CN113233860A - Arsenic filter cake curing treatment process - Google Patents
Arsenic filter cake curing treatment process Download PDFInfo
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- CN113233860A CN113233860A CN202110633756.XA CN202110633756A CN113233860A CN 113233860 A CN113233860 A CN 113233860A CN 202110633756 A CN202110633756 A CN 202110633756A CN 113233860 A CN113233860 A CN 113233860A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0463—Hazardous waste
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/12—Acids or salts thereof containing halogen in the anion
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/149—Iron-sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/003—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00775—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes the composition being used as waste barriers or the like, e.g. compositions used for waste disposal purposes only, but not containing the waste itself
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides an arsenic filter cake curing treatment process, and belongs to the technical field of solid waste treatment. The process comprises the following steps: s1, crushing the arsenic filter cake, sieving the crushed arsenic filter cake with a 100-mesh sieve, adding ferrous salt and an additive, and uniformly stirring to obtain a mixed material; wherein the mass ratio of the arsenic filter cake to the ferrous salt is 1:0.1-0.2, and the mass ratio of the arsenic filter cake to the additive is 1: 0.1-0.2; the additive is a mixture of aminomethyl phosphoric acid and citric acid; s2, adding cement and gypsum into the mixture obtained in the step S1, adding a proper amount of water, uniformly stirring, and curing and shaping to obtain an arsenic filter cake solidified body; wherein the mass ratio of the cement to the arsenic filter cake is 0.8-0.9: 1; the mass ratio of the gypsum to the arsenic filter cake is 0.2-0.3: 1. The invention has the advantages of simple treatment process, convenient operation, less material consumption and low cost. The obtained arsenic filter cake solidified body has higher stability, lower compatibilization ratio and low arsenic leaching content, and is suitable for landfill.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to an arsenic filter cake curing treatment process.
Background
At present, the harmless treatment of arsenic-containing solid waste is mainly a stabilizing/curing technology. The common stabilizing technology is to convert the less stable arsenic-containing solid waste into a substance with more stable physical and chemical properties by adding chemical agents, thereby reducing the dissolution and migration of harmful arsenic. However, this method has not been able to completely stabilize arsenic. Solidification technology refers to the process of converting hazardous waste into an immobile solid or forming a compact solid using a solidified material. The physical form of the product after the solidification treatment can be kept without a container, the product is convenient to transport and store, and the surface area of waste contacting the environment is reduced, so that the possibility of leakage of toxic and harmful components is reduced. The cement solidification has been widely used because of the advantages of easy material availability, good treatment effect and low cost. However, cement setting also has some disadvantages, such as: volume-expansion is a major problem to be solved by cement curing technology. In addition, since cement setting is only a physical encapsulation process, there is a problem that the toxic leaching rate of arsenic from the set body is high. However, the existing domestic cement curing technology has great defects, on one hand, the addition amount of cement is large, and the compatibilization is large; on the other hand, the solidified body after the cement is solidified can be safely stockpiled only by coating treatment.
The patent CN110394354A reports a method for fixing arsenic by transforming and combining arsenic sulfide slag in copper smelting, which adopts a method of adding a calcium-containing material, a stabilizer and a curing agent to perform combined action to stably solidify the arsenic-containing material (the material can be kept stable within the pH range of 5-12), thereby realizing the purpose of fixing arsenic. However, this method has a drawback that the amount of cement added is large.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the defects in the prior art, and to provide an arsenic filter cake solidification treatment process.
The invention provides an arsenic filter cake curing treatment process, which comprises the following steps:
s1, crushing the arsenic filter cake, sieving the crushed arsenic filter cake with a 100-mesh sieve, adding ferrous salt and an additive, and uniformly stirring to obtain a mixed material; wherein the mass ratio of the arsenic filter cake to the ferrous salt is 1:0.1-0.2, and the mass ratio of the arsenic filter cake to the additive is 1: 0.1-0.2; the additive is a mixture of aminomethyl phosphoric acid and citric acid;
s2, adding cement and gypsum into the mixture obtained in the step S1, adding a proper amount of water, uniformly stirring, and curing and shaping to obtain an arsenic filter cake solidified body; wherein the mass ratio of the cement to the arsenic filter cake is 0.8-0.9: 1; the mass ratio of the gypsum to the arsenic filter cake is 0.2-0.3: 1.
