CN114479874A - Red mud-based heavy metal curing agent and preparation method and application thereof - Google Patents
Red mud-based heavy metal curing agent and preparation method and application thereof Download PDFInfo
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- CN114479874A CN114479874A CN202210108492.0A CN202210108492A CN114479874A CN 114479874 A CN114479874 A CN 114479874A CN 202210108492 A CN202210108492 A CN 202210108492A CN 114479874 A CN114479874 A CN 114479874A
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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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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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
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a red mud-based heavy metal curing agent and a preparation method and application thereof, wherein the red mud-based heavy metal curing agent comprises the following components in parts by weight: 80-100 parts of red mud, 30-40 parts of steel slag, 20-40 parts of blast furnace slag, 20-30 parts of coal gangue, 30-50 parts of fly ash, 20-45 parts of carbide slag, 20-45 parts of waste gypsum, 5-20 parts of a stabilizer and 0-10 parts of an adsorbent. The material not only realizes the large consumption of industrial solid wastes, but also realizes the non-use of traditional cement, reduces the cement consumption, is green and environment-friendly, has simple preparation process, has good curing effect on heavy metals, meets the national requirements, has low cost and is suitable for popularization and application to the society.
Description
Technical Field
The invention relates to the field of heavy metal curing agents, and particularly provides a red mud-based heavy metal curing agent as well as a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Common soil and underground water pollution is mainly divided into two categories, namely inorganic pollution and organic pollution, wherein the inorganic pollution mainly comprises heavy metal pollution. Soil pollution is closely related to underground water pollution, and the pollution is easy to spread. The heavy metal pollution of soil is one of the most extensive, serious and intractable pollution in the polluted area of China, and the area of moderate and severe polluted farmland of China is more than 3 ten thousand square kilometers. Copper, lead and chromium are toxic elements commonly existing in heavy metal contaminated soil, have the characteristics of long-term property, non-mobility and the like, are enriched by plants after entering the soil, are accumulated through a food chain to influence the health of human beings, and cause serious adverse effects on the life health of local residents.
At present, heavy metal cement is cured and treated by using a mature material with a wide application range, but the production of cement consumes a large amount of mineral resources, so that the mineral resources are not renewable, a large amount of energy is consumed, and greenhouse gas is discharged, so that certain harm is caused to the environment, the utilization rate of industrial solid waste in China is not high, a large amount of industrial solid waste is stockpiled in the open air, and the problem of poor curing effect of the existing curing agent also exists.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a red mud-based heavy metal curing agent and a preparation method and application thereof. The material not only realizes the large consumption of industrial solid wastes, but also realizes the non-use of traditional cement, reduces the cement consumption, is green and environment-friendly, has simple preparation process, has good curing effect on heavy metals, meets the requirements, has low cost and is suitable for popularization and application.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a red mud-based efficient heavy metal curing agent, which comprises the following components in parts by weight: 80-100 parts of red mud, 30-40 parts of steel slag, 20-40 parts of blast furnace slag, 20-30 parts of coal gangue, 30-50 parts of fly ash, 20-45 parts of carbide slag, 20-45 parts of waste gypsum, 5-20 parts of a stabilizer and 0-10 parts of an adsorbent.
In a second aspect, the invention provides a preparation method of the red mud-based efficient heavy metal curing agent, which comprises the following steps:
mixing the steel slag, the blast furnace slag, the coal gangue, the fly ash, the stabilizer and the adsorbent to obtain a mixture A;
cooling, crushing and sieving the mixture A at room temperature to obtain a mixture B;
and mixing and stirring the mixture B, the red mud, the waste gypsum and the carbide slag uniformly to obtain the red mud-calcium carbide slag.
In a third aspect, the invention provides an application of the red mud-based efficient heavy metal curing agent in heavy metal curing;
or in the treatment of soil or groundwater contaminated by organic pollutants;
especially for solidifying heavy metals Cu, Pb or Cr in soil.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
the invention provides a red mud-based efficient heavy metal curing agent and a preparation method thereof, wherein the red mud has a loose and porous microstructure and high porosity, and is suitable for being used as a heavy metal ion adsorption material. The modified red mud has direct adsorption effect on heavy metal pollution ions, and can react with steel slag ore, slag and fly ash in a system to generate hydrate gel so as to further adsorb and precipitate heavy metal and organic pollutants.
The fly ash is also an easily obtained cheap industrial solid waste, the fly ash combined with the stabilizer improves the silicon content and the solidification capability, the effect of the fly ash and other industrial solid wastes for cooperatively treating heavy metal pollution ions is greater than the capability of the fly ash for treating heavy metal pollution factors by single components, the fly ash is beneficial to regulating soil nutrients, the regulation and control of the performance of the solidified soil are realized, and the soil quality recovery is promoted. Meanwhile, the excessive alkali can be combined with the excessive acid in the modified red mud to maintain the pH value of the soil.
