CN112125625A - Preparation method of carbon dioxide-cured anhydrous phosphogypsum-based product - Google Patents
Preparation method of carbon dioxide-cured anhydrous phosphogypsum-based product Download PDFInfo
- Publication number
- CN112125625A CN112125625A CN202010965044.3A CN202010965044A CN112125625A CN 112125625 A CN112125625 A CN 112125625A CN 202010965044 A CN202010965044 A CN 202010965044A CN 112125625 A CN112125625 A CN 112125625A
- Authority
- CN
- China
- Prior art keywords
- phosphogypsum
- carbon dioxide
- parts
- anhydrous
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C04B28/142—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 containing synthetic or waste calcium sulfate cements
- C04B28/143—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 containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0231—Carbon dioxide hardening
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The specification discloses a preparation method of an anhydrous phosphogypsum-based product cured by carbon dioxide, which comprises the steps of firstly, mixing and uniformly stirring anhydrous phosphogypsum, an exciting reagent, cement clinker, an active admixture and gypsum whisker according to a proportion to obtain a mixture; then slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, and stirring until the mixture is uniformly dispersed to obtain flowing slurry; and finally, quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product. The anhydrous phosphogypsum-based product prepared by the method has the advantages of good mechanical property, large surface hardness, good water resistance and water resistance coefficient of more than 0.8. The method not only effectively utilizes industrial wastes, has lower cost and realizes high added value utilization of the wastes, but also utilizes the waste greenhouse effect gas-carbon dioxide to reduce the emission of greenhouse gases, can protect the environment and inhibit the occurrence of greenhouse effect.
Description
Technical Field
The invention belongs to the technical field of building materials, relates to a gypsum modification technology, and particularly relates to a preparation method of an anhydrous phosphogypsum-based product cured by carbon dioxide.
Background
Phosphogypsum is an industrial byproduct of wet-process production of phosphoric acid in the phosphorization industry, and the main component of the phosphogypsum is dihydrate gypsum (Ca)2S04·2H20) Generally, dihydrate gypsum in the phosphogypsum accounts for 85-95%, and the phosphogypsum contains a small amount of impurities such as phosphorus, fluorine, organic matters and the like, and the content of the impurities is related to the components of phosphate ores used for production. The side yield of the phosphogypsum in China per year currently exceeds 8000 million tons, only about 20 percent of the phosphogypsum is utilized, a large amount of phosphogypsum is stockpiled as solid waste, the accumulated stockpiled phosphogypsum exceeds 2 hundred million tons, a large amount of land is occupied, and environmental pollution is caused. Accelerating the resource utilization of the phosphogypsum, and becoming a problem which needs to be solved urgently for the sustainable development of the phosphating industry.
The gypsum product has gaps and pore channels, is a porous structure, and the interior of the gypsum product is equivalent to a porous network, so that the internal surface area of the gypsum product is large, and the structure is related to the interaction force between gypsum crystals and the properties and the quantity of contact points between crystal particles, because of the large internal surface area, when the gypsum meets water, water flows into the gypsum along capillary pore channels to dissolve part of the gypsum, so that the strength is reduced, and the easy water absorption is mainly caused by three reasons that (1) because of construction requirements, the added water quantity is larger than the theoretical water quantity, the excessive water of the gypsum is evaporated after the gypsum is hardened, and a plurality of micropore gaps are formed in the gypsum, the pore channels are mutually communicated, and when the gypsum meets water, the water can permeate into the gypsum through the pore channels, the gypsum has poor water resistance, and the internal structure of the gypsum is damaged, so that the mechanical property of the gypsum is influenced; (2) a large number of hydrophilic groups exist on the surface of the gypsum, so that the surface of the gypsum is easy to absorb water; (3) the solubility of the gypsum is relatively high, the gypsum is dissolved when meeting water, and the contact points of crystals inside the gypsum are also dissolved, so that the strength of the gypsum is reduced.
The gypsum material has the advantages of strong air permeability, fire resistance, easily available raw materials, strong plasticity, low manufacturing cost and the like, and also has the defects of strong water absorption and easy moisture deformation, thereby greatly limiting the application field of the gypsum material.
