CN111825408A - Sludge curing agent prepared from steel slag modified phosphogypsum and use method thereof - Google Patents
Sludge curing agent prepared from steel slag modified phosphogypsum and use method thereof Download PDFInfo
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- CN111825408A CN111825408A CN202010578120.5A CN202010578120A CN111825408A CN 111825408 A CN111825408 A CN 111825408A CN 202010578120 A CN202010578120 A CN 202010578120A CN 111825408 A CN111825408 A CN 111825408A
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- steel slag
- sludge
- phosphogypsum
- curing agent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
-
- 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
- C04B28/18—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 mixtures of the silica-lime type
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Sludge (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a sludge curing agent prepared by steel slag modified phosphogypsum and a use method thereof, wherein the sludge curing agent comprises the following components: 40-70% of steel slag modified phosphogypsum powder, 30-60% of cementing agent and 1-10% of reinforcing agent; the steel slag modified phosphogypsum powder is prepared by mixing and modifying 5-25% of steel slag and 75-95% of phosphogypsum in percentage by mass. The phosphogypsum is modified by the steel slag, alkaline substances of the steel slag react with impurities containing soluble phosphoric acid, calcium phosphate and fluoride in the phosphogypsum to be converted into indissolvable precipitate substances, and the bonding force among crystals is increased, so that the cementing property of the phosphogypsum is improved, and meanwhile, acidic substances such as sulfuric acid, phosphoric acid and the like in the phosphogypsum are mixed with the steel slag to destroy a vitreous body structure in the steel slag, so that a compact silicate vitreous body structure in the steel slag is dissociated, the hydration activity of the steel slag is improved, and the strength of solidified sludge by the curing agent is.
Description
Technical Field
The invention belongs to the technical field of resource utilization of industrial solid wastes, and particularly relates to a sludge curing agent prepared from steel slag modified phosphogypsum and a using method thereof.
Background
Phosphogypsum is industrial waste residue generated in wet-process production of phosphoric acid, and mainly contains calcium sulfate dihydrate (CaSO)4·2H2O) is the same as natural gypsum and is called phosphogypsum because of the impurities such as phosphoric acid, calcium phosphate and the like. According to the statistics of the society of phosphorus compound fertilizer industry, the yield of phosphogypsum in China in 2018 reaches 7800 million tons, the comprehensive utilization rate is 39.7 percent, the newly increased stockpiling amount is more than 4000 million tons every year, the newly increased occupied area is more than 4000 hectares, the historical stockpiling amount is more than 3 hundred million tons, a large amount of phosphogypsum stockpiling occupies valuable land resources, and meanwhile, serious environmental pollution such as soil, water and the like can be caused. In recent years, the national issues of 'Yangtze river economic zone ecological environment protection planning', 'Yangtze river protection restoration attack and hardness fight action plan', and 'three phosphorus' comprehensive regulation and other policies successively put forward strict requirements on the yield and stockpiling of the phosphogypsum.
The steel slag is industrial waste slag generated in the steel making process of the steel industry, the resource utilization amount of the steel slag is limited due to the problems of low gelling activity, poor wear resistance, poor volume stability and the like, the annual output of the steel slag in China currently reaches 1.2 hundred million tons under the current comprehensive utilization condition of the steel slag, the historical stock quantity exceeds 10 hundred million tons, the comprehensive utilization rate of the steel slag is about 25 percent, along with the implementation of the environmental protection tax law and the solid waste pollution environment prevention and control law, strict requirements are provided for the disposal and utilization of industrial solid waste, and how to further improve the resource utilization amount of the phosphogypsum and the steel slag becomes a problem to be solved urgently in the phosphorus chemical industry and the steel industry.
A large amount of sludge is generated in the construction processes of river and lake dredging and hydraulic engineering, the traditional materials of the sludge curing agent at present are cement and lime, but the strength of the cement and the lime in curing the sludge is low, the cost is high, the novel sludge curing agent is usually a mixed material of slag, fly ash, quicklime and industrial gypsum, but the phosphogypsum is only used as a sulfate activator, the mixing amount ranges from 5% to 15%, and the utilization amount of the phosphogypsum is limited to a certain extent.
Disclosure of Invention
The invention aims to solve the problems of high cost and low curing strength of the existing sludge curing agent.
