CN113443843B - Composite gelling agent for arsenic-containing waste residue detoxification and preparation method and application thereof - Google Patents
Composite gelling agent for arsenic-containing waste residue detoxification and preparation method and application thereof Download PDFInfo
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- CN113443843B CN113443843B CN202110640289.3A CN202110640289A CN113443843B CN 113443843 B CN113443843 B CN 113443843B CN 202110640289 A CN202110640289 A CN 202110640289A CN 113443843 B CN113443843 B CN 113443843B
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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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B1/00—Dumping solid 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses a composite gelling agent for detoxifying arsenic-containing waste residues, and a preparation method and application thereof. The composite gelling agent is prepared from leaching slag rich in elements such as silicon, iron, calcium, aluminum, manganese and the like through alkaline hydrothermal, roasting and ball milling processes, can provide alkaline metal ions combined with arsenic, provide groups coordinated and adsorbed with the arsenic, and can generate ferrosilicon aluminate hydrate with high strength and low permeability to provide microcosmic wrapping so as to reduce the mobility of the arsenic and further achieve the aim of gelling and detoxifying the arsenic-containing waste slag. The composite gelling agent disclosed by the invention is wide in raw material preparation, simple in process, low in cost and short in period, has a stable treatment effect and a small volume ratio compared with the traditional cement curing, is easy to industrially apply, and can be safely buried and disposed, and all indexes of arsenic-containing waste residues after treatment can stably meet the limit requirements specified in hazardous waste landfill pollution control standards (GB 18598-2019).
Description
Technical Field
The invention belongs to the field of stabilizing treatment of arsenic-containing waste residues, and particularly relates to a composite gelling agent for detoxifying arsenic-containing waste residues, and a preparation method and application thereof.
Background
Arsenic is widely distributed in nature, mainly exists in the form of sulfide ore, such as orpiment, realgar, arsenopyrite and the like, is mainly used in pesticides, herbicides, insecticides and a plurality of alloys, but arsenide is a substance with strong toxicity, and arsenic poisoning can cause various pathological changes and even canceration. In the production process of non-ferrous smelting industry and chemical industry involving arsenic, arsenic-containing waste residues with different properties can be generated, such as arsenic sulfide residues generated by sulfurization of contaminated acid, calcium arsenic residues and iron arsenic residues generated by a lime-ferric salt method, arsenic-alkali residues generated by refining of crude antimony and the like, if the arsenic is not effectively treated and leached by rainwater in the nature, the arsenic is continuously dissolved out and permeates into peripheral soil and water, and the serious arsenic pollution problem can be caused.
The research on the arsenic-containing waste residue safety disposal technology reports that cement is used as a curing agent, sodium sulfide is used as a stabilizing agent to prepare a cured body, arsenic-containing neutralized slag with the arsenic content of less than 1.5% is treated, the arsenic leaching toxicity of the treated arsenic slag is 3 mg/L-4 mg/L, the limit value of hazardous waste landfill pollution control standard is not reached, and safe landfill disposal cannot be carried out;
CN108188145A discloses a stabilization method of arsenic-containing waste residue, which adopts water-soluble silicate and aluminum salt to carry out double decomposition reaction to wrap the arsenic-containing waste residue, so that the arsenic-containing waste residue is isolated from the external environment, and the stability of the arsenic-containing waste residue is further improved, but the method requires that the pH value of the micro-wrapped arsenic-containing waste residue is strictly controlled at 2-5, so that safe landfill disposal cannot be carried out;
CN106583422A discloses a preparation method of a novel biomass carbon arsenic stabilizer and a process for curing high-salt arsenic slag, the method cures arsenic in the arsenic slag through the cooperation of a self-made novel biomass carbon arsenic stabilizer, but the process is complex, and strict temperature control and electric field addition are required, so that industrial application is difficult to realize;
CN106362347A discloses a method for treating high-concentration arsenic slag, which adopts magnesium oxide, magnesium hydroxide, ferric sulfate and ferric oxide as stabilizers, lime for adjusting pH, cement as a curing agent, and arsenic leaching toxicity after treatment is lower than 2.5 mg/L, but the pH is not less than 13, secondary pollution is easy to cause under strong alkali condition, safe landfill disposal cannot be carried out, and the treatment period is longer.