Related patents for water-resistant modification of gypsum that have been published in recent years:
CN 201710933538.1A preparation method of a water-resistant gypsum block discloses a preparation method of a water-resistant gypsum block. Stirring gypsum powder and molten paraffin, freezing, crushing and sieving to obtain coated gypsum powder; pouring the coated gypsum powder and the calcium oxide powder into a mortar, grinding and sieving to obtain modified gypsum powder; stirring and mixing the modified gypsum powder, water and the modified carbonized rice hull powder to obtain mixed slurry; spraying a release agent on the mold, injecting the mixed slurry into the mold, standing, demolding, and maintaining at constant temperature and humidity to obtain a blank; and (3) placing the blank in a vacuum freeze drying box, and drying to obtain the water-resistant gypsum block. The method has more steps and complicated manufacture, and the interaction of the molten paraffin and the gypsum has great dependence, so that the further popularization is limited.
CN 201610184209.7A waterproof self-cleaning type heat preservation building gypsum powder and its preparation method discloses a waterproof self-cleaning type heat preservation building gypsum powder, adding nanometer aluminum powder into raw materials, mixing with water, generating hydrogen gas when meeting water, releasing to form porous structure, baking phosphogypsum, pulverizing, blowing to boiling state, and spraying vaporous hydrochloric acid solution. In the method, hydrogen is released due to the reaction, so that the building structure has certain uncontrollable property.
In order to further popularize the use of the phosphogypsum, the invention provides a novel phosphogypsum modification method, which utilizes the industrial waste phosphogypsum as a base material and modifies the base material in a carbon dioxide curing way to enhance the water resistance of the base material; in addition, the invention uses a large amount of industrial solid waste phosphogypsum, fully exerts the potential value of the phosphogypsum, fully utilizes the waste greenhouse gas-carbon dioxide, reduces the emission of greenhouse gas, can protect the environment and inhibit the occurrence of greenhouse effect.
Disclosure of Invention
The invention aims to solve the problems of the phosphogypsum and the common problems of gypsum, namely poor water resistance, insufficient crack resistance and the like, and provides a preparation method of a carbon dioxide cured anhydrous phosphogypsum-based product. In addition, carbon dioxide gas can be effectively fixed in the production process, and the environmental problem caused by carbon dioxide is solved.
In order to solve the above problems, the technical scheme adopted by the invention is as follows:
the preparation method of the carbon dioxide cured anhydrous phosphogypsum-based product is characterized by comprising the following raw material components in parts by weight:
70-100 parts of anhydrous phosphogypsum, 5-20 parts of exciting reagent, 2-14 parts of cement clinker, 5-15 parts of active admixture, 2-6 parts of gypsum whisker, 0.1-0.95 part of water reducing agent and 0.25-0.65 part of water by weight of the anhydrous phosphogypsum;
the preparation method comprises the following steps:
step 1, mixing and uniformly stirring anhydrous phosphogypsum, an exciting reagent, cement clinker, an active admixture and gypsum whisker in raw material components according to a proportion to obtain a mixture;
step 2, slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, and stirring until the mixture is uniformly dispersed to obtain flowing slurry;
and 3, quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product.
Preferably, the raw material components are as follows by weight:
75-95 parts of anhydrous phosphogypsum, 8-18 parts of exciting reagent, 4-10 parts of cement clinker, 8-14 parts of active admixture, 3-5 parts of gypsum whisker, 0.12-0.8 part of water reducing agent and 0.3-0.6 part of water by weight of the anhydrous phosphogypsum.
Preferably, the carbon dioxide curing conditions in the step 3 are that the temperature is 15-50 ℃, the humidity is 30-80%, and the concentration of carbon dioxide is 10-100%.
Preferably, the carbon dioxide curing conditions in the step 3 are that the temperature is 20-45 ℃, the humidity is 40-70%, the carbon dioxide concentration is 20-80%, and the specified curing age is 1-29 days.
Preferably, the anhydrous phosphogypsum is prepared by calcining dihydrate phosphogypsum at 500-700 ℃ for 15-90 minutes, wherein the mass fraction of calcium sulfate is more than 85%, the mass fraction of water-soluble phosphorus pentoxide is less than 0.7%, the mass fraction of water-soluble fluorine is less than 0.5%, the content of organic matters is less than 0.9%, and the residue of a 0.2mm square-hole sieve is less than 9%.
