CN109777437A - A kind of preparation method of heavy metal curing agent - Google Patents

A kind of preparation method of heavy metal curing agent Download PDF

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Publication number
CN109777437A
CN109777437A CN201910166930.7A CN201910166930A CN109777437A CN 109777437 A CN109777437 A CN 109777437A CN 201910166930 A CN201910166930 A CN 201910166930A CN 109777437 A CN109777437 A CN 109777437A
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China
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heavy metal
curing agent
red mud
preparation
metal curing
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CN201910166930.7A
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Inventor
李彬
戚江
张英杰
董鹏
关清卿
刘宇
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

The present invention discloses a kind of preparation method of heavy metal curing agent, will pulverize, is sieved after red mud drying, successively adds ferrous salt solution, black liquid, glyoxal, and microwave activates to obtain red mud composite particles;By shell and diatomite clean dry, pulverize respectively, high-temperature calcination after sieving;It will size mixing under red mud composite particles, conch meal, diatomite in powder, phosphate solution, thiamines room temperature, uniformly mix, be granulated after dry, heavy metal curing agent is prepared;Preparation process of the present invention is simple, raw material sources are extensive, the handling problems of red mud, black liquid and waste shell are solved simultaneously, curing agent has preferable mechanical strength, the ion exchangeable species content of heavy metal in soil can be effectively reduced, realize solidification to Compound Heavy Metals ion, while the release of contained microelement in shell, the organic matter in black liquid provide advantage for ecological environment of soil, provide feasible program for the redevelopment and heavy-metal composite pollution soil remediation of waste.

