CN111792902B - High-strength water-resistant phosphogypsum composite cementing material and preparation method thereof - Google Patents
High-strength water-resistant phosphogypsum composite cementing material and preparation method thereof Download PDFInfo
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- CN111792902B CN111792902B CN202010530908.9A CN202010530908A CN111792902B CN 111792902 B CN111792902 B CN 111792902B CN 202010530908 A CN202010530908 A CN 202010530908A CN 111792902 B CN111792902 B CN 111792902B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- 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
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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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
- 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 invention relates to a high-strength water-resistant phosphogypsum composite cementing material and a preparation method thereof, belongs to the field of building materials, and provides the high-strength water-resistant phosphogypsum composite cementing material and the preparation method thereof, wherein the high-strength water-resistant phosphogypsum composite cementing material comprises the following components in parts by weight: 100 parts of phosphorus building gypsum powder, 0.5-4 parts of rheological agent, 3-7 parts of cement, 4-10 parts of solid sulfur ash, 3-10 parts of gasified slag, 0.5-3 parts of zeolite powder, 1-4 parts of waterproof agent and 0.2-3 parts of calcium oxide. The rheological property, the mechanical property and the water resistance of the beta-type phosphogypsum slurry are obviously improved through the synergistic effect of the rheological technology and the waterproof modification technology; the industrial solid wastes such as solid sulfur ash, coal gasification slag and the like are used in the phosphogypsum product to improve the water resistance and the mechanical property of the phosphogypsum product. The invention can prepare the green, environment-friendly, low-cost and high-strength water-resistant phosphogypsum composite cementing material: the softening coefficient is 0.9-1.2, the saturated water absorption is less than 5%, the compression/bending strength is 25-45/5-13 MPa, and the ardealite composite material can be used in the damp-prone areas such as kitchens and bathrooms, and the application field of industrial byproduct ardealite products is widened.
Description
Technical Field
The invention relates to a high-strength water-resistant phosphogypsum composite cementing material and a preparation method thereof, belonging to the technical field of building materials.
Background
The industrial by-product phosphogypsum is a by-product produced by preparing phosphate fertilizer by a wet method, and the main component of the by-product is calcium sulfate dihydrate. As the domestic phosphorus fertilizer and phosphorus chemical products have huge demands, a large amount of industrial by-product phosphogypsum is inevitably produced in the production process. At present, the stockpiling amount of the phosphogypsum in China exceeds 5 hundred million tons, the yield is increased by 7000 million tons every year, the environment is polluted greatly, and the development of the phosphogypsum-based material accords with the national development strategy of green building materials and the policy of cyclic utilization of solid waste resources. The gypsum has the advantages of light weight, fire resistance, sound insulation, heat preservation and the like, and the recycling of industrial byproduct gypsum resources conforms to the general direction of national environmental protection and circular economy industrial policies, so that the building gypsum prepared from the industrial byproduct gypsum is widely promoted by the building industry.
The common phosphogypsum products on the market, particularly the products produced by adopting beta-type building phosphogypsum powder, have the problems of poor water resistance and low strength. The beta-type phosphogypsum crystal has a rough surface, contains a certain amount of phosphorus and fluorine impurities, has a plurality of cracks and has the compressive strength of only 4-7 MPa; the softening coefficient is low, and is usually 0.3-0.5; the saturated water absorption rate is high and reaches 25-40%, compared with alpha gypsum, the high-strength water-resistant gypsum product has the characteristics of large water demand, low strength and poor water resistance, and is more difficult to prepare, so that the application of the beta phosphogypsum is greatly limited.
Besides industrial by-product phosphogypsum, the problems of large stockpiling amount, environmental pollution, difficult absorption and the like of industrial solid wastes such as solid sulfur ash, gasified slag, coal gangue and the like exist, the performance of the composite rubber material can be improved by taking the phosphogypsum as a main base material and cooperating with other bulk solid waste solid sulfur ash, gasified slag and the like to prepare the composite rubber material, the absorption speed of the bulk solid wastes is accelerated, and the environment-friendly and economic benefits are outstanding. In conclusion, the technology of the invention has important significance for improving the performance of the industrial byproduct phosphogypsum and popularizing and applying the phosphogypsum.
Disclosure of Invention
The invention mainly solves the defects in the prior art, provides the high-strength water-resistant phosphogypsum composite cementing material and the preparation method thereof, effectively improves the water resistance of the beta-type phosphogypsum while improving the strength of the beta-type phosphogypsum, and can prepare the phosphorus building gypsum product with moisture resistance, water resistance and high strength on the whole.