Therefore, the invention provides a sludge curing agent prepared from steel slag modified phosphogypsum, which comprises the following components: 40-70% of steel slag modified phosphogypsum powder, 30-60% of cementing agent and 1-10% of reinforcing agent; the steel slag modified phosphogypsum powder is prepared by mixing and modifying 5-25% of steel slag and 75-95% of phosphogypsum in percentage by mass.
Furthermore, the specific surface area of the steel slag modified phosphogypsum powder is more than 400m2/kg。
Further, the cementing agent is formed by compounding slag, silica fume and red mud.
Further, the cementing agent comprises the following components in percentage by mass: 50-80% of slag, 5-15% of silica fume and 5-45% of red mud.
Further, the specific surface area of the cementing agent is more than 400m2/kg。
Further, the reinforcing agent is any one or a combination of more of calcium chloride, quicklime, water glass, aluminum chloride, calcium formate, glass fiber, calcium acetate and metakaolin.
In addition, the invention also provides a use method of the sludge curing agent prepared by using the steel slag modified phosphogypsum, which comprises the following steps:
1) crushing, screening, magnetically separating and grinding the steel slag, adding the processed steel slag and phosphogypsum into a stirring system according to the formula dosage, uniformly stirring the mixture, spraying acetic acid aqueous solution in the stirring process, putting the uniformly mixed mixture into a material-enclosing system for enclosing treatment, then drying, stir-frying and aging the mixture, grinding, and adding molasses residues as an additive to prepare steel slag modified phosphogypsum powder;
2) adding the steel slag modified phosphogypsum powder prepared in the step 1) into sludge to be solidified through a conveying system, and mechanically stirring and uniformly mixing the steel slag modified phosphogypsum powder and the sludge;
3) adding the cementing agent and the reinforcing agent into the sludge obtained in the step 2) according to the formula dosage, and fully contacting and mixing the sludge.
Further, the specific surface area of the steel slag after crushing, screening, magnetic separation and grinding in the step 1) is not less than 300m2/kg。
Further, the additive in the step 1) is any one or a combination of molasses residues, calcium acetate, starch residues and sodium carbonate.
Further, a sludge curing agent is doped into the sludge according to 15-30% of the dry weight of the sludge, and the sludge is uniformly stirred.
Compared with the prior art, the invention has the beneficial effects that:
(1) the sludge curing agent prepared by using the steel slag modified phosphogypsum provided by the invention utilizes the steel slag to modify the phosphogypsum firstly, alkaline substances of the steel slag react with impurities containing soluble phosphoric acid, calcium phosphate and fluoride in the phosphogypsum to be converted into insoluble precipitate substances, so that the cohesive force among crystals is increased, the cementing property of the phosphogypsum is improved, and simultaneously acidic substances such as sulfuric acid, phosphoric acid and the like in the phosphogypsum are mixed with the steel slag to destroy a vitreous body structure in the steel slag, so that a compact silicate vitreous body structure in the steel slag is dissociated, the hydration activity of the steel slag is improved, and the strength of the curing agent for.
(2) The sludge curing agent prepared by using the steel slag modified phosphogypsum provided by the invention is prepared from industrial solid waste, the cost is low, the doping amount of the steel slag modified phosphogypsum is high, the resource utilization amount of the phosphogypsum is increased, meanwhile, the phosphogypsum does not need high-temperature calcination treatment, the utilization cost of the phosphogypsum is reduced, and the strength of the sludge cured by the sludge curing agent is greatly improved compared with that of cement.