Preferably, the exciting reagent is a powdery material formed by mixing one or more of lime, caustic sludge and white mud, and the specific surface area of the powdery material is more than 360m2/kg。
Preferably, the pH value of the aqueous solution of the exciting reagent (quicklime, caustic sludge and white mud dissolved in water) is more than 13.
Preferably, the active admixture is a powdery material formed by mixing one or more of fly ash, slag powder, silica fume and gangue powder, and the specific surface area of the powdery material is more than 330m2/kg。
Preferably, the gypsum whisker is dihydrate phosphogypsum whisker, and the length of the dihydrate phosphogypsum whisker is 50-400 um; the length-diameter ratio is 3-12; whiteness is more than or equal to 98 percent, CaSO4The mass percentage content is more than or equal to 98 percent.
Preferably, the water reducing agent is any one or more of lignosulfonate, beta-methyl naphthalene sulfonate polycondensate, melamine formaldehyde polycondensate and polycarboxylate water reducing agent.
A carbon dioxide cured anhydrous phosphogypsum-based product, which is characterized by being prepared by any preparation method.
The reaction principle of the invention is as follows:
in order to solve the problems in the technical background, the invention takes the anhydrous phosphogypsum as a cementing material, and adds the excitant and the cement clinker to promote the dissolution of anhydrite, improve the crystallization supersaturation degree of dihydrate gypsum and accelerate the nucleation and growth rate of dihydrate gypsum crystals; and a sulfate-rich liquid phase is formed, so that the formation of dihydrate gypsum crystal structural elements is facilitated, the nucleation center of dihydrate gypsum crystals is increased, the growth habit of dihydrate gypsum crystals is changed, the hydrogen bond effect of solvent water is weakened, the dissolving capacity of the dihydrate gypsum crystals is improved, and the activity of the anhydrous phosphogypsum is stimulated. The invention utilizes the carbon dioxide curing technology, can further shorten the hardening time of the anhydrous phosphogypsum and better excite the anhydrous phosphogypsum by the cement clinker. Theoretically, the carbonization hardening is mainly by CO2Dissolving in water to form 2H+,CO3 2-And HCO3 -Ions, then with Ca in the material2+Or Mg2+Flocculent precipitate is generated, and the particles are mutually adsorbed to increase the strength of the cementing material. In the present invention, Ca is contained in the cement clinker and the active admixture2+With H +, CO3 2-And HCO3 -Ions can interact with a more compact structure, so that the surface hardness is higher, the strength is improved, and the water resistance is improved. Meanwhile, the added active admixture can separate out si ions and Al ions in the hydration process, and plays an important role in improving the waterproof performance of the gypsum. The added gypsum crystal whisker further improves the crack resistance of the gypsum. Thereby solving various problems caused by the introduction of the anhydrous phosphogypsum. All the components of the exciting and reinforcing materials are the same as those of the cementing materials, the compatibility is good, the carbon dioxide curing plays an important role, and the water resistance and the mechanical propertyCan be greatly improved, and has obvious effect.
The invention has the beneficial effects that:
the invention solves the defects of poor water resistance and low crack resistance of gypsum, improves the performance of the anhydrous phosphogypsum, solves the problems of land occupation, environmental pollution and resource waste caused by solid waste stacking, realizes the best use of the materials and has higher economic benefit and environmental benefit.
2 the material prepared by the invention has adjustable performance, stable structure and simple operation.
3 the anhydrous phosphogypsum cementing material prepared by the invention solves the problem of water resistance, the softening coefficient reaches more than 0.8, and the problem of limiting the application of the anhydrous phosphogypsum is solved.
4, the invention can effectively fix carbon dioxide gas in the production process and solve the environmental problem caused by carbon dioxide.
