) sodium bisulfite, Sulfothiorine, V-Brite B, citric acid are reducing medium, are 1:(1.5 ~ 1.7 in mass ratio): (0.3 ~ 0.5): (2.5 ~ 3.5) Homogeneous phase mixing;
2) gac, phosphatic rock, peat, diatomite are adsorption medium, are 1:(0.4 ~ 0.6 in mass ratio): (0.4 ~ 0.6): (0.8 ~ 1.2) Homogeneous phase mixing;
3) humic acid, stalk, sawdust, straw are Biomedia, are Homogeneous phase mixing 1:(1.0 ~ 1.2 in mass ratio): (0.8 ~ 1.0): (0.8 ~ 1.0);
4) reducing medium, adsorption medium, Biomedia, cement are 1:(0.5 ~ 0.7 in mass ratio): (0.6 ~ 0.8): (0.5 ~ 0.7) Homogeneous phase mixing, spray water makes to become paste blending agent;
5) by step 4) the paste blending agent maintenance that obtains 28 ~ 30 days;
6) by step 5) the paste blending agent that obtains makes the particle of 3.5 ~ 5mm;
7) by step 6) granule medium that obtains and quartz sand, soil is 1:(0.2 ~ 0.4 in mass ratio): (0.6 ~ 0.8) Homogeneous phase mixing, obtains target material.
Know-why of the present invention is:
Build successive type PRB in underground water pollution of chromium region, add above-mentioned materials, when pollution of chromium groundwater flow is through permeable reactive barrier, through quartz sand duct filteration, sexavalent chrome is attracted to soil, quartz sand surface; Granule medium slow releasing blending ingredients wherein simultaneously, sodium bisulfite, Sulfothiorine, V-Brite B reduction of hexavalent chromium:
2CrO 4 2-+3NaHSO 3+7H +→2Cr 3++3Na ++3SO 4 2-+5H 2O
8CrO 4 2-+3Na 2S 2O 3+34H +→8Cr 3++6Na ++6SO 4 2-+17H 2O
2CrO 4 2-+Na 2S 2O 4+8H +→2Cr 3++2Na ++2SO 4 2-+4H 2O
Citric acid provides reaction required sour environment, avoids Iron in Soil mineral formation FeO, Fe (OH) simultaneously 3precipitate in iron ore; Gac, phosphatic rock, peat, diatomite adsorption precipitate C r 3+, reduce the Cr in water after PRB process 3+content; Humic acid, stalk, sawdust, straw generate soil ulmin etc. under the Decomposition of soil microorganisms, provide the energy environment needed for microbe survival, and promote that in soil, indigenous microorganism is to the chromic absorption of remnants, precipitation further, indigenous microorganism is to Fe simultaneously 2+also there is Degradation, less Fe 2+etc. the secondary pollution problem brought.
The invention has the advantages that: a kind of permeable reactive barrier repairing underground water pollution of chromium, its particle reaction medium slow releasing, can sustained reaction for a long time, improve medium utilising efficiency; Multimedium effectively reduces the generation of precipitation, avoids that PRB hardens, blockage problem; The acting in conjunction of chemistry-microorganism, decreases secondary pollution simultaneously.The material cost that the present invention uses is lower, pollution-free.
Accompanying drawing explanation
Fig. 1 is the static treatment design sketch of the embodiment of the present invention 1, embodiment 2;
Fig. 2 is the PRB simulation process design sketch of the embodiment of the present invention 3, embodiment 4;
Embodiment
Further illustrate below in conjunction with specific embodiment.
Embodiment 1
1) sodium bisulfite, Sulfothiorine, V-Brite B, citric acid are reducing medium, are 1:1.6:0.4:3 Homogeneous phase mixing in mass ratio;
2) gac, phosphatic rock, peat, diatomite are adsorption medium, are 1:0.5:0.5:1.0 Homogeneous phase mixing in mass ratio;
3) humic acid, stalk, sawdust, straw are Biomedia, are Homogeneous phase mixing 1:1.1:0.9:0.9 in mass ratio;
4) reducing medium, adsorption medium, Biomedia, cement are 1:0.6:0.7:0.6 Homogeneous phase mixing in mass ratio, and spray water makes it to become paste blending agent;
5) by step 4) the paste blending agent maintenance that obtains 28 ~ 30 days;
6) by step 5) the paste blending agent that obtains makes the granule medium of 3.5 ~ 5mm;
7) by step 6) granule medium that obtains and quartz sand, soil is 1:0.3:0.7 Homogeneous phase mixing in mass ratio, obtains permeable reactive barrier material.