2013 CN 103449790A discloses a harmless treatment method of waste acid sludge, which provides a cement-like solidified body prepared by mixing a mixture consisting of portland cement, fly ash, slag and river sand with the waste acid sludge, triethanolamine is used as an additive, the mixing amount of the mixture is about 100 percent, and the compatibilization ratio is high;
2014.12 CN 104230242A discloses a method for preparing harmless curing brick of high arsenic sludge, which proposes that organic sulfur macromolecular compound, organic amine macromolecular compound and the like are used as arsenic chelating agent, finished silicate, aluminate and epoxy resin cementing material are used as cementing material, finished sulfate, fluorite mineral, sepiolite mineral and the like are used as curing excitant, and the curing agent is mixed with the high arsenic sludge to prepare a curing body, the compatibilization ratio is more than 1, the curing condition is rigorous and the period is long.
2016.4 CN 105499250A discloses a stabilizing treatment method for arsenic sulfide removal slag, which comprises the steps of mixing cement clinker, slag and copper slag to serve as an autonomous cementing material, using calcium chloride or sodium chloride as an additive, using carbide slag as a pretreatment agent to provide calcium ions to be combined with arsenic to prepare an arsenic sulfide slag solidified body, and obtaining the solidified body with higher strength by adopting autoclave curing, wherein the arsenic leaching toxicity meets GB5085.3-2007, namely the arsenic leaching toxicity is lower than 5 mg/L.
CN 106966620A discloses a coal gangue bottom slag and fly ash compound cementing material and a preparation method thereof, and proposes that a mixed material of coal gangue bottom slag, fly ash, quicklime and gypsum is ground to obtain the compound cementing material, and the cementing property reaches the national PC 32.5 standard.
CN 110746168A discloses a method for solidifying arsenic-containing sludge by steel slag and silica fume cementing material, which comprises the steps of mixing steel slag, silica fume and arsenic-containing sludge, using sodium silicate and sodium hydroxide as alkali activators, performing compression molding, and curing for 28d to obtain solidified blocks, thereby realizing the purpose of treating wastes with wastes, but the material mixing amount is too large, the volume-increasing ratio is greatly increased, and the curing period is too long.
Disclosure of Invention
The invention provides a composite gelling agent for detoxifying arsenic-containing waste residues, a preparation method and application thereof, aiming at arsenic-containing waste residues with low arsenic leaching toxicity, the prepared composite gelling agent is applied to gelling and detoxifying, and the detoxification method has the advantages of simple process, short treatment period, stable effect and small compatibilization ratio. After the arsenic-containing waste residue is subjected to gelling and detoxifying treatment, each index can stably meet the limit requirement specified in hazardous waste landfill pollution control Standard (GB 18598-2019), and safe landfill disposal can be performed.
The invention adopts the following technical scheme to achieve the aim,
the invention relates to a preparation method of a composite gelling agent for detoxification of arsenic-containing waste residues, which comprises the following steps:
adding industrial waste residue into water to obtain slurry, then adding diatomite and sodium hydroxide into the slurry to obtain a mixed solution, carrying out hydrothermal reaction at 150-200 ℃, carrying out solid-liquid separation, roasting the obtained solid phase at 150-200 ℃, carrying out ball milling, and sieving to obtain a composite gelling agent;
in the mixed solution, the molar ratio of silicon: (iron + calcium + aluminum) = 1.5-3.5.