The technical scheme adopted by the invention for solving the technical problems is as follows: a high-strength water-resistant phosphogypsum composite cementing material comprises the following components in parts by weight: 100 parts of phosphorus building gypsum powder, 0.5-4 parts of rheological agent, 3-7 parts of cement, 4-10 parts of solid sulfur ash, 3-10 parts of gasified slag, 0.5-3 parts of zeolite powder, 1-4 parts of waterproof agent and 0.2-3 parts of calcium oxide. The rheological agent comprises 8-10 parts of polycarboxylic water reducer, 1-3 parts of melamine water reducer, 1-4 parts of protein retarder and 0.1-0.5 part of borax; the waterproof agent comprises 0.2-2 parts of organic silicon polymer, 0.5-4 parts of silicone-acrylic emulsion and 0.01-0.24 part of sodium dodecyl sulfate. The high-strength water-resistant beta-type phosphogypsum can be prepared by compounding the raw materials. The invention obviously improves the rheological property, the mechanical property and the water resistance of the beta-type phosphogypsum slurry through the synergistic action of the rheological technology and the waterproof modification technology, and has strong construction operability; the industrial solid wastes such as the solid sulfur ash, the gasified slag and the like are used in the phosphogypsum product, the activities of the solid sulfur ash, the gasified slag and the like in the composite powder are excited, and the water resistance and the mechanical property of the gypsum product are improved. The softening coefficient of the prepared ardealite composite cementing material can reach 0.9-1.2, the saturated water absorption rate is less than 5%, and the compression/rupture strength is 25-45/5-13 MPa.
The further technical scheme is that the rheological agent comprises 8-10 parts of polycarboxylic acid water reducing agent, 1-3 parts of melamine water reducing agent, 1-4 parts of protein retarder and 0.1-0.5 part of borax; the polycarboxylic acid water reducing agent is solution type, the solid content is more than or equal to 20 percent, and the water reducing rate is more than 20 percent; the melamine water reducing agent is in a powder form, the water reducing rate is more than 20 percent, and the water content is less than or equal to 4 percent; the borax is chemical analysis pure grade sodium tetraborate decahydrate, and the purity is more than 99%.
The rheological agent can adjust the component dosage according to the required workability and the setting time, has obvious water reducing and slow setting effects, and can ensure that the phosphorous building gypsum achieves the self-leveling effect. The compound rheological agent can adjust the water-to-gel ratio of the phosphogypsum to be 0.25-0.5, prepare the phosphogypsum with low water-to-gel ratio and high strength, improve the pore size distribution and the macroporous defect of a gypsum hardened body, increase the compactness of a matrix and obviously improve the mechanical property of the matrix. The retarder and the water reducing agent are used in a composite mode, the synergistic effect is achieved, and the retarding and water reducing effects are effectively improved.
The action mechanism of the rheological agent is as follows: the retarder can achieve the purpose of retarding through modes of reducing the solubility of the hemihydrate gypsum, adsorbing on the surface of the growing dihydrate gypsum crystal, forming a complex with calcium ions and the like, particularly, the protein retarder has obvious retarding effect on beta-type gypsum, and can dissolve Ca out of the hemihydrate gypsum through self carboxyl or amino2+Reaction is carried out to lead Ca in the solution to be2+The concentration is reduced, the generation of dihydrate gypsum is delayed, and the strength is improvedUnder the condition of extremely small influence, the obvious retardation effect is achieved, and the setting time can be prolonged to 48 hours. The polycarboxylic acid water reducing agent and the melamine water reducing agent are compounded to have high water reducing effect, the water reducing agent is adsorbed on the surfaces of gypsum particles to promote the mutual dispersion of the gypsum particles, a flocculation structure is disintegrated, and the wrapped water is released, so that the flowability of gypsum is effectively increased, the polarity of hydrophilic groups in the water reducing agent is very strong, the water film can be adsorbed on the gypsum particles to form on the surfaces of the gypsum particles, a good lubricating effect is achieved, the sliding resistance among particles is reduced, and the flowability of the gypsum is further improved.
The rheological agent further comprises 0-0.08 part of air entraining agent, and the air entraining agent is anionic air entraining agent and comprises alpha-sodium alkenyl sulfonate. The action mechanism of the air entraining agent is as follows: the anionic air entraining agent molecules enable the surface liquid film of the air bubbles in water to carry the same negative charges, electrostatic repulsion is generated among the air bubbles, the thickness and the mechanical strength of the hydrated film of the alpha-sodium alkenyl sulfonate are large, the stability of the air bubbles is improved, and the co-rheological agent forms a good synergistic effect in the phosphogypsum slurry. A large amount of uniformly distributed, stable and closed micro-bubbles are introduced into the phosphogypsum slurry, so that the fluidity of the gypsum slurry during pouring or extrusion is improved; compensating the beta-type phosphogypsum and fine grain parts with poor aggregate gradation in the slurry, and improving the frost resistance at low temperature; the surface smoothness of the formed ardealite slurry is improved, and the defects of pitted surfaces, pits and the like are reduced.
The further technical scheme is that the waterproof agent comprises 0.2-2 parts of organic silicon polymer, 0.5-4 parts of silicone-acrylate emulsion and 0.01-0.24 part of sodium dodecyl sulfate; the organic silicon polymer is a self-made organic silicon waterproof agent; the solid content of the silicone-acrylate emulsion is more than or equal to 50 percent, and the viscosity is more than or equal to 2000mPa & s; the sodium dodecyl sulfate is of chemical analysis pure grade, and the purity is more than 99%.