The waste gypsum and the carbide slag have similar action with the red mud, have gelling property, can provide calcium ions in the reaction process, and the calcium ions can improve the conglomeration of the red mud, thereby improving the physical and mechanical properties of the solidified soil macroscopically. The ettringite component in the waste gypsum can generate copper sulfate with copper ions to realize copper ion curing, and the absorption effect of a red mud system is matched to realize the maximization of the heavy metal ion curing efficiency. The waste gypsum, the carbide slag and the red mud are matched, so that the solidification efficiency of the heavy metal can be improved to the maximum extent.
After various components in the stabilizer are combined with the modified red mud base material, heavy metals are easy to form combined compounds with poor solubility in an alkaline environment, so that the mobility of the heavy metals is weakened, and the toxicity of the heavy metals is greatly reduced. Wherein the special hydroxyhistidine and ammonium humate as organic components can provide a large number of specific and non-specific adsorption sites, and contain various active groups (such as COO-, -NH)2、＝NH、＝PO4S-, -O-, etc.) as a ligand to form a stable complex and an organic ligand by complexing or chelating with the heavy metal, thereby fixing the heavy metal.
The invention greatly improves the use proportion of the red mud in the curing agent, has the advantages of good use effect, low cost and simple preparation process, and is suitable for popularization.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect, the invention provides a red mud-based efficient heavy metal curing agent, which comprises the following components in parts by weight: 80-100 parts of red mud, 30-40 parts of steel slag, 20-40 parts of blast furnace slag, 20-30 parts of coal gangue, 30-50 parts of fly ash, 20-45 parts of carbide slag, 20-45 parts of waste gypsum, 5-20 parts of a stabilizer and 0-10 parts of an adsorbent.
In some embodiments, the red mud is an acid-treated or heat-treated modified red mud.
Preferably, the red mud is selected from bayer process red mud, sintering process red mud or mixed red mud.
More preferably, the particle size of the red mud is 45-200 meshes.
In some embodiments, the steel slag, blast furnace slag, coal gangue, fly ash, and carbide slag have a particle size of less than 60 mesh.
In some embodiments, the stabilizer is a mixture of stabilizer A and stabilizer B, wherein stabilizer A is selected from NaOH, KOH, Ca (OH)2Or Na2CO3The stabilizing agent B is selected from hydroxyl histidine or ammonium humate.
The stabilizer A creates an alkaline environment in the system to accelerate the generation of reaction hydrated gel and improve the curing efficiency; the stabilizer B as an organic component can provide a large number of specific and nonspecific adsorption sites, can be used as a ligand to perform complexation or chelation with heavy metals to form stable complexes and organic ligands, makes up the pollutant components which are not completely solidified in the red mud matrix system, and improves the stability.
Preferably, the molar ratio of the stabilizer A to the stabilizer B is 1-4: 5-8.
In some embodiments, the waste gypsum is selected from one or more of phosphogypsum, fluorgypsum, titanogypsum or soda gypsum.
In some embodiments, the adsorbent is selected from one or more of sepiolite, 5A zeolite or attapulgite, and the main function of the adsorbent is to ensure that the components are uniformly mixed when the preparation process is difficult to mix, and meanwhile, the adsorbent has a certain adsorption effect to ensure that the reaction is normally carried out.
In a second aspect, the invention provides a preparation method of the red mud-based efficient heavy metal curing agent, which comprises the following steps:
mixing steel slag, blast furnace slag, coal gangue and fly ash with a stabilizer and an adsorbent to obtain a mixture A;
cooling, crushing and sieving the mixture A at room temperature to obtain a mixture B;
and mixing and stirring the mixture B, the red mud, the waste gypsum and the carbide slag uniformly to obtain the red mud-calcium carbide slag.
In some embodiments, mix a is ground and passed through a 60 mesh screen.
In some embodiments, the red mud is an acid-treated or heat-treated modified red mud.
Preferably, the acid treatment method is as follows: soaking the red mud by using 0.1-0.5 mol/L hydrochloric acid or 0.2-1 mol/L nitric acid.
More preferably, the soaking time is 30min to 60 min.
Preferably, the heat treatment method comprises the following steps: calcining the red mud at 500-1000 ℃ for 60-90 min.
In a third aspect, the invention provides an application of the red mud-based efficient heavy metal curing agent in heavy metal curing;
or in the treatment of soil or groundwater contaminated by organic pollutants;
especially for solidifying heavy metals Cu, Pb or Cr in soil.
The present invention will be further described with reference to the following examples.