The method takes industrial waste residue rich in silicon, calcium, iron and aluminum as a raw material, and obtains a multi-component mineral system with efficient detoxification and gelling activity through component regulation, hydrothermal alkali excitation, roasting to remove crystallization water and ball milling activation treatment. According to the invention, by adopting reasonable component proportion of silicon iron, calcium aluminum and the like, a multi-component mineral system, namely a composite gelling agent precursor, of silicon, iron and aluminate with high hydrated gelling activity, ferroalumite minerals with strong adsorption characteristic, metal oxides specifically combined with arsenic and the like is generated through hydrothermal alkali excitation treatment, part of crystal water in the minerals is removed through roasting, the specific surface area of the minerals is improved through ball milling, the hydrated gelling activity of the minerals is further improved, and the composite gelling agent is finally prepared. The medicament can generate high-efficiency specific binding with free arsenic in the arsenic-containing waste residue, generate strong physical and coordination adsorption, and form a compact coating structure in a short time so as to reduce the mobility of the arsenic, thereby achieving the aim of detoxifying the arsenic-containing waste residue.
In the invention, the molar ratio in the mixed solution needs to be well controlled, if the molar ratio is unreasonable, the obtained multi-component minerals such as silicon, iron, aluminate, iron aluminite, metal oxide and the like, namely the composite gelling agent precursor, are treated by a hydrothermal process, the adsorption and hydration gelling activities of the multi-component minerals cannot be sufficiently excited, and the gelling and detoxifying effects of the composite gelling agent are influenced.
Meanwhile, in the preparation process of the composite gelling agent, both the reaction temperature of the hydrothermal reaction and the roasting temperature need to be effectively controlled, and if the hydrothermal reaction temperature is too low, the alkali excitation efficiency is affected, the reaction is not thorough, and the hydrothermal reaction temperature is too high, the iron-aluminum-vanadium mineral loses the adsorption activity due to alkali corrosion. When the roasting temperature is too low, mineral crystal water is difficult to remove completely, the hydration activity is inhibited, and when the roasting temperature is too high, the bauxite mineral is easy to generate thermal phase change transformation and lose the adsorption activity.
In addition, the inventor finds that ball milling is required after solid-phase roasting, even if no agglomeration occurs after solid-phase sintering, the ball milling is required, and the ball milling can further activate the roasted product, so that the adsorption effect is improved.
In a preferred scheme, the industrial waste residue comprises the following main components in percentage by mass: 10-30 wt% of silicon, 5-15 wt% of iron, 5-25 wt% of calcium, 5-15 wt% of aluminum and 2-10 wt% of manganese.
In the invention, the industrial waste residue contains iron alumite phase which is leached slag containing elements such as silicon, iron, calcium, aluminum, manganese and the like, including but not limited to manganese slag.
In the preferable scheme, the solid content of the industrial waste residue in the slurry is 20-30 wt%.
In a preferable scheme, the concentration of the sodium hydroxide in the mixed solution is 20-30 wt%.
In a preferred scheme, the time of the hydrothermal reaction is 180-300 min.
In a preferable scheme, the roasting time is 240-360 min.
In a preferred scheme, the ball-milling ball material ratio is 2-10: 1, the ball milling rotating speed is 80-200 rpm, the ball milling time is less than or equal to 15min, and preferably 5-15 min.
In the invention, after roasting is finished, the obtained product needs to be subjected to ball milling and further activated by ball milling, the ball milling time needs to be effectively controlled, and the ball milling time is too long, so that the activity of the obtained product is reduced.
In the preferred scheme, the number of the sieved meshes is 200-300 meshes, and undersize products are taken after sieving.
The invention also provides the composite gelling agent for detoxifying the arsenic-containing waste residue prepared by the preparation method.
The invention also provides the application of the composite gelling agent for detoxifying the arsenic-containing waste residue prepared by the preparation method, and the composite gelling agent is used for coagulating and detoxifying the arsenic-containing waste residue; the treatment process of the gelling detoxification comprises the following steps: grinding, sieving and mixing the arsenic-containing waste residues to obtain slurry, adjusting the pH value to 6-12, adding a composite gelling agent, reacting under stirring, and naturally curing to obtain the gelled detoxification material.