Sodium lauryl sulfate is a surfactant. The surfactant is an interface dispersant which has two opposite properties of lipophilicity and hydrophilcity in a molecule. The organic silicon polymer and the silicone-acrylate emulsion have poor compatibility, and the hydrophobic organic silicon polymer and the silicone-acrylate emulsion are mixed more uniformly by adding the sodium dodecyl sulfate to prepare a mixed solution with good compatibility, and meanwhile, the uniform dispersion of the waterproof agent in the gypsum is facilitated, and the action effect of the waterproof agent is improved.
The organic silicon polymer can form a continuous hydrophobic film on the surface of the gypsum crystal, changes the surface energy of the gypsum, changes the contact angle of the gypsum and water, makes water molecules agglomerated together to form liquid drops, blocks the infiltration of water, and achieves the aims of moisture prevention and water resistance of the whole body without influencing the structure of the gypsum crystal. The silicone-acrylate emulsion can also be formed into a film or filled in the pores of gypsum crystals, and is used in combination with the organic silicon polymer to play a synergistic effect, so that the water-resistant effect of the gypsum is remarkably improved.
The preparation method of the waterproof agent comprises the following steps:
(1) adding 0.1-0.8 part of acetic acid and 0.2-2 parts of vinyl trimethoxy silane into 100-140 parts of deionized water at the same time, and stirring for 15-30 minutes at 20-25 ℃ to enable the two to react sufficiently to obtain a silane solution A;
(2) dissolving 0.2-4 parts of ethyl acrylate in deionized water, and stirring to a clear state to obtain a solution B, wherein the weight ratio of ethyl acrylate: deionized water 1: (250-340);
(3) adding the prepared silane solution A, the prepared silane solution B, 0.1-1 part of polyoxyethylene, 0.5-2 parts of dodecafluoroheptyl ester and 0.2-2 parts of potassium persulfate into a reaction kettle together for emulsion polymerization, heating to 70 ℃ while stirring, and stirring at constant temperature for 1.5-2.0 hours;
(4) cooling the system obtained in the step (3) to 50-55 ℃, stirring at a constant temperature for 1.0-1.5 hours, and aging for 24 hours at normal temperature without layering and flocculation phenomena to obtain an organic silicon polymer;
(5) and uniformly stirring a mixed solution of 0.2-2 parts of organic silicon polymer, 0.5-4 parts of silicone-acrylic emulsion and 0.01-0.24 part of sodium dodecyl sulfate at 20-25 ℃ and at the rotating speed of 4000-6000 rpm to obtain a mixed solution with good adaptability, and aging the mixed solution at normal temperature for 24 hours without layering and agglomeration to obtain the composite waterproof agent.
The further technical proposal is that the phosphorus building gypsum powder is beta-type building phosphogypsum powder, and the semi-hydrated phosphorus building gypsum powderThe content of gypsum is more than or equal to 86 percent, the content of anhydrous gypsum is less than or equal to 5 percent, the content of dihydrate gypsum is less than or equal to 4 percent, and the specific surface area is more than 350m2A density of 2.4 to 2.8kg/m3. The beta-type gypsum crystal has rough surface and a plurality of cracks, and has the defects of large water consumption and low strength compared with the alpha-type gypsum, so that the beta-type gypsum is more difficult to prepare a high-strength gypsum product. The beta gypsum is mainly characterized by being acidic, the pH value is 3-6, and the main component is beta calcium sulfate hemihydrate; the hardening is fast, and the initial setting/final setting is 3-5/7-9 minutes; the strength is low, and the compressive strength is 4-7 MPa under the water consumption of the standard consistency; the softening coefficient is low, and is usually 0.3-0.5; the saturated water absorption rate is high and reaches 25-40%.
The further technical proposal is that the specific surface area of the solid sulfur ash is more than or equal to 400cm2The water demand is 105 percent and the activity is more than or equal to 80 percent.
The further technical proposal is that the water requirement of the gasified slag is 95 percent, the activity is more than or equal to 105 percent, and the specific surface area is more than or equal to 400cm2/g。
The solid sulfur ash and the gasified slag are industrial solid waste regeneration powder, mainly contain substances such as silicon dioxide, aluminum oxide, calcium oxide and the like, and have volcanic ash activity. The activity of the industrial solid waste regeneration powder is improved through the mechanical activation, and the volcanic ash activity of the industrial solid waste regeneration powder is further excited by the calcium oxide, the cement and the gypsum to generate hydration products such as hydrated calcium silicate (aluminum) and ettringite, so that the hydration products are filled in gypsum pores or covered on the surface of gypsum crystals to form an inorganic waterproof layer, and the mechanical property and the water resistance of the gypsum are obviously improved. The use of the industrial solid waste regenerated powder has obvious economic benefit and environmental protection benefit.
