CN106001094A - Remediation method for heavy metal pollution of neutral soil - Google Patents
Remediation method for heavy metal pollution of neutral soil Download PDFInfo
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- CN106001094A CN106001094A CN201610564422.0A CN201610564422A CN106001094A CN 106001094 A CN106001094 A CN 106001094A CN 201610564422 A CN201610564422 A CN 201610564422A CN 106001094 A CN106001094 A CN 106001094A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a remediation method for heavy metal pollution of neutral soil. The remediation method comprises the steps of dissolving a siloxane substance of which the structural formula is Si(OR)4 into an acid solution of alcohol or ether as a remediation reagent; mixing the mixture of the siloxane substance and the acid solution of alcohol or ether with neutral soil for reaction; and then, adding an aqueous solution of inorganic strong base or inorganic weak base for further reaction, wherein the R refers to one or more of methyl, ethyl and propyl. The remediation method for heavy metal pollution of neutral soil is low in cost, and simple, convenient and efficient to implement, and restored heavy metals can be stably maintained in soil for a long time.
Description
Technical field
The invention belongs to heavy metal pollution of soil and repair field, particularly to a kind of neutral soil heavy metal pollution restorative procedure.
Technical background
On April 17th, 2014, Chinese Ministry of Environmental Protection and Ministry of Land and Resources combine and disclose " whole nation Soil Pollution Investigation publication ",
Cause each side of the society extensive concern to China's soil pollution situation.Show according to investigation publication, the whole nation total the exceeding standard of soil
Rate is 16.1%, the most slightly, slightly, moderate and serious pollution point position ratio be respectively 11.2%, 2.3%, 1.5% and 1.1%.
From the point of view of pollution distribution state, soils in south china pollutes and overweights the north, and southwest, variable charge soil heavy metals exceeding standard scope are bigger.
On the whole, whole nation soil environment situation allows of no optimist, and some areas soil pollution is extremely serious, and soil remediation work is carved not
Rong Huan.
Common heavy metal pollution of soil restorative procedure have elution method, phytoremediation, microorganism remediation method, chemical extraction method,
Chemical oxidization method, stabilizing method etc..Said method all can obtain certain repairing effect, and be all to adopt for heavy metal characteristic
The mode taken.Its by by heavy metal ion from soil fundamental particle sur-face peeling, then enrichment is removed or fixing, but from entirety
For on there is the problems such as repair amount is big, cost is high, and repairing effect is the most lasting in these methods.
Summary of the invention
Inventor is in substantial amounts of soil remediation is put into practice, for the heavy metal in stable curing soil, according to different heavy metals
Characteristic, carried out substantial amounts of trial, employed the most different heavy metal stabilizing and curing agents and combination, but effect is not to the utmost
People's will, to this, inventor changes thinking, after soil property etc. has been carried out substantial amounts of further investigation, it is provided that one
Plant the restorative procedure of the neutral soil heavy metal pollution of low cost, the heavy metal that is efficiently coated and fixed simple, long-term.
The purpose of the present invention can be achieved through the following technical solutions: a kind of neutral soil heavy metal pollution restorative procedure, will
Structural formula is Si (OR)4Type siloxane material be dissolved in the acid solution of alcohol or ether, as repair reagent, with neutral soil
Mixing, reaction, the aqueous solution being subsequently adding inorganic strong alkali or inorganic weak bases reacts further；
Wherein, one or more during R represents methyl, ethyl or propyl group.
The restorative procedure of a kind of neutral soil heavy metal pollution, is Si (OR) by structural formula4Type siloxane material be dissolved in alcohol
Or in the acid solution of ether, as repairing reagent, mix with neutral soil, reaction, it is subsequently adding inorganic strong alkali or inorganic weak bases
Aqueous solution react further；
Wherein, one or more during R represents methyl, ethyl or propyl group.
The present invention farther includes following preferred technical scheme:
Preferably in scheme, described type siloxane material is tetraethyl orthosilicate or tetramethoxy-silicane.