In the preferable scheme, the arsenic content in the arsenic-containing waste residue is 1-25 wt%, and the arsenic leaching toxicity is less than or equal to 100 mg/L.
The arsenic-containing waste residue in the invention includes but is not limited to calcium arsenic residue and iron arsenic residue.
In a preferable scheme, the solid content of the slurry is 20-50 wt%.
In a preferable scheme, the mass ratio of the composite gelling agent to the arsenic-containing waste residue is 0.05-0.30: 1.
in the preferable scheme, the reaction time is 5 min-30 min, and the natural curing time is more than or equal to 18 h.
In the actual operation process, the gelled detoxification material can be pressed or injection molded before natural curing to obtain a cured body, and the compressive strength of the gelled detoxification material obtained after room-temperature curing is 1-10 MPa.
Compared with the prior art, the invention has the following characteristics:
(1) the invention has remarkable effect on arsenic-containing waste residues with arsenic content of 1-25 wt% and arsenic leaching toxicity less than or equal to 100 mg/L.
(2) The composite gelling agent is prepared by component regulation, hydrothermal alkali excitation, roasting to remove crystal water and ball milling, is rich in iron-containing aluminosilicate, iron-aluminoferrite and metal oxide, has greatly improved specific surface area and gelling activity, can be combined with arsenic more efficiently to form physical and coordination adsorption, and forms microscopic tight package in a short time so as to reduce the mobility of arsenic, thereby achieving the aim of detoxification.
(3) The method has the advantages of simple process, low treatment cost, short period, stable effect and small capacity-increasing ratio, various indexes of the arsenic-containing waste residue after treatment can stably reach the limit value requirements specified in hazardous waste landfill pollution control standard, the arsenic-containing waste residue can be directly filled into a flexible landfill site for safe landfill, and simultaneously can be pressed or molded by injection, a solidified block with higher strength can be obtained in a short time, the transportation, temporary storage or landfill are convenient, the industrial application and popularization are easy, and compared with the traditional cement solidification and the traditional slag gelatinization solidification, the method has obvious economic benefit and environmental benefit.
Drawings
FIG. 1 is a flow chart of the arsenic-containing waste residue gelling and detoxifying treatment method of the present invention.
FIG. 2 is an SEM photograph of composite gellant prepared in example 1.
FIG. 3 is an SEM photograph of the gel of example 1 after curing.
FIG. 4 is the XRD pattern of the gelled detoxification materials of example 1 after curing.
Detailed Description
The invention will be described in further detail with reference to the following figures and specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Example 1
Preparing a composite gelling agent:
the industrial waste residue used in the present embodiment is manganese residue generated from a certain electrolytic plant a, and comprises the following components by dry weight: 20.9wt% of silicon, 7.5wt% of iron, 5.6wt% of calcium, 8.3wt% of aluminum and 4.3wt% of manganese.
Adding water into manganese slag to prepare slurry, controlling the solid content of the manganese slag in the slurry to be 25wt%, then adding diatomite and sodium hydroxide into the slurry to obtain mixed solution, wherein the molar ratio of silicon to (iron + calcium + aluminum) in the mixed solution is 2.0, the concentration of the sodium hydroxide in the mixed solution is 24wt%, then carrying out hydrothermal reaction at 180 ℃ for 240min, filtering, roasting the obtained filter material at 180 ℃ for 300min, and carrying out ball milling on the roasted material, wherein the ball material ratio is 5: 1, rotating speed of 120rpm, ball milling time of 10min, then sieving with a 250-mesh sieve, and taking undersize products to obtain the composite gelling agent.
Detoxification treatment of arsenic-containing waste residues:
1. the treated arsenic-containing waste residue is calcium arsenic residue, the arsenic content is 8wt%, the arsenic leaching toxicity is 35mg/L, the pH value is 12.6, and the water content is 52%.
2. Weighing 500g of calcium-arsenic slag, putting the calcium-arsenic slag into a high-efficiency stirring container, adding water, stirring and pulping, adjusting the solid content to be 40wt%, and adjusting the pH value of the pulp to be 11.5 by using concentrated sulfuric acid.