Description

A kind of preparation method of heavy metal curing agent
Technical field
The present invention relates to heavy metal pollution of soil to administer field, is related to a kind of preparation method of heavy metal curing agent.
Background technique
Pollution waste residue of the red mud as aluminum oxide industry production discharge, is currently mainly used the disposition of stockpiling method, occupies big It measures land resource and will cause the salinization of soil and underground water pollution simultaneously because red mud contains high alkalinity, high salinity, store up The fugitive dust of generation will destroy the environment on periphery.Currently, being directed to the disposal of resources of red mud, a variety of methods have been explored, have been led to It crosses and prepares construction material, adsorbent, soil-repairing agent, catalyst etc. and can be realized the effective use of red mud.Wherein utilize red mud Preparing heavy metal soil-repairing agent can be realized the recycling of red mud, and can solve pollution problem, but due to red mud free alkali Rate of release is too fast, it will causes the basicity of soil excessively high, destroys ecological environment of soil.
For paper industry using plant fiber resource as primary raw material, production process water consumption is big, and pulping process generates useless Containing a large amount of cellulose, lignin and inorganic salts etc. in water, the serious of entire water pollution and ecological environment can be caused It destroys.Wherein lignin is the three-dimensional netted polyphenol quasi polymer of macromolecular, the functional group containing there are many, before application with higher Scape.The Liginon Resource in black liquid is made full use of, not only can solve the problem of lignin pollution, but also can realize following for conglomerate Ring development.
With the fast development of shellfish culture and processing industry, a large amount of waste shells of generation accumulate caused environment year by year Increasingly severe, not only to occupy a large amount of soil, while can also give out dense smell is polluted, environmental problem is caused.Shellfish Shell contains about 95% calcium carbonate, and it is a kind of nontoxic nothing that other, which are a small amount of organic conchiolin and trace elements K, sodium, phosphorus etc., Harmful natural resources.
Therefore, a kind of effective use red mud is found at present, the cooperative disposal method of black liquid and shell is applied to a huge sum of money Belong to combined contamination soil reparation, the problem of handling the rate of release of red mud free alkali well, be current urgent need to resolve.
Summary of the invention
The present invention for the defects or inadequacies for existing technologies, provide it is a kind of prepare conveniently, economical, effective red mud is multiple The preparation method of Counter weight metal curing agent, specifically includes the following steps:
(1) it will pulverize after red mud drying, cross 50 meshes, successively add ferrous salt solution, black liquid, glyoxal, 80 ~ Microwave is carried out at 120 DEG C and activates 10 ~ 30min, obtains red mud composite particles;
(2) by shell and diatomite clean dry, pulverize, sieve with 100 mesh sieve respectively, at 900 ~ 1500 DEG C high-temperature calcination 1 ~ 2h;
(3) it will mix and size mixing under red mud composite particles, conch meal, diatomite in powder, phosphate solution, thiamines room temperature, uniformly mix, It is granulated after drying, heavy metal curing agent particle is prepared.
The mass volume ratio mL:g of step (1) red mud dry powder and ferrous salt solution is 1:10 ~ 20, and red mud dry powder and papermaking are black The mass volume ratio mL:g of liquid is 1:10 ~ 50, and the mass ratio of glyoxal and black liquor is 1:2 ~ 10.
Step (1) ferrous salt is frerrous chloride or ferrous sulfate, and the concentration of ferrous salt solution is 0.5 ~ 1 mol/L.
The power of step (1) microwave activation is 800 ~ 1200W, frequency 1200MHz.
Step (3) red mud composite particles, conch meal, diatomite in powder, phosphate solution, thiamines mixing mass ratio be 40 ~ 60:15~30:10~20:1~5:1~5。
Step (3) phosphate is KH2PO4, Ca(H2PO4)2Or Na2HPO4, the concentration of phosphate solution is 0.5~3 mol/ L。
Step (3) is granulated using granulating disc, and revolving speed when granulation is 30 ~ 50r/min, and water ash mass ratio is 0.4~0.6。
Application method of the heavy metal curing agent prepared by the present invention in heavy-metal contaminated soil: curing agent particle is added Into in the soil of heavy metal pollution, hardener dose is the 3% ~ 10% of contaminated soil quality, and soil moisture content is 15~30%.
The beneficial effects of the present invention are:
(1) heavy metal curing agent is compounded using preparations such as discarded red muds and shell, it being capable of effectively Pb in curing soil2+、 As5+、Cr6+、Cd2+
(2) great amount of hydroxy group ferriferous oxide can be coated using the modified red mud particle surface of ferrous salt solution, with heavy metal from Complex reaction occurs for son, and ferrous ion can also be replaced with calcium ion on surface, forms layer of surface activating agent, reinforces to gold Belong to the combination of ion, the addition of ferrous ion can improve the gel situation of red mud particle, to a certain extent can also be by Cr6+Turn Turn to Cr3+, realize effectively passivation.
(3) lignin itself in black liquid has a variety of functional groups, wooden by microwave heating under alkali environment Ethoxyl etherification can occur with glyoxal for element, and reactivity is reinforced, substantially improved in conjunction with the ability of heavy metal ion, and micro- Wave heating can also greatly improve red mud compounding particle aperture and specific surface area, improve absorption property.
(4) shell after high-temperature calcination, diatomite generate CaO, SiO2Equal substances are formed using lignin as bridging, joint The reticular structure of ferro-aluminum colloidal silica, the adsorbent materials such as CaO are wrapped in, have certain mechanical strength, substantially improve solidifying Colloidality energy and absorption property;Phosphate and thiamines can reinforce the combination to metal ion, and free alkali is fixed on red mud In crystal and colloid in, rate of release slows down, and soil pH is maintained at 6.5 ~ 8.1, will not be by soda acid.