Preferably in scheme, described reparation reagent is 1:20-1:200 with the mass ratio of neutral soil.
Preferably in scheme, described inorganic strong alkali or inorganic weak bases are selected from sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia
In one or more.
Preferably in scheme, the aqueous solution of described inorganic strong alkali or inorganic weak bases and neutral soil mass ratio are 1:20-1:200.
Preferably in scheme, described type siloxane material is dissolved in the acid solution of alcohol or ether, stirs 5-240min, then
Uniformly mix with neutral soil again, reaction.
Preferably in scheme, described type siloxane material is 1:1-1:10 with the mass ratio of alcohol or ether.
Preferably in scheme, the mass ratio of described alcohol or ether and acid solution is 1:1-1:20.
Preferably in scheme, the pH of the aqueous solution of described inorganic strong alkali or inorganic weak bases is 8-10.
Preferably in scheme, described alcohol is ethanol or methanol, and described ether is ether；Described acid solution selected from hydrochloric acid, nitric acid or
One in sulfur aqueous acid, in wherein said acid solution, acid is 1:10-1:40 with the mass ratio of water.
Soil is mainly made up of fundamental particle (sand grains, soil micelle), organic matter, microorganism, moisture four major part, its
Middle fundamental particle accounts for soil dry weight more than 95%.The substantial amounts of ion of soil fundamental particle surface enrichment (is enriched with under sour environment
Hydrion, is enriched with hydroxide ion under alkaline environment), the heavy metal ion in aqueous solution is had strong absorption with fixing
Effect (exchange adsorption, Electrostatic Absorption under alkaline environment under sour environment).Moreover, the ion on fundamental particle surface is more
Condition can be provided for forming " cage " of long-term fixing heavy metal ion.
There is acid catalyzed reaction under the action of an acid in the reparation reagent of the present invention, owing to the supplied for electronic effect of alkyl (is i.e. applied to
On the O of Si-O-R), the oxygen (-O-) of hydrion meeting targeted attack electron rich, siloxanes can occur under hydrion is catalyzed
Hydrolysis obtains Si (OH)4Monomer.Soil fundamental particle be mainly composed of SiO2, Si (OH)4To SiO2Have affine
Property, Si (OH) under the effect of inorganic strong alkali or inorganic weak bases4Monomer and monomer, Si (OH)4Monomer and SiO2There is polycondensation
React and formed cross-linked network structure, and then heavy metal ion " is imprisoned " in soil.It is special that the present invention takes full advantage of soil
Property, it is proposed that one more traditional restorative procedure cost neutral soil lower, easy, efficient heavy metal pollution restorative procedure,
Heavy metal after reparation can " be imprisoned " in soil steadily in the long term.
It is different that the present invention has substantially from landfill method, cement solidification method, glass solidification method:
1, landfill method is to be transferred to have in the structure of leakage performance by contaminated soil seal up for safekeeping, and being mothballed soil cannot
Utilize.
2, cement solidification method is by contaminated soil and cement mixing, forms more firm block structure after drying, will with this
Heavy metal is fixing wherein, and after solidification, soil cannot utilize.
3, glass solidification method refers to utilize high temperature by the SiO in soil2Melted formation glass phase, fixes it with this by heavy metal
In, after solidification, soil cannot utilize.
Method provided by the present invention carries out surface process for soil fundamental particle, reaches by forming cage structure on its surface
Purpose to fixing heavy metal steady in a long-term, it is most important that this method is nearly free from shadow to the organic matter in soil, microorganism
Ring, do not affect the utilization of soil.
The present invention breaches the thinking of current soil recovery technique and confines, and carries out the exploration of administering method from soil characteristic, proposes
A kind of low cost, simplicity, efficient neutral soil heavy metal pollution restorative procedure, the heavy metal after reparation can be steady in a long-term
" imprison " in soil.
The present invention can reduce animal migration and the biological effectiveness of heavy metal in soil, makes polluted soil effectively be repaiied
Multiple, it is a kind of heavy-metal contaminated soil restorative procedure safe, harmless, effective.
The present invention is that heavy metal-polluted soil improvement provides a kind of brand-new, efficient path.
Detailed description of the invention
The following is the specific embodiment of the present invention, but the present invention is not limited to these embodiments.
Embodiment 1
Reparation comprises the following steps:
1, tetraethyl orthosilicate it is dissolved in the salpeter solution of ethanol and stirs 30min, obtaining repairing reagent, wherein, positive silicic acid
Ethyl ester is 1:5 with the mass ratio of ethanol, and ethanol is 1:5 with the mass ratio of salpeter solution, and nitric acid is 1:20 with the mass ratio of water；
2, (being scattered in ultra-pure water by this neutral soil by solid-to-liquid ratio 1:1, recording pH is with neutral soil will to repair reagent
7.0) uniformly mixing, being fully contacted with soil fundamental particle so that repairing reagent, wherein reparation reagent with the mass ratio of soil is
1:40；
3, the sodium hydroxide solution that pH is 8.5 is uniformly mixed, so that sodium hydroxide is molten with the soil after reparation agent treated
Liquid is fully contacted and completes heavy metal pollution reparation with repairing reagent, and wherein sodium hydroxide solution is 1:50 with the mass ratio of soil；
Result shows, the soil Cd content total with non-rehabilitating soil after repairing is consistent, in the soil after reparation
Exchange state Cd is reduced to 0.2mg/kg from 2.4mg/kg.
Comparative example 1
When the step 3 of omission embodiment 1, when only carrying out the step 1 in embodiment 1 and step 2, in soil, total Cd is constant,
But exchange state Cd is reduced to 1.5mg/kg from 2.4mg/kg
Embodiment 2
1, tetramethoxy-silicane it is dissolved in the hydrochloric acid solution of ether and stirs 60min formation reparation reagent, tetramethoxy-silicane
Alkane is 1:5 with the mass ratio of ether, and ether is 1:5 with the mass ratio of hydrochloric acid solution, and hydrochloric acid is 1:20 with the mass ratio of water；
2, (being scattered in ultra-pure water by this neutral soil by solid-to-liquid ratio 1:1, recording pH is with neutral soil will to repair reagent
7.0) uniformly mixing, being fully contacted with soil fundamental particle so that repairing reagent, wherein reparation reagent with the mass ratio of soil is
1:40；
3, the potassium hydroxide solution that pH is 8.5 is uniformly mixed, so that potassium hydroxide is molten with the soil after reparation agent treated
Liquid is fully contacted and completes heavy metal pollution reparation with repairing reagent, and wherein potassium hydroxide solution is 1:50 with the mass ratio of soil；
Result shows, the soil Cd content total with non-rehabilitating soil after repairing is consistent, in the soil after reparation
Exchange state Cd is reduced to 0.24mg/kg from 2.4mg/kg；
Comparative example 2
When the step 3 of omission embodiment 2, when only carrying out the step 1 in embodiment 2 and step 2, in soil, total Cd is constant,
But exchange state Cd is reduced to 1.3mg/kg from 2.4mg/kg.
Specific embodiment described herein is only to present invention spirit explanation for example.Technical field of the present invention
Described specific embodiment can be made various amendment or supplements or use similar mode to substitute by technical staff, but
Without departing from the spirit of the present invention or surmount scope defined in appended claims.
Claims (10)
1. the restorative procedure of a neutral soil heavy metal pollution, it is characterised in that be Si (OR) by structural formula4Type siloxane
Material is dissolved in the acid solution of alcohol or ether, as repair reagent, mix with neutral soil, react, be subsequently adding inorganic strong alkali or
The aqueous solution of inorganic weak bases reacts further；
Wherein, one or more during R represents methyl, ethyl or propyl group.