3. Adding 50g of composite gelling agent, stirring and reacting for 10min to obtain a gelling detoxification material, dividing the gelling detoxification material into five parts, respectively maintaining the materials indoors for 1d, 3d, 15d, 60d and 360d, and then performing leaching toxicity and corrosivity analysis, wherein the detection results are shown in table 1.
Table 1 example 1 gel detoxification test results
The result shows that the composite gelling agent obtained in the embodiment 1 can effectively ensure that the leaching toxicity of the gelled detoxification material arsenic is less than or equal to 1mg/L, the corrosivity meets the requirement that the pH value is within the range of 7-12, and the leaching toxicity is not obviously changed along with the prolonging of time, which indicates that the long-term stability of the gelled detoxification material is better.
Example 2
Preparing a composite gelling agent:
the industrial waste residue used in the embodiment is manganese residue generated by a certain electrolysis plant B, and comprises the following components: 22.1wt% of silicon, 9.5wt% of iron, 5.6wt% of calcium, 6.3wt% of aluminum and 3.2wt% of manganese.
Adding water into manganese slag to prepare slurry, controlling the solid content of the manganese slag in the slurry to be 28wt%, then adding diatomite and sodium hydroxide into the slurry to obtain mixed solution, wherein the molar ratio of silicon to (iron + calcium + aluminum) in the mixed solution is 3.2, the concentration of the sodium hydroxide in the mixed solution is 27wt%, then carrying out hydrothermal reaction at 200 ℃ for 300min, filtering, roasting the obtained filter material at 200 ℃ for 360 min, and carrying out ball milling on the roasted material, wherein the ball-material ratio is 10: 1, rotating speed of 200rpm, ball milling time of 15min, then sieving with a 300-mesh sieve, and taking undersize products to obtain the composite gelling agent.
Detoxification treatment of arsenic-containing waste residues:
1. the arsenic-containing waste residue treated by the embodiment is calcium-arsenic residue, the arsenic content is 11wt%, the arsenic leaching toxicity is 98mg/L, the pH value is 12.6, and the water content is 48%.
2. Weighing 500g of calcium-arsenic slag, putting the calcium-arsenic slag into a high-efficiency stirring container, adding water, stirring and pulping, and adjusting the solid content to be 25% and the pH value to be 11.5.
3. Adding 150g of composite gelling agent, stirring and reacting for 10min, after the reaction is finished, performing injection molding in two parts, demolding after 8h, continuously maintaining indoors for 16h and 64h respectively to obtain a solidified block, and performing leaching toxicity, corrosivity and pressure resistance detection analysis on the solidified block, wherein the results are shown in Table 2.
Table 2 example 2 cured block test results
| Item | Curing for 16h | Maintaining for 64h | GB18598-2019 |
| Arsenic leach toxicity (mg/L) | 0.65 | 0.57 | ≤1.2 |
| pH value | 11.82 | 11.72 | 7~12 |
| Compressive strength/MPa | 2.5 | 9.8 |
The result shows that the composite gelling agent can effectively ensure that the gelling detoxification material forms a solidified block with higher strength, and provides a good microcosmic wrapping framework.
Example 3
Preparing a composite gelling agent:
the industrial waste residue used in the present embodiment is manganese residue generated from a certain electrolysis plant C, and comprises the following components by dry weight: 15.8wt% of silicon, 5.5wt% of iron, 6.8wt% of calcium, 5.4wt% of aluminum and 5.5wt% of manganese.
Adding water into manganese slag to prepare slurry, controlling the solid content of the manganese slag in the slurry to be 20wt%, then adding diatomite and sodium hydroxide into the slurry to obtain mixed solution, wherein the molar ratio of silicon to (iron + calcium + aluminum) in the mixed solution is 1.5, the concentration of the sodium hydroxide in the mixed solution is 20wt%, then carrying out hydrothermal reaction at 150 ℃ for 180min, filtering, roasting the obtained filter material at 150 ℃ for 240min, and then carrying out ball milling on the roasted material, wherein the ball material ratio is 2: 1, rotating speed of 80rpm, ball milling for 5min, then sieving with a 200-mesh sieve, and taking undersize products to obtain the composite gelling agent.