Preferably, the arsenic content in the arsenic filter cake is 10-40 wt%.
Preferably, the ferrous salt comprises any one or more of ferrous sulfate and ferrous chloride.
Preferably, the molar ratio of the aminomethylphosphoric acid to the citric acid in the additive is 1: 0.8-1.2. More preferably 1:1.
Preferably, the cement comprises one or more of portland cement, portland slag cement, portland pozzolanic cement, aluminous cement, and zeolite cement. More preferably ordinary portland cement.
The technical scheme of the invention has the following advantages:
according to the invention, the ferrous salt and the additive are firstly adopted to treat the arsenic filter cake, and then the cement and the gypsum are used as the curing agent, so that the obtained arsenic filter cake cured body has higher stability, lower compatibilization ratio and less cement consumption. The product after the curing treatment is detected by a toxicity leaching experiment (TCLP), and the result shows that the toxicity leaching concentration of harmful elements such as arsenic in the leaching solution is far lower than the limit value specified in 'hazardous waste identification standard leaching toxicity identification GB 5085.3-2007', and the product can be stockpiled and buried. The method has the advantages of simple treatment process, convenient operation, small material consumption, low cost and wide application prospect.
Detailed Description
Example 1
An arsenic filter cake solidification treatment process comprises the following steps:
s1, crushing the arsenic filter cake, sieving the crushed arsenic filter cake with a 100-mesh sieve, adding ferrous salt and an additive, and uniformly stirring to obtain a mixed material; wherein the mass ratio of the arsenic filter cake to the ferrous salt is 1:0.15, and the mass ratio of the arsenic filter cake to the additive is 1: 0.15; the additive is a mixture of aminomethyl phosphoric acid and citric acid;
s2, adding cement and gypsum into the mixture obtained in the step S1, adding a proper amount of water, uniformly stirring, and curing and shaping to obtain an arsenic filter cake solidified body; wherein the mass of the cement and arsenic filter cake is 0.85: 1; the mass ratio of the gypsum to the arsenic filter cake is 0.25: 1.
Wherein the arsenic content in the arsenic filter cake is 10-40 wt%.
Wherein, the ferrous salt comprises any one or more of ferrous sulfate and ferrous chloride.
Wherein the molar ratio of the aminomethyl phosphoric acid to the citric acid in the additive is 1:1.
Wherein the cement comprises ordinary portland cement.
Example 2
An arsenic filter cake solidification treatment process comprises the following steps:
s1, crushing the arsenic filter cake, sieving the crushed arsenic filter cake with a 100-mesh sieve, adding ferrous salt and an additive, and uniformly stirring to obtain a mixed material; wherein the mass ratio of the arsenic filter cake to the ferrous salt is 1:0.1, and the mass ratio of the arsenic filter cake to the additive is 1: 0.2; the additive is a mixture of aminomethyl phosphoric acid and citric acid;
s2, adding cement and gypsum into the mixture obtained in the step S1, adding a proper amount of water, uniformly stirring, and curing and shaping to obtain an arsenic filter cake solidified body; wherein the mass of the cement and arsenic filter cake is 0.9: 1; the mass ratio of the gypsum to the arsenic filter cake is 0.2: 1.
Wherein the arsenic content in the arsenic filter cake is 10-40 wt%.
Wherein, the ferrous salt comprises any one or more of ferrous sulfate and ferrous chloride.
Wherein the molar ratio of the aminomethyl phosphoric acid to the citric acid in the additive is 1: 0.8.
Wherein the cement comprises one or more of portland cement, portland slag cement, pozzolanic portland cement, alumina cement, and zeolite cement.
Example 3
An arsenic filter cake solidification treatment process comprises the following steps:
s1, crushing the arsenic filter cake, sieving the crushed arsenic filter cake with a 100-mesh sieve, adding ferrous salt and an additive, and uniformly stirring to obtain a mixed material; wherein the mass ratio of the arsenic filter cake to the ferrous salt is 1:0.2, and the mass ratio of the arsenic filter cake to the additive is 1: 0.1; the additive is a mixture of aminomethyl phosphoric acid and citric acid;
s2, adding cement and gypsum into the mixture obtained in the step S1, adding a proper amount of water, uniformly stirring, and curing and shaping to obtain an arsenic filter cake solidified body; wherein the mass of the cement and arsenic filter cake is 0.8: 1; the mass ratio of the gypsum to the arsenic filter cake is 0.3: 1.