The method for treating the solid sulfur ash comprises the following steps: (1) uniformly mixing the raw solid sulfur ash slag with 1-3% of water to obtain powder A; (2) adding the powder A into a ball mill for grinding for 25-40 minutes to obtain powder B; (3) and drying the powder B at the temperature of 90-110 ℃ for 1-2 hours to obtain the solid sulfur ash powder. The sulfur-fixing ash slag is solid waste discharged after coal and a sulfur-fixing agent are mixed and are combusted at high temperature in a fluidized bed boiler. The prepared sulfur-fixing clinker is mixed with small amount of water and ground to eliminate free oxidationPoor volume stability due to calcium; the grinding realizes mechanical activation on the solid sulfur ash, so that the activity of the solid sulfur ash is improved; the solid sulfur ash is fully dried, so that the contained calcium sulfate dihydrate is converted into the semi-hydrated calcium sulfate and the anhydrous calcium sulfate, and the hydration hardening performance of the solid sulfur ash is further improved. The specific surface area of the prepared solid sulfur ash is more than or equal to 400cm2The water demand is 105 percent and the activity is more than or equal to 80 percent.
The method for treating the gasified slag comprises the following steps: (1) drying the raw coal gasification slag at 105 ℃ for 1-2 hours; (2) sieving the dried raw coal gasification slag through a 1.16mm sieve to obtain coarse coal gasification slag; (3) placing the gasified coarse slag in a ball mill for grinding for 35-50 minutes to obtain the product with the specific surface area of more than or equal to 400cm2Per gram of coal gasification slag. The coal gasification slag is solid waste generated in the coal-to-liquid technology, the texture of the coal gasification slag is not hard, the coal gasification slag can be utilized by simple ball milling, and the process is simple and convenient. The gasified slag has the characteristic of porosity, has relatively high water content, needs to be fully dried to reduce the water content and increase the mechanical activation efficiency; the raw slag is sieved by a 1.16mm sieve, so that fine slag with high carbon content in the coarse slag can be removed, and the loss of the gasified coal slag is reduced. The water requirement of the prepared coal gasification slag is 95%, the activity is more than or equal to 105%, and the coal gasification slag is superior to S95 mineral powder and I-grade fly ash.
The further technical scheme is that the zeolite powder is 300-400 meshes and chemical composition SiO250 to 70 mass% of Al2O3The content is 10 to 20 mass%.
The zeolite powder is inorganic inert powder, and the addition of the zeolite powder can improve the workability of the gypsum and improve the mechanical property of the gypsum; the zeolite powder is filled in the pores of the gypsum matrix, so that the compactness of the matrix is increased, and the effects of reinforcement and crack resistance are achieved. The zeolite powder is a porous material and has strong adsorption capacity, so that harmful impurities in the gypsum can be adsorbed to a certain degree, and the quality of the gypsum product is improved; in addition, the zeolite powder contains a certain amount of active silicon dioxide and aluminum oxide, has good compatibility with gypsum, can generate a certain chemical reaction with an exciting agent to generate a gel substance, and is beneficial to the performance of the gypsum.
The calcium oxide has the further technical scheme that the calcium oxide has the functions of exciting coal gasification slag and sulfur fixation slag, and solidifying phosphorus and fluorine impurities in the phosphogypsum, so that the pH value of a phosphogypsum system is changed, soluble phosphorus and fluorine in the phosphogypsum are converted into inert insoluble salt, and the adverse effect on a phosphogypsum cementing material is reduced.
The calcium oxide is alkaline and can ionize OH in water-，OH-The polarization effect promotes the dissolution of Al, Si, Ca and other ions in cement, solid sulfur ash and gasified slag, accelerates the generation of hydration products of calcium silicate hydrate (aluminum) and ettringite and other substances, and improves the mechanical property and water resistance of the system; the cement, the solid sulfur ash and the coal gasification slag are hydraulic cementing materials, and the generation of hydration products is increased under the action of calcium oxide and water, so that the mechanical property of the gypsum after being soaked in water is improved, and the softening coefficient can reach more than 1.
The further technical scheme is that the preparation method of the high-strength water-resistant phosphogypsum composite cementing material comprises the following steps:
(1) weighing a polycarboxylic acid water reducing agent, a melamine water reducing agent, a protein retarder, borax and an air entraining agent according to the parts by weight, dissolving in 1/3 mixed water, and uniformly stirring to obtain a retarding rheological agent;
(2) dissolving the composite waterproof agent in the rest of the mixing water and uniformly stirring to obtain a solution A;
(3) uniformly mixing cement, gasified slag, solid sulfur slag and zeolite powder in a dry mode to obtain composite powder;
(4) uniformly mixing the composite powder, calcium oxide and phosphorus building gypsum powder in a dry mode to obtain mixed powder B;
(5) slowly adding the retarding rheological agent and the solution A into the mixed powder B, and uniformly stirring to obtain gypsum slurry;
(6) and (3) pouring the gypsum slurry into a mould, removing the mould after hardening, and drying and curing the gypsum test piece at 40-50 ℃ to constant weight to obtain the high-strength water-resistant phosphogypsum composite rubber material test piece.