Detailed Description
The following examples further describe embodiments of the present invention in detail. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The invention provides a preparation method of an anhydrous phosphogypsum-based product cured by carbon dioxide, which adopts the following raw material components by weight:
70-100 parts of anhydrous phosphogypsum, 5-20 parts of exciting reagent, 2-14 parts of cement clinker, 5-15 parts of active admixture, 2-6 parts of gypsum whisker, 0.1-0.95 part of water reducing agent and 0.25-0.65 part of water by weight of the anhydrous phosphogypsum;
the preparation method comprises the following steps:
step 1, mixing and uniformly stirring anhydrous phosphogypsum, an exciting reagent, cement clinker, an active admixture and gypsum whisker in raw material components according to a proportion to obtain a mixture;
step 2, slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, and stirring until the mixture is uniformly dispersed to obtain flowing slurry;
and 3, quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product.
The raw materials of the embodiment of the invention are as follows:
preferably, the raw material components are as follows by weight:
75-95 parts of anhydrous phosphogypsum, 8-18 parts of exciting reagent, 4-10 parts of cement clinker, 8-14 parts of active admixture, 3-5 parts of gypsum whisker, 0.12-0.8 part of water reducing agent and 0.3-0.6 part of water by weight of the anhydrous phosphogypsum.
The anhydrous phosphogypsum is prepared by calcining the dihydrate phosphogypsum at the temperature of 500-700 ℃ for 15-90 minutes, wherein the mass fraction of calcium sulfate is more than 85%, the mass fraction of water-soluble phosphorus pentoxide is less than 0.7%, the mass fraction of water-soluble fluorine is less than 0.5%, the content of organic matters is less than 0.9%, and the residue on a 0.2mm square-hole sieve is less than 9%.
The exciting reagent is a powdery material (dissolved in water and having a pH value of more than 13) formed by mixing one or more of lime, caustic sludge and white mud, and the specific surface area of the powdery material is more than 360m2/kg。
The active admixture is selected from one or more of pulverized fuel ash, slag powder, silica fume and gangue powder, and the specific surface area of the powdery material is more than 330m2/kg。
The gypsum whisker is dihydrate phosphogypsum whisker, and the length of the dihydrate phosphogypsum whisker is 50-400 mu m; the length-diameter ratio is 3-12; whiteness is more than or equal to 98 percent, CaSO4The mass percentage content is more than or equal to 98 percent.
The water reducing agent is one or more of lignosulfonate, beta-methylnaphthalene sulfonate polycondensate, melamine formaldehyde polycondensate and polycarboxylate water reducing agent.
The carbon dioxide curing conditions in the step 3 are that the temperature is 15-50 ℃, the humidity is 30-80%, the concentration of carbon dioxide is 10-100%, and the carbon dioxide curing conditions can be further preferably that the temperature is 20-45 ℃, the humidity is 40-70%, and the concentration of carbon dioxide is 20-80%. The curing period is generally 1-29 days, preferably 28 days.
Example 1
The preparation method of the carbon dioxide cured anhydrous phosphogypsum-based product comprises the following components in parts by weight:
75 parts of anhydrous phosphogypsum, 8 parts of quick lime, 4 parts of cement clinker, 8 parts of active admixture fly ash, 3 parts of gypsum whisker and 0.2 part of water reducer lignosulfonate. And the amount of water is 0.6 of the weight of the anhydrous phosphogypsum.
The preparation method comprises the following steps:
the method comprises the following steps: mixing the mixture for the anhydrous phosphogypsum-based product according to a certain proportion, uniformly stirring, slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, stirring until the mixture is uniformly dispersed to obtain flowing slurry
Step two: and (3) quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product. The curing conditions were 20 ℃ temperature, 40% humidity, 20% carbon dioxide concentration, and a specified age of 28 days.
Example 2
The preparation method of the carbon dioxide cured anhydrous phosphogypsum-based product comprises the following components in parts by weight:
95 parts of anhydrous phosphogypsum, 18 parts of alkaline residue, 10 parts of cement clinker, 14 parts of active admixture slag powder, 5 parts of gypsum whisker and 0.8 part of water reducer beta-methylnaphthalene sulfonate polycondensate. And the amount of water is 0.3 of the weight of the anhydrous phosphogypsum.
The preparation method comprises the following steps:
the method comprises the following steps: mixing the mixture for the anhydrous phosphogypsum-based product according to a certain proportion, uniformly stirring, slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, stirring until the mixture is uniformly dispersed to obtain flowing slurry
Step two: and (3) quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product. The curing conditions were 45 ℃ temperature, 70% humidity, 80% carbon dioxide concentration, and the specified age was 28 days.