(3) The sludge curing agent prepared by using the steel slag modified phosphogypsum provided by the invention is mixed with sludge in the process of curing the sludge, so that water and organic matters in the sludge are quickly absorbed, dissolved and crystallized on the surface of sludge particles, and free water in the sludge is reduced; the addition of the cementing agent and the reinforcing agent further stimulates the steel slag modified phosphogypsum powder to participate in hydration hardening reaction, and under the action of the cementing agent and the reinforcing agent, the steel slag and the phosphogypsum are subjected to hydration reaction in the sludge to generate needle-shaped or thin rod-shaped hydraulic minerals such as calcium sulphoaluminate, calcium chloroaluminate, calcium chloroferrite, calcium sulphoferrite and the like to fill pores in the sludge, so that the compactness of the solidified sludge is increased; the cementing agent generates a reticular calcium silicate hydrate gel under the action of the reinforcing agent, and increases the adhesive force among needle-shaped or fine-rod-shaped hydraulic mineral, gypsum crystal and sludge particles, thereby improving the mechanical strength of the sludge solidification body.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a sludge curing agent prepared from steel slag modified phosphogypsum, which comprises the following components: 40-70% of steel slag modified phosphogypsum powder, 30-60% of cementing agent and 1-10% of reinforcing agent; the steel slag modified phosphogypsum powder is prepared by mixing and modifying 5-25% of steel slag and 75-95% of phosphogypsum in percentage by mass.
The preparation process of the steel slag modified phosphogypsum powder comprises the following steps: crushing, screening, magnetic separation and grinding the steel slag, wherein the specific surface area of the steel slag after grinding is not less than 300m2Adding the treated steel slag and the phosphogypsum into a stirring system according to the formula dosage, uniformly stirring the mixture, and stirring the mixtureSpraying acetic acid aqueous solution for spraying in the process, putting the uniformly mixed mixture into a material sealing system for material sealing treatment for 24-96 h, stir-frying the mixture for 1-5 h at 120-200 ℃ by a frying pan, aging for more than 24h, adding 0.02-3% of additive (one or more of molasses slag, calcium acetate, starch slag and sodium carbonate) for grinding to obtain steel slag modified phosphogypsum powder, wherein the specific surface area of the steel slag modified phosphogypsum powder is more than 400m2/kg。
The cementing agent is formed by compounding slag, silica fume and red mud, and comprises the following components in percentage by mass: 50-80% of slag, 5-15% of silica fume and 5-45% of red mud; the specific surface area of the cementing agent is more than 400m2/kg。
The reinforcing agent is any one or a combination of calcium chloride, quicklime, water glass, aluminum chloride, calcium formate, glass fiber, calcium acetate and metakaolin.
The concrete process of curing the sludge by using the sludge curing agent prepared by the steel slag modified phosphogypsum comprises the following steps: firstly, adding the prepared steel slag modified phosphogypsum powder into sludge to be solidified through a conveying system, and mechanically stirring and uniformly mixing the steel slag modified phosphogypsum powder and the sludge; then, adding the cementing agent and the reinforcing agent into the sludge treated by the steel slag modified phosphogypsum powder according to the formula dosage, and fully contacting and mixing the sludge. Wherein the sludge curing agent is doped into the sludge according to 15-30% of the dry weight of the sludge.
The effect of the sludge curing agent prepared by using the steel slag modified phosphogypsum of the invention on curing sludge is explained by the following specific examples.
Example 1:
the sludge curing agent prepared by using the steel slag modified phosphogypsum provided by the embodiment comprises the following raw materials in percentage by mass: 65% of steel slag modified phosphogypsum powder, 35% of cementing agent (27% of slag, 4% of silica fume and 4% of red mud) and 3% of reinforcing agent; wherein the mass ratio of the phosphogypsum to the steel slag in the steel slag modified phosphogypsum powder is 4: 1.
The sludge curing agent prepared by the formula of the embodiment and the existing P.O 32.5 cement are respectively added into the river sludge under the same conditions and are uniformly mixed, wherein the adding amount of the sludge curing agent is 20% of the dry weight of the river sludge, and the sludge curing agent of the embodiment is mixed with the river sludge by adopting the method for curing the sludge by using the sludge curing agent prepared by the steel slag modified phosphogypsum. The treated river sludge is put into a cement paste mixer to be uniformly stirred and loaded into a test mould, and then the test mould is put into a cement standard curing box to be cured for a corresponding age to test the strength of the cured sludge test piece, and the test results are shown in table 1.
Table 1:
as can be seen from Table 1, when the sludge curing agent prepared in the example is compared with P.O 32.5 cement cured sludge under the same conditions, the compressive strength of the sludge cured test blocks 7d and 28d is higher than that of the P.O 32.5 cement cured sludge, and is respectively improved by 21.10% and 57.14%.