The high-strength water-resistant phosphogypsum composite cementing material prepared by the invention improves the water resistance by using a composite mode of organic water resistance and inorganic water resistance. The organic and inorganic composite waterproof mechanism is as follows: the addition of cement, coal gasification slag and solid sulfur ash slag introduces calcium silicate hydrate, ettringite and the like into the matrix, and the calcium silicate hydrate calcium silicate, the ettringite and the like cover the surface of the dihydrate gypsum to form a compact wrapping layer or are filled in the pores of the dihydrate gypsum to form an inorganic waterproof layer, so that the density and the strength of the system are increased; the organic silicon polymer is dissolved to form a film and is distributed in a gypsum system, and a hydrophobic film formed by the organic silicon polymer is combined on the surface of an inorganic hydration product through a hydrophilic group along with the hydration and the water evaporation of an inorganic material to form an organic waterproof layer, so that the invasion of water can be hindered, and the film forming effect can also greatly improve the breaking strength of the gypsum. The excellent water-resistant effect can keep the relatively low humidity of the gypsum test piece in a humid environment, thereby having a certain mildew-proof effect.
The invention has the beneficial effects that:
(1) the high-strength water-resistant phosphogypsum composite cementing material prepared by the invention is prepared by using beta-type building phosphogypsum powder, the water resistance of gypsum is further improved by using a waterproof agent, the softening coefficient of the gypsum is 0.9-1.2, the saturated water absorption rate is below 5%, and the high-strength water-resistant phosphogypsum composite cementing material is not only used in indoor dry areas, but also can be used in damp areas such as kitchens, bathrooms and the like, so that the application range of related gypsum products is expanded.
(2) The high-strength water-resistant phosphogypsum composite cementitious slurry prepared by the invention has good fluidity and construction performance, the mechanical property and workability of a gypsum base material are improved by adjusting the components and the using amount of the rheological agent and the air entraining agent, the water reducing and retarding effects are obvious, the phosphorous building gypsum can achieve the self-leveling effect, and the compression/bending strength is 25-45/5-13 MPa. A large amount of uniformly distributed, stable and closed micro bubbles are introduced into the phosphogypsum slurry to compensate the beta-type phosphogypsum and fine particles with poor aggregate gradation in the slurry, improve the frost resistance at low temperature, and improve the defects of pitted surfaces, pits and the like of phosphogypsum products.
(3) The high-strength water-resistant phosphogypsum composite cementing material prepared by the invention has a simple preparation method, uses a large amount of industrial solid waste regenerated powder, improves the mechanical property and water resistance of gypsum, and reduces the cost of gypsum products. The industrial solid waste regenerated powder has simple preparation process and obvious economic benefit and environmental protection benefit when used.
(4) The high-strength water-resistant phosphogypsum composite cementing material prepared by the invention is environment-friendly, can greatly consume industrial byproduct phosphogypsum, improves the quality of gypsum products by a phosphogypsum high-strength water-resistant modification technology, has excellent composite cementing performance, is safe and reliable as green, environment-friendly and energy-saving building material products, and can promote the development of phosphogypsum-based green building materials and the policy of recycling solid waste resources.
Drawings
FIG. 1 is a graph comparing the gypsum flow in comparative group 1 and example 3;
FIG. 2 is a comparative water drop plot of the cross-section of the gypsum test pieces in comparative group 1 and example 3;
Detailed Description
The technical solution of the present invention will be further specifically described below by way of examples.
Comparative group 1
The components and contents of comparative group 1: 100 parts of beta-type building phosphogypsum powder and 60 parts of water.
The preparation method of the common phosphogypsum comprises the following steps:
(1) adding water into the gypsum powder, and stirring for 2 minutes to obtain gypsum slurry;
(2) and (3) injecting the gypsum slurry into a mould, removing the mould after hardening, and drying and curing the gypsum test piece for 24 hours at 45 ℃ to obtain the common phosphogypsum test piece.
Comparative group 2
The comparative group 2 consists of the following components in parts by weight: 2.5 parts of waterproof agent, 5 parts of cement, 5 parts of solid sulfur ash, 1 part of zeolite powder, 100 parts of beta-phosphorus building gypsum powder, 0.2 part of calcium oxide, 0.5 part of rheological agent and 37 parts of water.
The formula of the waterproof agent comprises 1 part of organic silicon polymer, 1.5 parts of silicone-acrylate emulsion and 0.15 part of sodium dodecyl sulfate; the formula of the rheological agent comprises 9 parts of polycarboxylic water reducer, 2 parts of melamine water reducer, 2 parts of protein retarder and 0.1 part of borax.
Comparative group 3
The comparative group 3 consisted of the following components in parts by weight: 2.5 parts of waterproof agent, 5 parts of solid sulfur ash, 10 parts of gasified slag, 1 part of zeolite powder, 100 parts of beta-phosphorus building gypsum powder, 0.2 part of calcium oxide, 0.5 part of rheological agent and 37 parts of water.
The formula of the waterproof agent comprises 1 part of organic silicon polymer, 1.5 parts of silicone-acrylate emulsion and 0.15 part of sodium dodecyl sulfate; the formula of the rheological agent comprises 10 parts of polycarboxylic water reducer, 1 part of melamine water reducer, 2 parts of protein retarder and 0.1 part of borax.