Example 3
The preparation method of the carbon dioxide cured anhydrous phosphogypsum-based product comprises the following components in parts by weight:
85 parts of anhydrous phosphogypsum, 13 parts of white mud, 7 parts of cement clinker, 11 parts of active admixture silica fume, 4 parts of gypsum whisker and 0.5 part of water reducer melamine formaldehyde polycondensate. And the amount of water is 0.45 of the weight of the anhydrous phosphogypsum.
The preparation method comprises the following steps:
the method comprises the following steps: mixing the mixture for the anhydrous phosphogypsum-based product according to a certain proportion, uniformly stirring, slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, stirring until the mixture is uniformly dispersed to obtain flowing slurry
Step two: and (3) quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product. The curing conditions were 37.5 ℃ of temperature, 55% of humidity, 50% of carbon dioxide concentration, and a specified age of 28 days.
Example 4
The preparation method of the carbon dioxide cured anhydrous phosphogypsum-based product comprises the following components in parts by weight:
80 parts of anhydrous phosphogypsum, 10 parts of quick lime, 6 parts of cement clinker, 10 parts of active admixture coal gangue powder, 4 parts of gypsum whisker and 0.5 part of water reducer polycarboxylate. And the amount of water is 0.45 of the weight of the anhydrous phosphogypsum.
The preparation method comprises the following steps:
the method comprises the following steps: mixing the mixture for the anhydrous phosphogypsum-based product according to a certain proportion, uniformly stirring, slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, stirring until the mixture is uniformly dispersed to obtain flowing slurry
Step two: and (3) quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product. The curing conditions were 30 ℃ temperature, 55% humidity, 60% carbon dioxide concentration, and the specified age was 28 days.
Example 5
The preparation method of the carbon dioxide cured anhydrous phosphogypsum-based product comprises the following components in parts by weight:
95 parts of anhydrous phosphogypsum, 15 parts of alkaline residue, 8 parts of cement clinker, 12 parts of active admixture fly ash, 5 parts of gypsum whisker and 0.8 part of water reducer lignosulfonate. And the amount of water is 0.4 of the weight of the anhydrous phosphogypsum.
The preparation method comprises the following steps:
the method comprises the following steps: mixing the mixture for the anhydrous phosphogypsum-based product according to a certain proportion, uniformly stirring, slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, stirring until the mixture is uniformly dispersed to obtain flowing slurry
Step two: and (3) quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product. The curing conditions are 35 ℃ of concentration, 60% of humidity and 70% of carbon dioxide concentration, and the specified age is 28 days.
Comparative example 1
The maintenance conditions were changed to normal indoor maintenance, and the others were not changed, compared to example 4.
Comparative example 2
Relative to example 4, no gypsum whiskers were added, the others were unchanged.
In all the above examples, the performance of the carbon dioxide cured anhydrous phosphogypsum-based product in example 4 is optimal, the final setting time is 65Min, the compressive strength of 3 days reaches 12.5MPa, the flexural strength of 3 days reaches 6.2MPa, the softening coefficient reaches 0.85, the water absorption rate of 2h is 10.1%, and the water absorption rate of 24h is 14.2%. However, the maintenance conditions were changed to normal indoor maintenance, and the others were not changed, relative to example 4. The performance is better in example 4. In comparative example 2, no gypsum whisker was added to example 4, and the rest was not changed. Therefore, the performance is better in comparative example 2.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. The preparation method of the carbon dioxide cured anhydrous phosphogypsum-based product is characterized by comprising the following raw material components in parts by weight:
70-100 parts of anhydrous phosphogypsum, 5-20 parts of exciting reagent, 2-14 parts of cement clinker, 5-15 parts of active admixture, 2-6 parts of gypsum whisker, 0.1-0.95 part of water reducing agent and 0.25-0.65 part of water by weight of the anhydrous phosphogypsum;
the preparation method comprises the following steps:
step 1, mixing and uniformly stirring anhydrous phosphogypsum, an exciting reagent, cement clinker, an active admixture and gypsum whisker in raw material components according to a proportion to obtain a mixture;
step 2, slowly adding water into the obtained mixture, simultaneously adding a water reducing agent, and stirring until the mixture is uniformly dispersed to obtain flowing slurry;
and 3, quickly injecting the obtained slurry into a mold, putting the mold into a carbon dioxide curing box for curing, curing to a specified age, and removing the mold to obtain the carbon dioxide cured anhydrous phosphogypsum-based product.