Example 2:
the sludge curing agent prepared by using the steel slag modified phosphogypsum provided by the embodiment comprises the following raw materials in percentage by mass: 40% of steel slag modified phosphogypsum powder, 65% of cementing agent (50% of slag, 6% of silica fume, 9% of red mud) and 6% of reinforcing agent; wherein the mass ratio of the phosphogypsum to the steel slag in the steel slag modified phosphogypsum powder is 3: 1.
The sludge curing agent prepared by the formula of the embodiment and the existing P.O 32.5 cement are respectively added into the river sludge under the same conditions and are uniformly mixed, wherein the adding amount of the sludge curing agent is 25% of the dry weight of the river sludge, and the sludge curing agent of the embodiment is mixed with the river sludge by adopting the method for curing the sludge by using the sludge curing agent prepared by the steel slag modified phosphogypsum. The treated river sludge is put into a cement paste mixer to be uniformly stirred and loaded into a test mould, and then the test mould is put into a cement standard curing box to be cured for a corresponding age to test the strength of the cured sludge test piece, and the test results are shown in table 2.
Table 2:
as can be seen from Table 2, when the sludge curing agent prepared in the example is compared with P.O 32.5 cement cured sludge under the same conditions, the compressive strength of the sludge cured test blocks 7d and 28d is higher than that of the P.O 32.5 cement cured sludge, and is respectively improved by 24.34 percent and 70.10 percent.
Example 3:
the sludge curing agent prepared by using the steel slag modified phosphogypsum provided by the embodiment comprises the following raw materials in percentage by mass: 70% of steel slag modified phosphogypsum powder, 35% of cementing agent (20% of slag, 4% of silica fume and 11% of red mud) and 10% of reinforcing agent. Wherein the mass ratio of the phosphogypsum to the steel slag in the steel slag modified phosphogypsum powder is 3: 1.
The sludge curing agent prepared in the embodiment is added into sludge to be cured according to the corresponding sequence in the method for preparing the sludge curing agent curing sludge by using the steel slag modified phosphogypsum, simultaneously, the steel slag and the phosphogypsum are respectively dried, ground, directly and uniformly mixed with a cementing agent and a reinforcing agent to be used as a control group sample and directly doped into the sludge, the doping amount of the sludge curing agent in the embodiment and the control group is 30% of the dry weight of the sludge in the river channel, the sludge curing agent is uniformly stirred by a cement paste stirrer and is loaded into a test mould, and the test result is shown in table 3 after being placed into a cement standard curing box for curing for a corresponding age to test the strength.
Table 3:
as can be seen from Table 3, the compressive strengths of the solidified sludge blocks 7d and 28d measured by the solidified sludge method using the sludge curing agent of the embodiment are higher than the compressive strengths of the solidified sludge prepared by directly mixing the steel slag, the phosphogypsum, the cementing agent and the reinforcing agent in the control group, and are respectively increased by 13.81% and 19.18%.
The above examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims and any design similar or equivalent to the scope of the invention.
Claims (10)
1. The sludge curing agent prepared from the steel slag modified phosphogypsum is characterized by comprising the following components: 40-70% of steel slag modified phosphogypsum powder, 30-60% of cementing agent and 1-10% of reinforcing agent; the steel slag modified phosphogypsum powder is prepared by mixing and modifying 5-25% of steel slag and 75-95% of phosphogypsum in percentage by mass.
2. The sludge curing agent prepared from steel slag modified phosphogypsum as claimed in claim 1, wherein the specific surface area of the steel slag modified phosphogypsum powder is more than 400m2/kg。
3. The sludge curing agent prepared by using the steel slag modified phosphogypsum as claimed in claim 1, wherein the cementing agent is formed by compounding slag, silica fume and red mud.
4. The sludge curing agent prepared by using the steel slag modified phosphogypsum as claimed in claim 3, wherein the cementing agent comprises the following components in percentage by mass: 50-80% of slag, 5-15% of silica fume and 5-45% of red mud.
5. The sludge curing agent prepared by using the steel slag modified phosphogypsum as claimed in claim 3, wherein the specific surface area of the cementing agent is more than 400m2/kg。
6. The sludge curing agent prepared by using the steel slag modified phosphogypsum as claimed in claim 1, wherein the reinforcing agent is any one or more of calcium chloride, quicklime, water glass, aluminum chloride, calcium formate, glass fiber, calcium acetate and metakaolin.