Detoxification treatment of arsenic-containing waste residues:
1. the arsenic-containing slag used in the embodiment is iron-arsenic slag, the arsenic content is 21%, the arsenic leaching toxicity is 75mg/L, the pH value is 1.38, and the water content is 44%.
2. Weighing 500g of iron-arsenic slag, putting the iron-arsenic slag into a high-efficiency stirring container, adding water, stirring and pulping, and adjusting the solid content to be 35% and the pH to be 6.5.
3. Adding 75g of composite gelling agent, stirring and reacting for 30min to obtain a gelling detoxification material, dividing the gelling detoxification material into five parts, respectively maintaining the materials indoors for 1d, 3d, 15d, 60d and 360d, and then performing leaching toxicity and corrosivity analysis, wherein the detection results are shown in Table 4.
Table 4 example 3 gel detoxification test results
The result shows that the composite gelling agent prepared under the condition can effectively ensure that the leaching toxicity of the gelled detoxification material arsenic is less than or equal to 1.2mg/L, the corrosivity meets the condition that the pH value is in the range of 7-12, and the leaching toxicity does not change obviously with the time, which indicates that the long-term stability of the gelled detoxification material is better.
In addition, according to the technology, a 10000 ton/year arsenic-containing material treatment production line is built in 2013 by a certain smelting enterprise in Hunan province, an arsenic-containing solid waste disposal project is built in 2012, the toxicity of arsenic leaching in the treated arsenic-containing gelled detoxification material is stable below 1mg/L and is stably lower than the entrance limit value of hazardous waste landfill pollution control standard, and the harmless disposal of the arsenic-containing solid waste is realized.
Comparative example 1
The other conditions are the same as example 1, except that the composite gelling agent is prepared from fly ash as a raw material, and the composite gelling agent comprises the following components in percentage by dry weight: 26.9wt% of silicon, 4.0wt% of iron, 2.6wt% of calcium, 16.6wt% of aluminum and 1.9wt% of magnesium. And curing the gelled detoxication material for 1d for detection and analysis of leaching toxicity and corrosivity, wherein the arsenic leaching toxicity is 2.56mg/L, the pH value of the leaching solution is 11.59, and the arsenic leaching toxicity of the gelled detoxication material exceeds the limit of GB 18598-2019.
Because the fly ash is the ash generated at high temperature, different from leaching slag such as manganese slag, and because of the lack of an iron-aluminum alum phase, the adsorption activity of the prepared composite gelling agent is greatly reduced, and the detoxification effect is influenced.
Comparative example 2
The other conditions were the same as in example 2 except that the hydrothermal reaction temperature was 100 ℃. The results are shown in Table 3.
Table 3 comparative example cured block test results
| Item | Curing for 16h | Maintaining for 64h | GB18598-2019 |
| Arsenic leach toxicity (mg/L) | 1.58 | 1.55 | ≤1.2 |
| pH value | 11.81 | 11.74 | 7~12 |
| Compressive strength/MPa | 0.3 | 1.5 |
Because the hydrothermal temperature is low, the hydrothermal alkali shock method is not thorough, mineral adsorption and gelling activity in the composite gelling agent are influenced, and the detoxification effect and the compressive strength of a solidified block are influenced.
Comparative example 3
The other conditions were the same as in example 3 except that the calcination temperature was 300 ℃. Curing the gelled detoxication material for 1d, and performing detection and analysis on leaching toxicity and corrosivity to obtain arsenic leaching toxicity of 3.12mg/L, wherein the pH value of the leaching solution is 7.95, and the arsenic leaching toxicity of the gelled detoxication material exceeds the limit of GB 18598-2019.