2. A process for the preparation of anhydrous phosphogypsum-based products according to claim 1, characterized in that: the raw material components are as follows by weight:
75-95 parts of anhydrous phosphogypsum, 8-18 parts of exciting reagent, 4-10 parts of cement clinker, 8-14 parts of active admixture, 3-5 parts of gypsum whisker, 0.12-0.8 part of water reducing agent and 0.3-0.6 part of water by weight of the anhydrous phosphogypsum.
3. A process for the preparation of anhydrous phosphogypsum-based products according to claim 1, characterized in that: the carbon dioxide curing conditions in the step 3 are that the temperature is 15-50 ℃, the humidity is 30-80%, and the concentration of the carbon dioxide is 10-100%.
4. A process for the preparation of anhydrous phosphogypsum-based products according to claim 3, characterized in that: the carbon dioxide curing conditions in the step 3 are that the temperature is 20-45 ℃, the humidity is 40-70%, the carbon dioxide concentration is 20-80%, and the specified curing age is 1-29 days.
5. A process for the preparation of anhydrous phosphogypsum-based products according to claim 1, characterized in that: the anhydrous phosphogypsum is prepared by calcining dihydrate phosphogypsum at 500-700 ℃ for 15-90 minutes, wherein the mass fraction of calcium sulfate is more than 85%, the mass fraction of water-soluble phosphorus pentoxide is less than 0.7%, the mass fraction of water-soluble fluorine is less than 0.5%, the content of organic matters is less than 0.9%, and the residue of a 0.2mm square-hole sieve is less than 9%.
6. A process for the preparation of anhydrous phosphogypsum-based products according to claim 1, characterized in that: the exciting reagent is a powdery material formed by mixing one or more of lime, caustic sludge and white mud, and the specific surface area of the powdery material is more than 360m2/kg。
7. The process for the preparation of anhydrous phosphogypsum-based products according to claim 6, characterized in that: the pH value of the aqueous solution of the exciting reagent is more than 13.
8. A process for the preparation of anhydrous phosphogypsum-based products according to claim 1, characterized in that: the active admixture is a powdery material formed by mixing one or more of fly ash, slag powder, silica fume and gangue powder, and the specific surface area of the powdery material is more than 330m2/kg。
9. Process for the preparation of anhydrous phosphogypsum-based products according to claim 1, which is carried out in the presence of a catalystIs characterized in that: the gypsum whisker is dihydrate phosphogypsum whisker, and the length of the dihydrate phosphogypsum whisker is 50-400 mu m; the length-diameter ratio is 3-12; whiteness is more than or equal to 98 percent, CaSO4The mass percentage content is more than or equal to 98 percent.