Above-mentioned for 5g PRB material is put in 1L containing static immersing in the hexavalent chromium solution of 200mg/L; Timing measures Cr in solution 6+content;
Embodiment 2
1) sodium bisulfite, Sulfothiorine, V-Brite B, citric acid are reducing medium, are 1:1.5:0.3:2.5 Homogeneous phase mixing in mass ratio;
2) gac, phosphatic rock, peat, diatomite are adsorption medium, are 1:0.4:0.4:0.8 Homogeneous phase mixing in mass ratio;
3) humic acid, stalk, sawdust, straw are Biomedia, are Homogeneous phase mixing 1:1.0:0.8:0.8 in mass ratio;
4) reducing medium, adsorption medium, Biomedia, cement are 1:0.5:0.6:0.5 Homogeneous phase mixing in mass ratio, and spray water makes it to become paste blending agent;
5) by step 4) the paste blending agent maintenance that obtains 28 ~ 30 days;
6) by step 5) the paste blending agent that obtains makes the granule medium of 3.5 ~ 5mm;
7) by step 6) granule medium that obtains and quartz sand, soil is 1:0.2:0.6 Homogeneous phase mixing in mass ratio, obtains permeable reactive barrier material.
Above-mentioned for 50g PRB material is put in 1L containing static immersing in the hexavalent chromium solution of 2000mg/L; Timing measures Cr in solution 6+content;
Embodiment 3
1) sodium bisulfite, Sulfothiorine, V-Brite B, citric acid are reducing medium, are 1:1.7:0.5:3.5 Homogeneous phase mixing in mass ratio;
2) gac, phosphatic rock, peat, diatomite are adsorption medium, are 1:0.6:0.6:1.2 Homogeneous phase mixing in mass ratio;
3) humic acid, stalk, sawdust, straw are Biomedia, are Homogeneous phase mixing 1:1.2:1.0:1.0 in mass ratio;
4) reducing medium, adsorption medium, Biomedia, cement are 1:0.7:0.8:0.7 Homogeneous phase mixing in mass ratio, and spray water makes it to become paste blending agent;
5) by step 4) the paste blending agent maintenance that obtains 28 ~ 30 days;
6) by step 5) the paste blending agent that obtains makes the granule medium of 3.5 ~ 5mm;
7) by step 6) granule medium that obtains and quartz sand, soil is 1:0.4:0.8 Homogeneous phase mixing in mass ratio, obtains permeable reactive barrier material.
Build simulation PRB device, add the above-mentioned PRB material of 5g, add the hexavalent chromium solution of 1L containing 200mg/L, ooze under nature; Lower sepage is continued flow through same PRB simulator repeatedly; Measure repeatedly Cr in percolate 6+content;
Embodiment 4
1) PRB material is prepared by embodiment 1;
2) build simulation PRB device, add the above-mentioned PRB material of 50g, add the hexavalent chromium solution of 1L containing 2000mg/L, ooze under nature;
3) by step 2) under sepage continue to flow through same PRB simulator repeatedly;
4) Cr in percolate is measured repeatedly 6+content;
Embodiment 5
1) PRB material is prepared by above-described embodiment 1;
2) build PRB simulator capable of circulation, add the above-mentioned PRB material of 100g, pass into the hexavalent chromium solution containing 50mg/L, coutroi velocity is at 0.5 ~ 0.7m/d;
3) circular flow 2 years, timing measures water inlet, water outlet Cr 6+content;
From embodiment 1 and embodiment 2, above-mentioned PRB material slow releasing reaction medium in water, the sexavalent chrome gradually in treatment soln, for the sexavalent chrome sewage of middle and high concentration, static treatment effect reaches more than 90% (see accompanying drawing 1).
From embodiment 3 and enforcement 4, the sexavalent chrome effluent stream of middle and high concentration is when above-mentioned PRB material, above-mentioned PRB material slow releasing reaction medium, the sexavalent chrome in disposing of sewage gradually, 3 times dynamic PRB treatment effect reaches more than 80% (see accompanying drawing 2).
From embodiment 5, the sexavalent chrome effluent cycle of lower concentration flows through above-mentioned PRB material after 2 years, Cr 6+removal effect reaches more than 99%, and water outlet Cr 6+content is still less than into water Cr 6+content (see table 1), illustrates that the reaction medium in above-mentioned PRB material can slow releasing more than 2 years.