Example one
The red mud-based efficient heavy metal curing agent comprises the following components in parts by weight: 85 parts of modified red mud, 35 parts of steel slag, 30 parts of blast furnace slag, 25 parts of coal gangue, 30 parts of fly ash, 30 parts of carbide slag, 30 parts of phosphogypsum and 5 parts of stabilizer;
the modified red mud is Bayer process red mud, and the particle size of the red mud is 100 meshes;
the modified red mud is activated by hydrochloric acid with the concentration of 0.25mol/L, and the acid treatment time is 30 min.
The particle sizes of the steel slag, the blast furnace slag, the coal gangue, the fly ash and the carbide slag are less than 60 meshes;
the stabilizer is NaOH, Ca (OH)2And hydroxyhistidine mixture, NaOH, Ca (OH)2And hydroxyhistidine in a molar ratio of 1:1:5。
the preparation method of the red mud-based efficient heavy metal curing agent comprises the following steps:
the first process step: mixing the steel slag, blast furnace slag, coal gangue, fly ash and a stabilizer to obtain a mixture A, cooling and crushing at room temperature, and sieving by a 60-mesh nylon sieve to obtain a mixture B;
and a second step: and mixing and stirring the mixture B, the modified red mud, the waste gypsum and the carbide slag uniformly to obtain a mixture C, thus obtaining the efficient heavy metal curing agent.
Example two
A red mud-based efficient heavy metal curing agent comprises the following components in parts by weight: 90 parts of modified red mud, 40 parts of steel slag, 40 parts of blast furnace slag, 30 parts of coal gangue, 35 parts of fly ash, 40 parts of carbide slag, 40 parts of phosphogypsum, 10 parts of stabilizer and 6 parts of adsorbent;
the modified red mud is Bayer process red mud, and the particle size of the red mud is 100 meshes;
the modified red mud is activated by hydrochloric acid with the concentration of 0.5mol/L, and the acid treatment time is 40 min;
the particle sizes of the steel slag, the blast furnace slag, the coal gangue, the fly ash and the carbide slag are less than 60 meshes;
the stabilizer is KOH, Ca (OH)2And ammonium humate mixture, KOH, Ca (OH)2The molar ratio of the ammonium humate to the ammonium humate is 2:2: 5.
The adsorbent is sepiolite.
The preparation method of the red mud-based efficient heavy metal curing agent comprises the following steps:
the first process step: mixing steel slag, blast furnace slag, coal gangue, fly ash, a stabilizer and an adsorbent to obtain a mixture A, cooling and crushing at room temperature, and sieving by a 60-mesh nylon sieve to obtain a mixture B;
and a second step: and mixing and stirring the mixture B, the modified red mud, the waste gypsum and the carbide slag uniformly to obtain a mixture C, thus obtaining the efficient heavy metal curing agent.
EXAMPLE III
A red mud-based efficient heavy metal curing agent comprises the following components in parts by weight: 100 parts of modified red mud, 40 parts of steel slag, 35 parts of blast furnace slag, 30 parts of coal gangue, 40 parts of fly ash, 40 parts of carbide slag, 40 parts of fluorgypsum, 10 parts of a stabilizer and 6 parts of an adsorbent.
The modified red mud is Bayer process red mud, and the particle size of the red mud is 80 meshes.
The modified red mud is red mud subjected to thermal activation at 600 ℃, and the thermal activation time is 60 min.
The particle sizes of the steel slag, the blast furnace slag, the coal gangue, the fly ash and the carbide slag are less than 60 meshes.
The stabilizer is a mixture of NaOH and ammonium humate, and the molar ratio of the NaOH to the ammonium humate is 2: 5.
The adsorbent is 5A zeolite.
The preparation method of the red mud-based efficient heavy metal curing agent comprises the following steps:
the first process step: mixing the steel slag, blast furnace slag, coal gangue and fly ash with a stabilizer to obtain a mixture A, cooling and crushing at room temperature, and sieving by a 60-mesh nylon sieve to obtain a mixture B;
and a second step: and mixing and stirring the mixture B, the modified red mud, the waste gypsum and the carbide slag uniformly to obtain a mixture C, thus obtaining the efficient heavy metal curing agent.
Comparative example 1
The differences with respect to example 1 are: the red mud was untreated red mud, and the rest was the same as in example 1.
Comparative example 2
The differences with respect to example 1 are: the fly ash was omitted and the rest was the same as in example 1.
Comparative example 3
The differences with respect to example 1 are: the stabilizer was omitted and the procedure was as in example 1.
Comparative example 4
The differences with respect to example 1 are: the coal gangue was omitted, and the rest was the same as in example 1.
Comparative example 5
The differences with respect to example 1 are: the carbide slag was omitted, and the procedure was otherwise the same as in example 1.