(5) ground such as the organic matter and microelement such as potassium, phosphorus, nitrogen that contain in black liquid and shell, which discharge, can effectively improve Soil ecology suitability.
(6) operation of the present invention process is simple, and material source is easy to get extensively, and the modification of red mud is synchronous with the modification of lignin It carries out, Coordination Treatment realizes the comprehensive treatment of soil and the resource utilization of waste.
Specific embodiment
Below by embodiment, invention is further described in detail, but the present invention is not limited only to the content, it is all Made any modifications, equivalent replacements, and improvements etc. within the spirit and principles in the present invention should all include in protection of the invention Range etc.
Embodiment 1
A kind of preparation method of heavy metal curing agent, the specific steps are as follows:
(1) it will pulverize after red mud drying, cross 50 meshes, successively add solution of ferrous chloride, black liquid, glyoxal, Microwave is carried out at 80 DEG C and activates 10min, obtains red mud composite particles, wherein the quality volume of red mud dry powder and solution of ferrous chloride It is 1:10 than mL:g, solution of ferrous chloride concentration is 0.5mol/L, and the mass volume ratio mL:g of red mud dry powder and black liquid is The mass ratio of 1:10, glyoxal and black liquor is 1:5, and the power of microwave activation is 800W, and frequency is 1200MHz;
(2) it by shell and diatomite clean dry, pulverizes, sieves with 100 mesh sieve, the high-temperature calcination 2h at 900 DEG C;
(3) by diatomite in powder made from conch meal made from red mud composite particles made from step (1), step (2), step (2), Phosphate solution, thiamines are that 40:15:10:1:1 is mixed according to mass ratio, and phosphate solution is that concentration is 0.5mol/L's KH2PO4Solution is sized mixing under room temperature, is uniformly mixed, and is granulated after dry with granulating disc, revolving speed 30r/min, and water ash mass ratio is 0.4, heavy metal curing agent particle is prepared, grain diameter is 1 ~ 3 mm.
The curing agent particle that preparation is completed is added to the soil of heavy metal pollution, hardener dose is contaminated soil quality 3%, soil moisture content is maintained at 20%, and the concentration of heavy metal ion of the contaminated soil of simulation is as shown in table 1 below, after 15 days, lead Ion-exchange state decrease by 87.71%;The ion-exchange state of arsenic decreases by 89.54%;The ion-exchange state of chromium decreases by To 86.58%;The ion-exchange state of cadmium decreases by 87.47%.
Table 1
Pb2+ As5+ Cr6+ Cd2+
Concentration (mg/kg) 100 100 100 100
Embodiment 2
A kind of preparation method of heavy metal curing agent, the specific steps are as follows:
(2) it will pulverize after red mud drying, cross 50 meshes, successively add solution of ferrous chloride, black liquid, glyoxal, Microwave is carried out at 100 DEG C and activates 20min, obtains red mud composite particles, wherein the mass body of red mud dry powder and solution of ferrous chloride Product is 1:15 than mL:g, and solution of ferrous chloride concentration is 1mol/L, and the mass volume ratio mL:g of red mud dry powder and black liquid is The mass ratio of 1:15, glyoxal and black liquor is 1:10, and the power of microwave activation is 1000W, and frequency is 1200MHz;
(2) it by waste shell and diatomite clean dry, pulverizes, sieves with 100 mesh sieve, the high-temperature calcination 1h at 1500 DEG C;
(3) by diatomite in powder made from conch meal made from red mud composite particles made from step (1), step (2), step (2), Phosphate solution, thiamines are that 55:25:15:2:3 is mixed according to mass ratio, and phosphate solution is the Ca that concentration is 2mol/L (H2PO4)2Solution is sized mixing under room temperature, is uniformly mixed, and is granulated after dry with granulating disc, revolving speed 50r/min, water ash mass ratio It is 0.5, heavy metal curing agent particle is prepared, grain diameter is 1 ~ 3 mm.
The curing agent particle that preparation is completed is added to the soil of heavy metal pollution, curing dose used is contaminated soil 5%, soil moisture content is maintained at 15%, and the concentration of heavy metal ion of the contaminated soil of simulation is same as Example 1, after 15 days, The ion-exchange state of lead decreases by 89.73%;The ion-exchange state of arsenic decreases by 91.74%;The ion-exchange state range of decrease of chromium Reach 88.61%;The ion-exchange state of cadmium decreases by 89.37%.
Embodiment 3
A kind of preparation method of heavy metal curing agent, the specific steps are as follows:
(3) it will pulverize after red mud drying, cross 50 meshes, successively add ferrous sulfate solution, black liquid, glyoxal, Microwave is carried out at 120 DEG C and activates 30min, obtains red mud composite particles, wherein the mass body of red mud dry powder and ferrous sulfate solution Product is 1:20 than mL:g, and ferrous sulfate solution concentration is 0.8mol/L, the mass volume ratio mL:g of red mud dry powder and black liquid For 1:50, the mass ratio of glyoxal and black liquor is 1:2, and the power of microwave activation is 1200W, and frequency is 1200MHz;
(2) it by waste shell and diatomite clean dry, pulverizes, sieves with 100 mesh sieve, the high-temperature calcination 1.5h at 1200 DEG C;
(3) by diatomite in powder made from conch meal made from red mud composite particles made from step (1), step (2), step (2), Phosphate solution, thiamines are that 60:30:20:5:5 is mixed according to mass ratio, and phosphate solution is that concentration is 3mol/L's Na2HPO4Solution is sized mixing under room temperature, is uniformly mixed, and is granulated after dry with granulating disc, revolving speed 40r/min, water ash mass ratio It is 0.6, heavy metal curing agent particle is prepared, grain diameter is 1 ~ 3 mm.
The curing agent particle that preparation is completed is added to the soil of heavy metal pollution, curing dose used is contaminated soil 10%, soil moisture content is maintained at 30%, and the concentration of heavy metal ion of the contaminated soil of simulation is same as Example 1, after 15 days, The ion-exchange state of lead decreases by 92.15%;The ion-exchange state of arsenic decreases by 95.29%;The ion-exchange state range of decrease of chromium Reach 92.93%;The ion-exchange state of cadmium decreases by 93.21%.