The reason is that the roasting temperature is too high, so that the iron-aluminum alum in the precursor of the composite gelling agent is transformed and loses the adsorption activity, and the detoxification effect is influenced.
Comparative example 4
The other conditions are the same as example 1, except that the calcined material is not ball-milled, but is directly sieved through a 250-mesh sieve, and undersize products are taken to obtain the composite gelling agent. And curing the gelled detoxication material for 1d for detection and analysis of leaching toxicity and corrosivity, wherein the arsenic leaching toxicity is 1.38mg/L, the pH value of the leaching solution is 11.58, and the arsenic leaching toxicity of the gelled detoxication material slightly exceeds the limit of GB 18598-2019.
The composite gelatinizing agent is not ball milled and activated, so that the micro specific surface area is limited, the mineral crystal lattice is relatively complete, the adsorption performance is affected and the detoxifying effect is reduced.
It should be understood that the above-described specific embodiments are merely illustrative of the present invention and are not intended to limit the present invention. Obvious variations or modifications which are within the spirit of the invention are possible within the scope of the invention.
Claims (8)
1. A preparation method of a composite gelling agent for arsenic-containing waste residue detoxification is characterized by comprising the following steps: the method comprises the following steps: adding industrial waste residue into water to obtain slurry, then adding diatomite and sodium hydroxide into the slurry to obtain a mixed solution, carrying out hydrothermal reaction at 150-200 ℃, carrying out solid-liquid separation, roasting the obtained solid phase at 150-200 ℃, then carrying out ball milling, and sieving to obtain a composite gelling agent;
in the mixed solution, the molar ratio of silicon: (iron + calcium + aluminum) = 1.5-3.5;
the industrial waste residue and the iron-containing alumen phase comprise the following main components in percentage by mass: 10-30 wt% of silicon, 5-15 wt% of iron, 5-25 wt% of calcium, 5-15 wt% of aluminum and 2-10 wt% of manganese;
the ball-material ratio of the ball milling is 2-10: 1, the rotation speed of ball milling is 80 rpm-200 rpm, and the ball milling time is less than or equal to 15 min.
2. The preparation method of the composite gelling agent for detoxification of arsenic-containing waste residue as claimed in claim 1, wherein the preparation method comprises the following steps: in the slurry, the solid content of the industrial waste residue is 20-30 wt%.
3. The preparation method of the composite gelling agent for arsenic-containing waste residue detoxification as claimed in claim 1, wherein the preparation method comprises the following steps: in the mixed solution, the concentration of the sodium hydroxide is 20-30 wt%.
4. The preparation method of the composite gelling agent for arsenic-containing waste residue detoxification as claimed in claim 1, wherein the preparation method comprises the following steps: the hydrothermal reaction time is 180-300 min, and the roasting time is 240-360 min.
5. The composite gelling agent for detoxification of arsenic-containing waste residue prepared by the preparation method according to any one of claims 1 to 4.
6. The application of the composite gelling agent for detoxification of arsenic-containing waste residue prepared by the preparation method according to any one of claims 1 to 4 is characterized in that: the composite gelling agent is used for gelling and detoxifying arsenic-containing waste residues; the treatment process of the gelling detoxification comprises the following steps: grinding, sieving and mixing the arsenic-containing waste residues to obtain slurry, adjusting the pH value to 6-12, adding a composite gelling agent, reacting under stirring, and naturally curing to obtain the gelled detoxification material.
7. The application of the composite gelling agent for arsenic-containing waste residue detoxification as claimed in claim 6, wherein the composite gelling agent comprises: the arsenic-containing waste residue contains 1-25 wt% of arsenic and the leaching toxicity of arsenic is less than or equal to 100 mg/L; the solid content in the slurry is 20-50 wt%; the mass ratio of the composite gelling agent to the arsenic-containing waste residue is 0.05-0.30: 1.
8. the application of the composite gelling agent for arsenic-containing waste residue detoxification as claimed in claim 6, wherein the composite gelling agent comprises: the reaction time is 5 min-30 min, and the natural curing time is more than or equal to 18 h.
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