Table 1 cycle P RB simulates removal effect

Claims (5)

1. repair a permeable reactive barrier material for underground water pollution of chromium, it is characterized in that, according to mass ratio meter, be made up of following component:
Reaction medium 1
Quartz sand 0.2 ~ 0.4
Soil 0.6 ~ 0.8;
Described reaction medium is particulate material, median size 3.5 ~ 5mm; Described reaction medium, according to mass ratio meter, is made up of following component:
。
2. a kind of permeable reactive barrier material repairing underground water pollution of chromium according to claim 1, is characterized in that described reducing medium, according to mass ratio meter, is made up of following component:
。
3. a kind of permeable reactive barrier material repairing underground water pollution of chromium according to claim 1, is characterized in that described adsorption medium, according to mass ratio meter, is made up of following component:
。
4. a kind of permeable reactive barrier material repairing underground water pollution of chromium according to claim 1, is characterized in that described adsorption medium, according to mass ratio meter, is made up of following component:
。
5. repair a preparation method for the permeable reactive barrier material of underground water pollution of chromium, it is characterized in that, by following steps:
1) sodium bisulfite, Sulfothiorine, V-Brite B, citric acid are reducing medium, are 1:(1.5 ~ 1.7 in mass ratio): (0.3 ~ 0.5): (2.5 ~ 3.5) Homogeneous phase mixing;
2) gac, phosphatic rock, peat, diatomite are adsorption medium, are 1:(0.4 ~ 0.6 in mass ratio): (0.4 ~ 0.6): (0.8 ~ 1.2) Homogeneous phase mixing;
3) humic acid, stalk, sawdust, straw are Biomedia, are Homogeneous phase mixing 1:(1.0 ~ 1.2 in mass ratio): (0.8 ~ 1.0): (0.8 ~ 1.0);
4) reducing medium, adsorption medium, Biomedia, cement are 1:(0.5 ~ 0.7 in mass ratio): (0.6 ~ 0.8): (0.5 ~ 0.7) Homogeneous phase mixing, spray water makes it to become paste blending agent;
5) by step 4) the paste blending agent maintenance that obtains 28 ~ 30 days;
6) by step 5) the paste blending agent that obtains makes the granule medium of 3.5 ~ 5mm;
7) by step 6) granule medium that obtains and quartz sand, soil is 1:(0.2 ~ 0.4 in mass ratio): (0.6 ~ 0.8) Homogeneous phase mixing, obtains permeable reactive barrier material.
CN201510191672.XA 2015-04-21 2015-04-21 Permeable reactive barrier material for groundwater chromium pollution remediation and preparation method thereof Active CN104803486B (en)

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CN105399245A (en) * 2015-12-18 2016-03-16 江苏维尔利环保科技股份有限公司 Remediation device of hexavalent chromium-polluted underground water, and remediation method thereof
CN105502671A (en) * 2016-01-12 2016-04-20 陕西科技大学 PRB filler for repairing Pb/Cd pollution and preparation method and effect verification method thereof
CN107158804A (en) * 2017-05-10 2017-09-15 上田环境修复股份有限公司 A kind of filtering material, its preparation method and application for being used to filter copper ions and the exceeded foundation ditch water of nickel ion
CN110451624A (en) * 2019-09-06 2019-11-15 中南大学 The permeable coefficient tensor material of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH
CN111112312A (en) * 2019-12-16 2020-05-08 安徽洁然环境科技有限公司 Restoration application of PRB material based on high permeability cement base in long-acting control field
CN114263231A (en) * 2021-12-29 2022-04-01 北京建工环境修复股份有限公司 Supporting material for building permeable reactive barrier and application thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105399245A (en) * 2015-12-18 2016-03-16 江苏维尔利环保科技股份有限公司 Remediation device of hexavalent chromium-polluted underground water, and remediation method thereof
CN105502671A (en) * 2016-01-12 2016-04-20 陕西科技大学 PRB filler for repairing Pb/Cd pollution and preparation method and effect verification method thereof
CN107158804A (en) * 2017-05-10 2017-09-15 上田环境修复股份有限公司 A kind of filtering material, its preparation method and application for being used to filter copper ions and the exceeded foundation ditch water of nickel ion
CN110451624A (en) * 2019-09-06 2019-11-15 中南大学 The permeable coefficient tensor material of repairing hexavalent chromium polluted underground water within the scope of a kind of width pH
CN110451624B (en) * 2019-09-06 2020-11-03 中南大学 Permeable reaction wall material for repairing hexavalent chromium polluted underground water within wide pH range
CN111112312A (en) * 2019-12-16 2020-05-08 安徽洁然环境科技有限公司 Restoration application of PRB material based on high permeability cement base in long-acting control field
CN114263231A (en) * 2021-12-29 2022-04-01 北京建工环境修复股份有限公司 Supporting material for building permeable reactive barrier and application thereof
CN114263231B (en) * 2021-12-29 2023-11-14 北京建工环境修复股份有限公司 Supporting material for building permeable reactive barrier and application thereof

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