Comparative example 6
The differences with respect to example 1 are: the waste gypsum was omitted, and the procedure was otherwise the same as in example 1.
Comparative example 7
The differences with respect to example 1 are: steel slag was omitted, and the procedure was otherwise the same as in example 1.
Comparative example 8
The differences with respect to example 1 are: the slag of the upper furnace is saved slightly, and the rest is the same as that of the embodiment 1.
Performance index
The red mud-based efficient heavy metal curing agent obtained in the examples 1-3 and the comparative examples 1-8 is applied to the pollution treatment of the soil with the heavy metal detection exceeding the standard.
1. Selecting a test land with heavy metal pollution exceeding the standard, planning a treatment range, and sampling and detecting soil before treatment.
2. The test land is sowed with 100kg of the red mud-based heavy metal curing agent prepared in examples 1-3 and comparative examples 1-8 per square meter, and the test land is ploughed and turned by a tiller after the curing agent is sowed.
3. And (4) curing the test land for 7 days, and taking a test land soil sample for detection after 7 days of curing.
After the test is finished, soil is taken for pollutant leaching toxicity test, an inductively coupled plasma mass spectrometry method is adopted as a test method, an inductively coupled plasma emission spectrometer is adopted as a test instrument, and test results are shown in table 1:
TABLE 1
The red mud-based efficient heavy metal curing agent obtained in the examples 1 to 3 can meet the relevant requirements in hazardous waste identification standard leaching toxicity identification (GB5085.3 to 2007) when used for a pollutant leaching toxicity test.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A red mud-based efficient heavy metal curing agent is characterized in that: the paint comprises the following components in parts by weight: 80-100 parts of red mud, 30-40 parts of steel slag, 20-40 parts of blast furnace slag, 20-30 parts of coal gangue, 30-50 parts of fly ash, 20-45 parts of carbide slag, 20-45 parts of waste gypsum, 5-20 parts of a stabilizer and 0-10 parts of an adsorbent.
2. The red mud-based efficient heavy metal curing agent according to claim 1, which is characterized in that: the red mud is modified red mud subjected to acid treatment or heat treatment;
preferably, the red mud is selected from bayer process red mud, sintering process red mud or mixed red mud;
more preferably, the particle size of the red mud is 45-200 meshes.
3. The red mud-based efficient heavy metal curing agent according to claim 1, which is characterized in that: the grain diameters of the steel slag, the blast furnace slag, the coal gangue, the fly ash and the carbide slag are less than 60 meshes.
4. The red mud-based efficient heavy metal curing agent according to claim 1, which is characterized in that: the stabilizer is a mixture of stabilizer A and stabilizer B, wherein the stabilizer A is selected from NaOH, KOH, Ca (OH)2Or Na2CO3One or more of the above; the stabilizer B is selected from hydroxyl histidine or ammonium humate;
preferably, the molar ratio of the stabilizer A to the stabilizer B is 1-4: 5-8.
5. The red mud-based efficient heavy metal curing agent according to claim 1, which is characterized in that: the waste gypsum is one or more selected from phosphogypsum, fluorgypsum, titanium gypsum or soda gypsum.
6. The red mud-based efficient heavy metal curing agent according to claim 1, which is characterized in that: the adsorbent is selected from one or more of sepiolite, 5A zeolite or attapulgite.
7. The preparation method of the red mud-based high-efficiency heavy metal curing agent as set forth in any one of claims 1 to 6, which is characterized in that: the method comprises the following steps:
mixing steel slag, blast furnace slag, coal gangue, fly ash and a stabilizer to obtain a mixture A;
cooling, crushing and sieving the mixture A at room temperature to obtain a mixture B;
and mixing and stirring the mixture B, the red mud, the waste gypsum and the carbide slag uniformly to obtain the red mud-calcium carbide slag.
8. The preparation method of the red mud-based high-efficiency heavy metal curing agent according to claim 7, which is characterized in that: and crushing the mixture A and then sieving the mixture A by a 60-mesh sieve.
9. The preparation method of the red mud-based high-efficiency heavy metal curing agent according to claim 7, which is characterized in that: the red mud is modified red mud subjected to acid treatment or heat treatment;
preferably, the acid treatment method is as follows: soaking the red mud by using 0.1-0.5 mol/L hydrochloric acid or 0.2-1 mol/L nitric acid;
further preferably, the soaking time is 30 min-60 min;
preferably, the heat treatment method comprises the following steps: calcining the red mud at 500-1000 ℃ for 60-90 min.
10. The application of the red mud-based high-efficiency heavy metal curing agent of any one of claims 1 to 6 in heavy metal curing;
or in the treatment of soil or groundwater contaminated by organic pollutants;
especially for the solidification of heavy metals Cu, Pb or Cr in soil.
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