Comparative group 4
Comparative group 4 consisted of the following components in parts by weight: 2.5 parts of waterproof agent, 7 parts of cement, 10 parts of gasified slag, 1 part of zeolite powder, 100 parts of beta-phosphorus building gypsum powder, 0.2 part of calcium oxide, 0.5 part of rheological agent and 37 parts of water.
The formula of the waterproof agent comprises 1 part of organic silicon polymer, 1.5 parts of silicone-acrylate emulsion and 0.15 part of sodium dodecyl sulfate; the formula of the rheological agent comprises 10 parts of polycarboxylic water reducer, 1 part of melamine water reducer, 2 parts of protein retarder and 0.1 part of borax.
Comparative group 5
Comparative group 5 consisted of the following components in parts by weight: 2.5 parts of waterproof agent, 5 parts of cement, 4 parts of solid sulfur ash, 5 parts of gasified slag, 1 part of zeolite powder, 100 parts of beta-phosphorus building gypsum powder, 0.2 part of calcium oxide, 0.5 part of rheological agent and 37 parts of water.
The formula of the waterproof agent comprises 2 parts of organic silicon polymer and 0.15 part of lauryl sodium sulfate; the formula of the rheological agent comprises 10 parts of polycarboxylic water reducer, 1 part of melamine water reducer, 2 parts of protein retarder and 0.1 part of borax.
Comparative group 6
Comparative group 6 consisted of the following components in parts by weight: 2.5 parts of waterproof agent, 4 parts of cement, 5 parts of solid sulfur ash, 5 parts of gasified slag, 1 part of zeolite powder, 100 parts of beta-phosphorus building gypsum powder, 0.2 part of calcium oxide, 0.5 part of rheological agent and 37 parts of water.
The formula of the waterproof agent comprises 4 parts of silicone-acrylate emulsion and 0.2 part of sodium dodecyl sulfate; the formula of the rheological agent comprises 10 parts of polycarboxylic water reducer, 1 part of melamine water reducer, 2 parts of protein retarder and 0.1 part of borax.
Example 1
A high-strength water-resistant phosphogypsum composite cementing material is composed of the following components in parts by weight: 2.5 parts of waterproof agent, 5 parts of cement, 5 parts of solid sulfur ash, 5 parts of gasified slag, 1 part of zeolite powder, 100 parts of beta-phosphorus building gypsum powder, 0.2 part of calcium oxide, 0.5 part of rheological agent and 37 parts of water.
The formula of the waterproof agent comprises 1 part of organic silicon polymer, 1.5 parts of silicone-acrylate emulsion and 0.15 part of sodium dodecyl sulfate; the formula of the rheological agent comprises 9 parts of polycarboxylic water reducer, 2 parts of melamine water reducer, 2 parts of protein retarder and 0.1 part of borax.
Example 2
A high-strength water-resistant phosphogypsum composite cementing material is composed of the following components in parts by weight: 1.5 parts of waterproof agent, 6 parts of cement, 6 parts of solid sulfur ash, 5 parts of gasified slag, 0.5 part of zeolite powder, 1 part of calcium oxide, 100 parts of phosphorus building gypsum powder, 1 part of rheological agent and 35 parts of water.
The formula of the waterproof agent comprises 0.2 part of organic silicon polymer, 0.5 part of emulsion and 0.01 part of lauryl sodium sulfate; the formula of the rheological agent comprises 8 parts of polycarboxylic water reducer, 1 part of melamine water reducer, 1 part of protein retarder and 0.2 part of borax.
Example 3
The preparation method of the high-strength water-resistant phosphogypsum composite cementing material comprises the following components in parts by weight: 4 parts of waterproof agent, 7 parts of cement, 10 parts of solid sulfur ash, 10 parts of gasified slag, 3 parts of zeolite powder, 3 parts of calcium oxide, 100 parts of phosphorus building gypsum powder, 4 parts of rheological agent and 28 parts of water.
The formula of the waterproof agent comprises 2 parts of organic silicon polymer, 4 parts of silicone-acrylate emulsion and 0.24 part of sodium dodecyl sulfate; the formula of the rheological agent comprises 10 parts of polycarboxylic water reducer, 3 parts of melamine water reducer, 4 parts of protein retarder, 0.5 part of borax and 0.08 part of alpha-sodium alkenyl sulfonate.
Example 4
A high-strength water-resistant phosphogypsum composite cementing material is composed of the following components in parts by weight: 1 part of waterproof agent, 7 parts of cement, 6 parts of solid sulfur ash, 6 parts of gasified slag, 1.5 parts of calcium oxide, 100 parts of phosphorus building gypsum powder, 1 part of rheological agent, 35 parts of water and 0.5 part of zeolite powder.
The formula of the rheological agent comprises 10 parts of polycarboxylic water reducer, 3 parts of melamine water reducer, 2 parts of protein retarder and 0.1 part of borax. The formula of the waterproof agent comprises 2 parts of organic silicon polymer, 4 parts of silicone-acrylate emulsion and 0.24 part of sodium dodecyl sulfate.