10. A process for the preparation of anhydrous phosphogypsum-based products according to claim 1, characterized in that: the water reducing agent is any one or more of lignosulfonate, beta-methyl naphthalene sulfonate polycondensate, melamine formaldehyde polycondensate and polycarboxylate water reducing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010965044.3A CN112125625B (en) | 2020-09-15 | 2020-09-15 | Preparation method of carbon dioxide-cured anhydrous phosphogypsum-based product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010965044.3A CN112125625B (en) | 2020-09-15 | 2020-09-15 | Preparation method of carbon dioxide-cured anhydrous phosphogypsum-based product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112125625A true CN112125625A (en) | 2020-12-25 |
| CN112125625B CN112125625B (en) | 2022-06-07 |
Family
ID=73846941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010965044.3A Active CN112125625B (en) | 2020-09-15 | 2020-09-15 | Preparation method of carbon dioxide-cured anhydrous phosphogypsum-based product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112125625B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113264747A (en) * | 2021-05-26 | 2021-08-17 | 天应(深圳)生态建材科技有限公司 | 3D printing phosphogypsum concrete product and maintenance method thereof |
| CN115385716A (en) * | 2022-08-04 | 2022-11-25 | 西南科技大学 | Baking-free lightweight aggregate and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628349A (en) * | 2015-02-06 | 2015-05-20 | 武汉理工大学 | Phosphogypsum based high flow state grouting material |
| CN109053112A (en) * | 2018-10-10 | 2018-12-21 | 河南理工大学 | A kind of building material and its method using desulfurized gypsum and quick lime preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0903142A2 (en) * | 2009-08-05 | 2011-04-19 | Vsevolod Mymrine | the methods of using phosphate plaster to manufacture building materials |
-
2020
- 2020-09-15 CN CN202010965044.3A patent/CN112125625B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628349A (en) * | 2015-02-06 | 2015-05-20 | 武汉理工大学 | Phosphogypsum based high flow state grouting material |
| CN109053112A (en) * | 2018-10-10 | 2018-12-21 | 河南理工大学 | A kind of building material and its method using desulfurized gypsum and quick lime preparation |
Non-Patent Citations (1)
| Title |
|---|
| 彭佳慧等: "磷石膏基无水石膏胶结材研究", 《混凝土与水泥制品》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113264747A (en) * | 2021-05-26 | 2021-08-17 | 天应(深圳)生态建材科技有限公司 | 3D printing phosphogypsum concrete product and maintenance method thereof |
| CN113264747B (en) * | 2021-05-26 | 2023-05-12 | 天应(深圳)生态建材科技有限公司 | 3D printing phosphogypsum concrete product and maintenance method thereof |
| CN115385716A (en) * | 2022-08-04 | 2022-11-25 | 西南科技大学 | Baking-free lightweight aggregate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112125625B (en) | 2022-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111978061B (en) | Preparation method of high-water-resistance anhydrous phosphogypsum cementing material | |
| CN111792902B (en) | High-strength water-resistant phosphogypsum composite cementing material and preparation method thereof | |
| CN112125625B (en) | Preparation method of carbon dioxide-cured anhydrous phosphogypsum-based product | |
| CN101492276A (en) | Novel clay soil polyporous materials and method of producing the same | |
| CN113336516A (en) | Cementing material prepared from multi-element solid wastes and cooperative regulation and control method thereof | |
| CN111825408A (en) | Sludge curing agent prepared from steel slag modified phosphogypsum and use method thereof | |
| CN115093150A (en) | Modifier for improving setting and hardening performance and carbonization resistance of phosphogypsum-based cementing material | |
| CN115028416B (en) | Low-shrinkage concrete using industrial waste residues and preparation method thereof | |
| CN108249811B (en) | Concrete anti-cracking expanding agent and preparation method thereof | |
| CN109809722B (en) | Calcium-magnesium sulfate double-salt cementing material and preparation method and application thereof | |
| CN109553355A (en) | A kind of C40P12 subway concrete and preparation method thereof | |
| CN104861406A (en) | Graft modification method for fly ash | |
| CN111847956A (en) | Phosphogypsum-based cement retarder and preparation method and application thereof | |
| CN114149187B (en) | Preparation method of modified phosphogypsum-based reinforced and toughened cementing material | |
| CN110550927A (en) | Industrial waste gypsum mortar prepared by industrial tail gas synergy and toxicity solving method | |
| CN114920473A (en) | Multi-element low-carbon less-clinker composite cement and preparation method thereof | |
| CN113735545A (en) | Concrete product containing phosphogypsum fly ash cement and preparation method thereof | |
| CN112645674A (en) | Preparation method of phosphogypsum-based high-fluidity water-resistant mortar | |
| CN112159130A (en) | Geopolymer cementing material for temporary spray anchor support engineering and preparation method thereof | |
| CN112897908A (en) | Retarding high-strength ordinary portland cement and its preparing process and application | |
| CN109553358A (en) | A kind of C45P8 subway concrete and preparation method thereof | |
| CN109503084A (en) | A kind of C45P6 subway concrete and preparation method thereof | |
| CN109608132A (en) | A kind of C45P10 subway concrete and preparation method thereof | |
| CN109456009A (en) | A kind of C60P10 subway concrete and preparation method thereof | |
| CN115057635B (en) | High-strength cement clinker and production process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |