CN110041938A - A kind of heavy metal-polluted soil stabilizer and preparation method thereof - Google Patents
A kind of heavy metal-polluted soil stabilizer and preparation method thereof Download PDFInfo
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- CN110041938A CN110041938A CN201910402953.3A CN201910402953A CN110041938A CN 110041938 A CN110041938 A CN 110041938A CN 201910402953 A CN201910402953 A CN 201910402953A CN 110041938 A CN110041938 A CN 110041938A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Life Sciences & Earth Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a kind of heavy metal-polluted soil stabilizers and preparation method thereof, it is related to heavy metal-polluted soil stabilizer technical field, using polyacrylamide and carboxymethyl chitosan as primary raw material, it first passes through row Manny and hereby reacts and polyacrylamide is modified, then carboxymethyl chitosan is introduced into polyacrylamide macromolecule, the stabilizer with flocculation and absorption chelating dual function is prepared, to improve stabilizer to the stability and stabilization efficiency of heavy metal.
Description
Technical field
The present invention relates to soil stabilizer technical field, a kind of heavy metal-polluted soil stabilizer and its preparation side are particularly related to
Method.
Background technique
Heavy metal pollution of soil is global environmental problem, and main pollution be based on inorganic pollution, wherein
The heavy metals such as Cd, Ni, As, Cu, Hg, Pb, Cr, Zn are major pollutants.Heavy metal stabilization technology is added surely into soil
Determine agent and change the physics of soil, chemical property, by changing the mechanism such as pH and oxidation-reduction potential, precipitating, absorption, ion exchange
Change the occurrence status of heavy metal in the soil, so that its biological effectiveness and migration are reduced, to reduce the danger to environment
Evil property.
Applicant has found when studying existing heavy metal-polluted soil stabilizer, generallys use single stable agent at present, or
Using the contaminated by heavy metals soil of the stabilizer treatment of Organic-inorganic composite, there is treatment effects to pay no attention to for above stabilizer
Think, and the disadvantages for the treatment of effect is unstable.
Summary of the invention
In view of this, it is an object of the invention to propose a kind of heavy metal-polluted soil stabilizer and preparation method thereof, to improve
The treatment effect and treatment effeciency of stabilizer.
Based on a kind of above-mentioned purpose preparation method of heavy metal-polluted soil stabilizer provided by the invention, include the following steps,
Formaldehyde and dimethylamine are weighed, the two is then stirred 45~60min of hybrid reaction, then polyacrylamide is added into solution
Solution reacts 1~1.5h at 45~60 DEG C of temperature, the 1~1.5h that is cooled to room temperature that the reaction was continued, adjusts pH value of solution to 9~11
Afterwards, carboxymethyl chitosan solution is added, 2~4h is reacted at 80~120 DEG C of temperature, 10~20Mpa of pressure, cooling, centrifugation, from
Heart object is washed to solution and is in neutrality, filtering, and filtrate is dry at 40~50 DEG C.
Optionally, the mass ratio of the material of the polyacrylamide, formaldehyde and dimethylamine is 1:1.5~3:1.
Optionally, the concentration of the polyacrylamide solution is 2.5~5.5mol/L.
Optionally, the solution for adjusting pH value of solution is sodium hydroxide.
Optionally, the concentration of the carboxymethyl chitosan solution is 3.5~6mol/L.
Optionally, the mass ratio of the carboxymethyl chitosan and polyacrylamide is 1:1.1~1.8.
A kind of heavy metal-polluted soil stabilizer is prepared using the preparation method of the heavy metal-polluted soil stabilizer.
Optionally, usage amount is 3~8wt.% of soil.
From the above it can be seen that the present invention provides a kind of heavy metal-polluted soil stabilizer and preparation method thereof, with poly- third
Acrylamide and carboxymethyl chitosan are primary raw material, first pass through row Manny and hereby react and are modified to polyacrylamide, then will
Carboxymethyl chitosan is introduced into polyacrylamide macromolecule, prepares the stabilization with flocculation and absorption chelating dual function
Agent, to improve the soil that stabilizer is polluted the stability and stabilization efficiency of heavy metal, acquisition by heavy metal Cu, Cr, Pb, Zn
Earth analyzes stabilization effect using TCLP and BCR continuous extraction, and it is soil that as a result additive amount is worked as on surface
When 5.5wt.%, the stabilization rate to Cu, Cr, Pb, Zn is respectively 98.76%, 90.18%, 88.62% and 91.33%, performance
Higher stabilization efficiency out.
Specific embodiment
For below by the description to embodiment, for example related manufacturing process of a specific embodiment of the invention and operation
Application method etc., is described in further detail, to help those skilled in the art to inventive concept of the invention, technical solution
There is more complete, accurate and deep understanding.
It is undesirable that there are treatment effects in order to solve heavy metal soil stabilizer in the prior art, and treatment effect is unstable
The shortcomings that, a kind of preparation method of heavy metal-polluted soil stabilizer provided in an embodiment of the present invention includes the following steps, weighs formaldehyde
And dimethylamine, the two is then stirred 45~60min of hybrid reaction, then polyacrylamide solution is added into solution,
1~1.5h is reacted at 45~60 DEG C of temperature, the 1~1.5h that is cooled to room temperature that the reaction was continued adjusts pH value of solution to after 9~11, is added
Carboxymethyl chitosan solution reacts 2~4h at 80~120 DEG C of temperature, 10~20Mpa of pressure, cooling, and centrifugation is centrifuged object water
It is washed till solution to be in neutrality, filter, filtrate is dry at 40~50 DEG C.
Polyacrylamide (PAM), formaldehyde (HCHO) and dimethylamine (NH (CH3)2) carry out Manny hereby react generation it is amine-methylated
Polyacrylamide is modified polyacrylamide, then by modified polyacrylamide and carboxymethyl under alkaline environment
Chitosan carries out substitution reaction again, and carboxymethyl chitosan group is introduced into polyacrylamide strand, organic macromolecule chain
It is flocculated by bridging and heavy metal ion is fixed the absorption chelatropic reaction of heavy metal ion, prevent heavy metal ion from existing
Infiltration in soil, thus the heavy metal ion in stable soil.
In some optional embodiments, the preparation method of a kind of heavy metal-polluted soil stabilizer of embodiment 1 provided by the invention,
Include the following steps,
It is 1:2:1 by the mass ratio of the material of polyacrylamide, formaldehyde and dimethylamine, weighs formaldehyde and dimethylamine and polypropylene
Polyacrylamide is dissolved in deionized water by amide, is configured to the polyacrylamide solution that concentration is 3.5mol/L, spare, so
Afterwards both formaldehyde and dimethylamine are stirred hybrid reaction 50min under room temperature state, then are added into the solution after reaction
Polyacrylamide solution, for the abundant progress of modified-reaction, controlling the rate that polyacrylamide solution is added dropwise is 30~50mL/
Then mixed liquor is stirred to react 80min under temperature 50 C by min, be cooled to room temperature continuation and react in 50~80r/min of revolving speed
On the one hand 70min is conducive to the abundant progress of reaction, another party is for dimethylamine using two-step reaction under heating and room temperature
Sufficiently reaction, is added to excessive formaldehyde, stepwise reaction is conducive to the volatilization of extra formaldehyde；It prevents from making due to heating reaction always
At by-product generation, influence the performance of last principal product.Then the solution after reaction is adjusted using sodium hydroxide
For pH value of solution to after 9~11, addition concentration is 5mol/L carboxymethyl chitosan solution, and guarantees carboxymethyl chitosan and polyacrylamide
The mass ratio of amine is 1:1.5, and mixed liquor is poured into autoclave, reacts 2.5h at 100 DEG C of temperature, pressure 15Mpa, cold
But to after room temperature, reaction solution is centrifuged 6min under 4000r/min revolving speed, collects centrifugation object and be washed to solution and is in neutrality, vacuum
It is after suction filtration, filtrate is dry at 45 DEG C, obtain powdered stabilizer.The reaction equation of specific preparation process is as follows:
Polyacrylamide (PAM), formaldehyde (HCHO) and dimethylamine (NH (CH3)2) under certain condition carry out Manny hereby react
It generates Amino-methylated Polyacrylamide (APAM)；
Amino-methylated Polyacrylamide (APAM) reacting under alkaline condition with carboxymethyl chitosan
- OH and-NH on chitosan2With the ability being complexed with metal, at the same polyacrylamide to heavy metal from
Son can play adhesive effect by the chemical action etc. of physics, to improve the stabilization to heavy metal.
In some optional embodiments, by the technological parameter of table 1, different stabilizers has been prepared.
1 different technical parameters of table
Stabilizer prepared by the 8 kinds of stabilizers and embodiment 1 of above-mentioned preparation is numbered, respectively 1~9# of stabilizer.
1, the processing of contaminated soil
Contaminated soil is derived from the soil of the Surface mulch in the chemical plant of Xuancheng, dries after the soil fetched is rejected foreign matter, grinds
50 meshes are pressed through, soil is yellow soil, is shown in Table 2 using the physicochemical property that routine test method obtains soil, tests a huge sum of money for soil sample
The grade III Standard comparing result for belonging to content and " standard of soil environment quality " (GB15618-1995) is shown in Table 3.
The basic physical and chemical of 2 contaminated soil of table
| Initial water content/% | Air-dry water content/% | pH | Porosity | Organic matter/% |
| 15.3 | 4.21 | 6.5 | 0.414 | 2.58 |
3 heavy metal content in soil of table/mgkg-1
| Heavy metal | Contaminated soil content | Grade III Standard |
| Cu | 783 | 400 |
| Cr | 397.9 | 300 |
| Pb | 512 | 500 |
| Zn | 1112 | 500 |
From table 1 and mark as can be seen that the pH of contaminated soil is close to neutrality, partially such as faintly acid, the content of organic matter 2.58%, weight
Metallic copper (Cu), chromium (Cr), lead (Pb) and zinc (Zn) content are the 1.95 of grade III Standard, 1.33,1.02 and 2.22 times respectively, right
Soil causes different degrees of pollution.