Example 5
A high-strength water-resistant phosphogypsum composite cementing material is composed of the following components in parts by weight: 2.5 parts of a waterproof agent, 2.5 parts of calcium oxide, 100 parts of phosphorus building gypsum powder, 3 parts of a rheological agent, 29 parts of water, 7 parts of cement, 8 parts of solid sulfur ash, 6 parts of gasified slag and 2 parts of zeolite powder.
The formula of the waterproof agent comprises 1.5 parts of organic silicon polymer, 3 parts of silicone-acrylate emulsion and 0.2 part of sodium dodecyl sulfate; the formula of the rheological agent comprises 10 parts of polycarboxylic water reducer, 3 parts of melamine water reducer, 3 parts of protein retarder, 0.4 part of borax and 0.04 part of alpha-sodium alkenyl sulfonate.
The preparation method of the water repellent of comparative groups 2 to 6 and examples 1 to 5 is as follows:
(1) adding 0.5 part of acetic acid and 1 part of vinyl trimethoxy silane into 120 parts of deionized water at the same time, and stirring at 25 ℃ for 20 minutes to ensure that the two react fully to obtain a silane solution A;
(2) dissolving 3 parts of ethyl acrylate in deionized water, and stirring to a clear state to obtain a solution B, wherein the weight ratio of ethyl acrylate: deionized water 1: 300, respectively;
(3) adding the prepared silane solution A, the prepared silane solution B, 0.5 part of polyethylene oxide, 1.5 parts of dodecafluoroheptyl ester and 1.5 parts of potassium persulfate into a reaction kettle together for emulsion polymerization reaction, heating to 70 ℃ while stirring, and stirring at constant temperature for 2.0 hours;
(4) cooling the system obtained in the step (3) to 50 ℃, stirring at constant temperature for 1 hour, and aging at normal temperature for 24 hours without layering and flocculation phenomena to obtain an organic silicon polymer;
(5) and stirring the mixed solution of the organic silicon polymer, the silicone-acrylic emulsion and the sodium dodecyl sulfate for 25 minutes at 20 ℃ and 5000rpm to obtain a mixed solution with good adaptability, and aging the mixed solution for 24 hours at normal temperature without layering and agglomeration to obtain the waterproof agent.
The phosphogypsum high-strength water-resistant composite cementing material of the comparative groups 2-6 and the embodiments 1-5 is prepared by the following steps:
(1) weighing a polycarboxylic water reducer, a melamine water reducer, a protein retarder, borax and an air entraining agent according to the parts by weight, dissolving the materials in 1/3 mixed water, and stirring for 2 minutes to obtain a rheological agent;
(2) dissolving the waterproof agent in the rest of the mixing water and uniformly stirring to obtain a solution A;
(3) dry-mixing cement, coal gasification slag, solid sulfur ash and zeolite powder for 1.5 minutes to obtain composite powder;
(4) dry-mixing the composite powder, calcium oxide and phosphorus building gypsum powder for 1.5 minutes to obtain mixed powder B;
(5) slowly adding the rheological agent and the solution A into the mixed powder B, and stirring for 2.5 minutes after the addition to obtain gypsum slurry;
(6) and (3) pouring the gypsum slurry into a mould, removing the mould after hardening, and drying and curing the gypsum test piece at 45 ℃ to constant weight to obtain the high-strength water-resistant phosphogypsum composite cementing material.
The high-strength water-resistant phosphogypsum composite cementing materials prepared in comparative groups 1-6 and examples 1-5 are subjected to performance tests, wherein the slurry test results are shown in table 1, the test piece (40 × 160mm) performance test results are shown in table 2, the gypsum slurry fluidity is shown in figure 1, and the water drop picture of the section of the gypsum test piece is shown in figure 2. The performance test refers to the homogeneity test methods of GB/T9776-.
TABLE 1 Performance test results for gypsum slurries
TABLE 2 Gypsum test piece Performance test results
In conclusion, the invention obviously improves the rheological property, the mechanical property and the water resistance of the beta-type phosphogypsum slurry through the synergistic effect of the rheological technology and the waterproof modification technology and the synergistic effect among the components; the industrial solid wastes such as solid sulfur ash, coal gasification slag and the like are used in the phosphogypsum product to improve the water resistance and the mechanical property of the phosphogypsum product. The invention can prepare the green, environment-friendly, low-cost and high-strength water-resistant phosphogypsum composite cementing material: the softening coefficient is 0.9-1.2, the saturated water absorption is less than 5%, the compression/bending strength is 25-45/5-13 MPa, and the ardealite composite material can be used in the damp-prone areas such as kitchens and bathrooms, and the application field of industrial byproduct ardealite products is widened.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited to the above embodiments, and various changes and modifications may be made by those skilled in the art without departing from the scope of the invention.