Wherein the arsenic content in the arsenic filter cake is 10-40 wt%.
Wherein, the ferrous salt comprises any one or more of ferrous sulfate and ferrous chloride.
Wherein the molar ratio of the aminomethyl phosphoric acid to the citric acid in the additive is 1: 1.2.
Wherein the cement comprises one or more of portland cement, portland slag cement, pozzolanic portland cement, alumina cement, and zeolite cement.
Comparative example 1
Wherein the molar ratio of the aminomethyl phosphoric acid to the citric acid in the additive is 1: 0.5. The rest is the same as example 1.
Comparative example 2
Wherein the additive is methylamino phosphoric acid. The rest is the same as example 1.
Comparative example 3
Wherein the additive is citric acid. The rest is the same as example 1.
Comparative example 4
Wherein the mol ratio of the aminomethyl phosphoric acid to the citric acid in the additive is 1: 1.5. The rest is the same as example 1.
Comparative example 5
Wherein no additives are used. The rest is the same as example 1.
The arsenic filter cake solidified materials obtained in examples and comparative examples were subjected to toxicity leaching according to the "toxicity leaching method for solid waste leaching-sulfuric acid-nitric acid method" (HJ/T299-2007), and the results are shown in Table 1.
TABLE 1
| Arsenic leaching amount (mg/L) | |
| Example 1 | 1.81 |
| Example 2 | 2.36 |
| Example 3 | 2.41 |
| Comparative example 1 | 5.5 |
| Comparative example 2 | 5.7 |
| Comparative example 3 | 5.6 |
| Comparative example 4 | 6.9 |
As can be seen from Table 1, the leaching contents of As in examples 1 to 3 are all lower than 5mg/L, and the results meet the requirements of GB5085.3-2007 (solid waste identification standard-leaching toxicity identification), and the safe stockpiling or landfill can be carried out. The leaching content of As in the comparative examples is more than 5mg/L, which is not in accordance with the specification. Indicating that the additive has synergistic effect of aminomethyl phosphoric acid and citric acid.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. The arsenic filter cake curing treatment process is characterized by comprising the following steps of:
s1, crushing the arsenic filter cake, sieving the crushed arsenic filter cake with a 100-mesh sieve, adding ferrous salt and an additive, and uniformly stirring to obtain a mixed material; wherein the mass ratio of the arsenic filter cake to the ferrous salt is 1:0.1-0.2, and the mass ratio of the arsenic filter cake to the additive is 1: 0.1-0.2; the additive is a mixture of aminomethyl phosphoric acid and citric acid;
s2, adding cement and gypsum into the mixture obtained in the step S1, adding a proper amount of water, uniformly stirring, and curing and shaping to obtain an arsenic filter cake solidified body; wherein the mass ratio of the cement to the arsenic filter cake is 0.8-0.9: 1; the mass ratio of the gypsum to the arsenic filter cake is 0.2-0.3: 1.
2. The arsenic filter cake curing process according to claim 1, wherein the arsenic content in the arsenic filter cake is 10-40 wt%.
3. The arsenic filter cake curing process of claim 1, wherein the ferrous salt comprises any one or more of ferrous sulfate and ferrous chloride.
4. The arsenic filter cake solidification treatment process of claim 1, wherein the molar ratio of the aminomethylphosphoric acid to the citric acid in the additive is 1: 0.8-1.2.
5. The arsenic filter cake curing process of claim 1, wherein the cement comprises one or more of portland cement, portland slag cement, portland pozzolanic cement, aluminous cement, and zeolite cement.
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Citations (8)
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|---|---|---|---|---|
| EP0352096A2 (en) * | 1988-07-19 | 1990-01-24 | Safe-Waste Systems, Inc. | Compositions to encapsulate chromium, arsenic, and other toxic metals in wastes |
| CN1809752A (en) * | 2003-03-31 | 2006-07-26 | 科学与工业研究委员会 | Method for preparing photoreactive polymers with immobilized biomolecules thereon |
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| WO2015104466A1 (en) * | 2014-01-10 | 2015-07-16 | Greenmade Development Limited | Hydraulic cements based on cement or on cement clinker or on lime, on calcium sulphate, and on a pozzolanic component; process for the manufacture thereof and uses thereof |
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-
2021
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