2, stabilizer performance test
Weighing above-mentioned the contaminated soil 450g, 50g handled well is portion, is placed in the beaker of 9 250mL, to burning
1~9# stabilizer of preparation of the embodiment of the present invention is added in cup, every kind of stabilizer is respectively provided with three pitch-based spheres, 3wt.%,
Deionized water is added by solid-to-liquid ratio 1:2 in 5.5wt.% and 8wt.%, and continues after stirring 40min, places 30 after sealing naturally
It, and control is used as using the soil sample for not applying stabilizer.
Stabilizer is as follows to the calculation formula of the stabilization rate of heavy metal in soil:
In formula: δ is to stablize rate；C0The leaching content of heavy metal in soil, mg/kg when not add stabilizer；C1It is steady to add
Determine the leaching content of heavy metal in soil after agent, mg/kg.
3, test analysis
(1) influence of the stabilizer to heavy metal leaching content
Test result is as shown in table 4~6.The data that table 4~6 is shown are respectively that stabilizer additive amount is 3wt.%,
The data of 5.5wt.% and 8wt.%.
4 stabilizer additive amount of table is the various stabilized metal rates of 3wt.%
5 stabilizer additive amount of table is the various stabilized metal rates of 5.5wt.%
6 stabilizer additive amount of table is the various stabilized metal rates of 8wt.%
Different stabilizers is to identical Leaching of Heavy Metals concentration and same stable agent to different Leaching of Heavy Metals concentration
Show different effect.When additive amount is the 5.5wt.% of soil, the stabilization rate to Cu, Cr, Pb, Zn is respectively
98.76%, 90.18%, 88.62% and 91.33%.
It should be understood by those ordinary skilled in the art that: the discussion of any of the above embodiment is exemplary only, not
It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under thinking of the invention, above embodiments
Or can also be combined between the technical characteristic in different embodiments, step can be realized with random order, and be existed such as
Many other variations of the upper different aspect of the invention, for simplicity, they are not provided in details.
The embodiment of the present invention be intended to cover fall into all such replacements within the broad range of appended claims,
Modifications and variations.Therefore, all within the spirits and principles of the present invention, any omission, modification, equivalent replacement, the improvement made
Deng should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of heavy metal-polluted soil stabilizer, which is characterized in that include the following steps, weigh formaldehyde and diformazan
Then the two is stirred 45~60min of hybrid reaction, then polyacrylamide solution is added into solution by amine, in temperature 45
1~1.5h is reacted at~60 DEG C, the 1~1.5h that is cooled to room temperature that the reaction was continued adjusts pH value of solution to after 9~11, carboxymethyl is added
Chitosan solution reacts 2~4h at 80~120 DEG C of temperature, 10~20Mpa of pressure, and cooling, centrifugation, centrifugation object is washed to molten
Liquid is in neutrality, filtering, and filtrate is dry at 40~50 DEG C.
2. the preparation method of heavy metal-polluted soil stabilizer according to claim 1, which is characterized in that the polyacrylamide
The mass ratio of the material of amine, formaldehyde and dimethylamine is 1:1.5~3:1.
3. the preparation method of heavy metal-polluted soil stabilizer according to claim 1, which is characterized in that the polyacrylamide
The concentration of solution is 2.5~5.5mol/L.
4. the preparation method of heavy metal-polluted soil stabilizer according to claim 1, which is characterized in that the adjusting pH value of solution
Solution be sodium hydroxide.
5. the preparation method of heavy metal-polluted soil stabilizer according to claim 1, which is characterized in that the carboxymethyl chitosan
The concentration of sugar juice is 3.5~6mol/L.
6. the preparation method of heavy metal-polluted soil stabilizer according to claim 1, which is characterized in that the carboxymethyl chitosan
The mass ratio of sugar and polyacrylamide is 1:1.1~1.8.
7. a kind of heavy metal-polluted soil stabilizer, which is characterized in that steady using any heavy metal-polluted soil of claim 1~6
The preparation method for determining agent is prepared.
8. heavy metal-polluted soil stabilizer according to claim 7, which is characterized in that usage amount is 3 that usage amount is soil
~8wt.%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112453040A (en) * | 2020-10-14 | 2021-03-09 | 重庆大学 | Leaching remediation method for chromium-lead composite contaminated soil |
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2019
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| CN112453040A (en) * | 2020-10-14 | 2021-03-09 | 重庆大学 | Leaching remediation method for chromium-lead composite contaminated soil |
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Application publication date: 20190723 |