7. The use method of the sludge curing agent prepared from the steel slag modified phosphogypsum as claimed in any one of claims 1 to 6, is characterized by comprising the following steps:
1) crushing, screening, magnetically separating and grinding the steel slag, adding the processed steel slag and phosphogypsum into a stirring system according to the formula dosage, uniformly stirring the mixture, spraying acetic acid aqueous solution in the stirring process, putting the uniformly mixed mixture into a material-enclosing system for enclosing treatment, then drying, stir-frying and aging the mixture, grinding the mixture, and adding an additive to prepare steel slag modified phosphogypsum powder;
2) adding the steel slag modified phosphogypsum powder prepared in the step 1) into sludge to be solidified through a conveying system, and mechanically stirring and uniformly mixing the steel slag modified phosphogypsum powder and the sludge;
3) adding the cementing agent and the reinforcing agent into the sludge obtained in the step 2) according to the formula dosage, and fully contacting and mixing the sludge.
8. The use method of the sludge curing agent prepared by using the steel slag modified phosphogypsum as claimed in claim 7, wherein the specific surface area of the steel slag after crushing, screening, magnetic separation and grinding in the step 1) is not less than 300m2/kg。
9. The use method of the sludge curing agent prepared by using the steel slag modified phosphogypsum as claimed in claim 7, wherein the additive in the step 1) is any one or more of molasses slag, calcium acetate, starch slag and sodium carbonate.
10. The use method of the sludge curing agent prepared from the steel slag modified phosphogypsum, according to claim 7, is characterized in that the sludge curing agent is mixed into the sludge according to 15-30% of the dry weight of the sludge, and is uniformly stirred.
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| CN113135729A (en) * | 2021-04-25 | 2021-07-20 | 上海市建筑科学研究院有限公司 | Construction powder and slurry for high-sulfur mixing pile and preparation and application of construction powder and slurry |
| CN113563038A (en) * | 2021-07-14 | 2021-10-29 | 北京荣露材料科技有限公司 | Method for producing wood-wool board by using phosphogypsum |
| CN115259729A (en) * | 2022-08-19 | 2022-11-01 | 湖北昌耀新材料工程技术研究有限责任公司 | Excessive-sulfur phosphogypsum-slag cementing material modifier, application thereof and excessive-sulfur phosphogypsum-slag cementing material composition |
| CN115304331A (en) * | 2022-08-26 | 2022-11-08 | 武汉轻工大学 | Environment-friendly composite industrial waste solidified sludge and preparation method thereof |
| CN116553850A (en) * | 2023-04-25 | 2023-08-08 | 昆明理工大学 | Phosphogypsum stable curing method |
| CN117986001A (en) * | 2024-04-07 | 2024-05-07 | 大连长锦科技有限公司 | Curing agent based on multiple solid wastes and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135729A (en) * | 2021-04-25 | 2021-07-20 | 上海市建筑科学研究院有限公司 | Construction powder and slurry for high-sulfur mixing pile and preparation and application of construction powder and slurry |
| CN113563038A (en) * | 2021-07-14 | 2021-10-29 | 北京荣露材料科技有限公司 | Method for producing wood-wool board by using phosphogypsum |
| CN115259729A (en) * | 2022-08-19 | 2022-11-01 | 湖北昌耀新材料工程技术研究有限责任公司 | Excessive-sulfur phosphogypsum-slag cementing material modifier, application thereof and excessive-sulfur phosphogypsum-slag cementing material composition |
| CN115259729B (en) * | 2022-08-19 | 2023-11-07 | 湖北昌耀新材料工程技术研究有限责任公司 | Sulfurized phosphogypsum-slag cementing material modifier, application thereof and composition of same |
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| CN116553850A (en) * | 2023-04-25 | 2023-08-08 | 昆明理工大学 | Phosphogypsum stable curing method |
| CN117986001A (en) * | 2024-04-07 | 2024-05-07 | 大连长锦科技有限公司 | Curing agent based on multiple solid wastes and preparation method and application thereof |
| CN117986001B (en) * | 2024-04-07 | 2024-05-31 | 大连长锦科技有限公司 | Curing agent based on multiple solid wastes and preparation method and application thereof |
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