Claims (7)

1. a kind of preparation method of heavy metal curing agent, which is characterized in that specifically includes the following steps:
(1) it will pulverize after red mud drying, cross 50 meshes, successively add ferrous salt solution, black liquid, glyoxal, 80 ~ Microwave is carried out at 120 DEG C and activates 10 ~ 30min, obtains red mud composite particles;
(2) it by waste shell and diatomite clean dry, pulverizes, sieves with 100 mesh sieve respectively, high temperature is forged at 900 ~ 1500 DEG C Burn 1 ~ 2h;
(3) it will mix and size mixing under red mud composite particles, conch meal, diatomite in powder, phosphate solution, thiamines room temperature, uniformly mix, It is granulated after drying, heavy metal curing agent particle is prepared.
2. the preparation method of heavy metal curing agent according to claim 1, which is characterized in that step (1) red mud dry powder and Asia The mass volume ratio mL:g of iron salt solutions is 1:10 ~ 20, the mass volume ratio mL:g of red mud dry powder and black liquid be 1:10 ~ 50, the mass ratio of glyoxal and black liquor is 1:2 ~ 10.
3. the preparation method of heavy metal curing agent according to claim 1, which is characterized in that step (1) ferrous salt is chlorination Ferrous or ferrous sulfate, the concentration of ferrous salt solution are 0.5 ~ 1 mol/L.
4. the preparation method of heavy metal curing agent according to claim 1, which is characterized in that the function of step (1) microwave activation Rate is 800 ~ 1200W, frequency 1200MHz.
5. the preparation method of heavy metal curing agent according to claim 1, which is characterized in that step (3) red mud composite particles, The mass ratio that conch meal, diatomite in powder, phosphate solution, thiamines mix is 40 ~ 60:15 ~ 30:10 ~ 20:1 ~ 5:1 ~ 5.
6. the preparation method of heavy metal curing agent according to claim 1, which is characterized in that step (3) phosphate is KH2PO4, Ca(H2PO4)2Or Na2HPO4, the concentration of phosphate solution is 0.5~3 mol/L.
7. the preparation method of heavy metal curing agent according to claim 1, which is characterized in that step (3) uses disc granulation Machine is granulated, and revolving speed when granulation is 30 ~ 50r/min, and water ash mass ratio is 0.4 ~ 0.6.
CN201910166930.7A 2019-03-06 2019-03-06 A kind of preparation method of heavy metal curing agent Pending CN109777437A (en)

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CN110330978A (en) * 2019-05-22 2019-10-15 深圳市深港产学研环保工程技术股份有限公司 Soil-repairing agent and soil remediation method
CN113416012A (en) * 2021-07-05 2021-09-21 常熟理工学院 Method for preparing curing agent by using concrete waste residues

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Publication number Priority date Publication date Assignee Title
CN110330978A (en) * 2019-05-22 2019-10-15 深圳市深港产学研环保工程技术股份有限公司 Soil-repairing agent and soil remediation method
CN110330978B (en) * 2019-05-22 2021-05-25 深圳市深港产学研环保工程技术股份有限公司 Soil remediation agent and soil remediation method
CN113416012A (en) * 2021-07-05 2021-09-21 常熟理工学院 Method for preparing curing agent by using concrete waste residues
CN113416012B (en) * 2021-07-05 2022-08-26 常熟理工学院 Method for preparing curing agent by using concrete waste residues

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