Claims (7)
1. The high-strength water-resistant phosphogypsum composite cementing material is characterized by comprising the following components in parts by weight: 100 parts of phosphorus building gypsum powder, 0.5-4 parts of rheological agent, 3-7 parts of cement, 4-10 parts of solid sulfur ash, 3-10 parts of gasified slag, 0.5-3 parts of zeolite powder, 1-4 parts of waterproof agent and 0.2-3 parts of calcium oxide; the rheological agent comprises 8-10 parts of polycarboxylic water reducer, 1-3 parts of melamine water reducer, 1-4 parts of protein retarder and 0.1-0.5 part of borax; the waterproof agent comprises 0.2-2 parts of organic silicon polymer, 0.5-4 parts of silicone-acrylic emulsion and 0.01-0.24 part of sodium dodecyl sulfate;
the polycarboxylic acid water reducing agent is solution type, the solid content is more than or equal to 20 percent, and the water reducing rate is more than 20 percent; the melamine water reducing agent is in a powder form, the water reducing rate is more than 20 percent, and the water content is less than or equal to 4 percent; the borax is chemical analysis pure grade sodium tetraborate decahydrate, and the purity is more than 99 percent;
the rheological agent also comprises 0-0.08 part of air entraining agent, wherein the air entraining agent is anionic air entraining agent and comprises alpha-sodium alkenyl sulfonate;
the preparation method of the waterproof agent comprises the following steps:
(1) adding 0.1-0.8 part of acetic acid and 0.2-2 parts of vinyl trimethoxy silane into 100-140 parts of deionized water at the same time, and stirring for 15-30 minutes at 20-25 ℃ to enable the two to react sufficiently to obtain a silane solution A;
(2) dissolving 0.2-4 parts of ethyl acrylate in deionized water, and stirring to a clear state to obtain a solution B, wherein the weight ratio of ethyl acrylate: deionized water ratio of 1: (250-340);
(3) adding the prepared silane solution A, the prepared silane solution B, 0.1-1 part of polyoxyethylene, 0.5-2 parts of dodecafluoroheptyl ester and 0.2-2 parts of potassium persulfate into a reaction kettle together for emulsion polymerization, heating to 70 ℃ while stirring, and stirring at constant temperature for 1.5-2.0 hours;
(4) cooling the system obtained in the step (3) to 50-55 ℃, stirring at a constant temperature for 1.0-1.5 hours, and aging for 24 hours at normal temperature without layering and flocculation phenomena to obtain an organic silicon polymer;
(5) and uniformly stirring a mixed solution of 0.2-2 parts of organic silicon polymer, 0.5-4 parts of silicone-acrylic emulsion and 0.01-0.24 part of sodium dodecyl sulfate at 20-25 ℃ and at the rotating speed of 4000-6000 rpm to obtain a mixed solution with good adaptability, and aging the mixed solution at normal temperature for 24 hours without layering and agglomeration to obtain the waterproof agent.
2. The high-strength water-resistant phosphogypsum composite cementing material as claimed in claim 1, wherein the solid content of the silicone-acrylic emulsion is more than or equal to 50%, and the viscosity is more than or equal to 2000mPa s; the sodium dodecyl sulfate is of chemical analysis pure grade, and the purity is more than 99%.
3. The high-strength water-resistant phosphorus as claimed in claim 1The gypsum composite cementing material is characterized in that the phosphorus building gypsum powder is beta-type building phosphogypsum powder, the content of semi-hydrated gypsum of the beta-type building phosphogypsum powder is more than or equal to 86 percent, the content of anhydrous gypsum is less than or equal to 5 percent, the content of dihydrate gypsum is less than or equal to 4 percent, and the specific surface area is more than 350m 2A density of 2.4 to 2.8kg/m 3 。
4. The high-strength water-resistant phosphogypsum composite cementing material of claim 1, which is characterized in that the specific surface area of the clinker is not less than 400cm 2The water demand is 105 percent and the activity is more than or equal to 80 percent.
5. The high-strength water-resistant phosphogypsum composite cementing material as claimed in claim 1, wherein the water requirement of the gasified slag is 95%, the activity is not less than 105%, and the specific surface area is not less than 400cm 2 /g。
6. The high-strength water-resistant phosphogypsum composite cementing material as claimed in claim 1, characterized in that the zeolite powder is 300-400 mesh and chemical composition SiO is SiO250 to 70 mass% of Al2 O3The content is 10 to 20 mass%.
7. The high-strength water-resistant phosphogypsum composite cementitious material according to any one of claims 1 to 6, characterized in that the preparation method comprises the following steps:
(1) weighing a polycarboxylic acid water reducing agent, a melamine water reducing agent, a protein retarder, borax and an air entraining agent according to the parts by weight, dissolving in 1/3 mixed water, and uniformly stirring to obtain a rheological agent;
(2) dissolving the waterproof agent in the rest of the mixing water and uniformly stirring to obtain a solution A;
(3) uniformly mixing cement, gasified slag, solid sulfur slag and zeolite powder in a dry mode to obtain composite powder;
(4) uniformly mixing the composite powder, calcium oxide and phosphorus building gypsum powder in a dry mode to obtain mixed powder B;
(5) slowly adding the rheological agent and the solution A into the mixed powder B, and uniformly stirring to obtain gypsum slurry;
(6) and (3) pouring the gypsum slurry into a mould, removing the mould after hardening, and drying and curing the gypsum test piece at 40-50 ℃ to constant weight to obtain the high-strength water-resistant phosphogypsum composite rubber material test piece.
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