Restorative procedure the most according to claim 1, it is characterised in that described type siloxane material is tetraethyl orthosilicate or tetramethyl
TMOS.
Restorative procedure the most according to claim 1 and 2, it is characterised in that described reparation reagent and the mass ratio of neutral soil
For 1:20-1:200.
Restorative procedure the most according to claim 1, it is characterised in that described inorganic strong alkali or inorganic weak bases selected from sodium hydroxide,
One or more in potassium hydroxide, calcium hydroxide or ammonia.
5. according to the restorative procedure described in claim 1 or 4, it is characterised in that described inorganic strong alkali or the aqueous solution of inorganic weak bases
It is 1:20-1:200 with neutral soil mass ratio.
Restorative procedure the most according to claim 1, it is characterised in that described type siloxane material is dissolved in the acid of alcohol or ether
In solution, stir 5-240min, uniformly mix with neutral soil the most again, reaction.
Restorative procedure the most according to claim 6, it is characterised in that described type siloxane material with the mass ratio of alcohol or ether is
1:1-1:10。
8. according to the restorative procedure described in claim 6 or 7, it is characterised in that described alcohol or ether with the mass ratio of acid solution are
1:1-1:20。
9. according to the restorative procedure described in claim 6 or 7, it is characterised in that described inorganic strong alkali or the aqueous solution of inorganic weak bases
PH be 8-10.
10., according to the restorative procedure described in claim 6 or 7, it is characterised in that described alcohol is ethanol or methanol, described ether is
Ether；Described acid solution one in hydrochloric acid, nitric acid or sulfur aqueous acid, in wherein said acid solution, acid and the matter of water
Amount ratio is 1:10-1:40.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108326019A (en) * | 2018-01-22 | 2018-07-27 | 环境保护部南京环境科学研究所 | A kind of soil remediation method based on modified attapulgite |
| CN109226222A (en) * | 2018-09-03 | 2019-01-18 | 南华大学 | A kind of application of surfactant, leacheate and restorative procedure for uranium contaminated soil |
| CN113245360A (en) * | 2021-06-29 | 2021-08-13 | 什邡市优禾工业产品设计工作室 | Ecological soil remediation method |
| CN113337289A (en) * | 2021-06-29 | 2021-09-03 | 什邡市优禾工业产品设计工作室 | Natural soil remediation agent |
| CN116376558A (en) * | 2023-04-07 | 2023-07-04 | 中化环境修复(上海)有限公司 | Composition for soil remediation, soil remediation agent and application thereof |
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| CN101664755A (en) * | 2009-09-29 | 2010-03-10 | 农业部环境保护科研监测所 | Method for preparing in-situ passivation restoring material of soil heavy metal with copolycondensation method |
| CN101664756A (en) * | 2009-09-29 | 2010-03-10 | 农业部环境保护科研监测所 | Passivation material for in-situ restoration of soil polluted by heavy metal, and preparation and use method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108326019A (en) * | 2018-01-22 | 2018-07-27 | 环境保护部南京环境科学研究所 | A kind of soil remediation method based on modified attapulgite |
| CN109226222A (en) * | 2018-09-03 | 2019-01-18 | 南华大学 | A kind of application of surfactant, leacheate and restorative procedure for uranium contaminated soil |
| CN113245360A (en) * | 2021-06-29 | 2021-08-13 | 什邡市优禾工业产品设计工作室 | Ecological soil remediation method |
| CN113337289A (en) * | 2021-06-29 | 2021-09-03 | 什邡市优禾工业产品设计工作室 | Natural soil remediation agent |
| CN116376558A (en) * | 2023-04-07 | 2023-07-04 | 中化环境修复(上海)有限公司 | Composition for soil remediation, soil remediation agent and application thereof |
| CN116376558B (en) * | 2023-04-07 | 2024-04-30 | 中化环境修复(上海)有限公司 | Composition for soil remediation, soil remediation agent and application thereof |
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| CN106001094B (en) | 2020-03-27 |
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