WO2020199400A1 - Machine-spraying surface gypsum plaster having purification function and preparation method therefor - Google Patents

Machine-spraying surface gypsum plaster having purification function and preparation method therefor Download PDF

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Publication number
WO2020199400A1
WO2020199400A1 PCT/CN2019/094250 CN2019094250W WO2020199400A1 WO 2020199400 A1 WO2020199400 A1 WO 2020199400A1 CN 2019094250 W CN2019094250 W CN 2019094250W WO 2020199400 A1 WO2020199400 A1 WO 2020199400A1
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WIPO (PCT)
Prior art keywords
plaster
machine
phosphogypsum
curing agent
purification function
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PCT/CN2019/094250
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French (fr)
Chinese (zh)
Inventor
尹东杰
王鹏起
谭丹君
简铭
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北新集团建材股份有限公司
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Publication of WO2020199400A1 publication Critical patent/WO2020199400A1/en

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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
    • 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
    • C04B28/14—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
    • 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
    • C04B2111/00017—Aspects relating to the protection of the environment
    • 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
    • C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection

Definitions

  • This application relates to but not limited to the field of building materials, in particular, to but not limited to a machine spray surface plaster plaster with purification function and a preparation method thereof.
  • Plastering gypsum is a new leveling material that has developed rapidly in recent years. It is mainly made of gypsum as the main cementing material, adding admixtures, admixtures, etc., and is widely used in the leveling and decoration of interior walls and ceilings. . In construction projects, plastering gypsum has good workability, fluidity, water retention, thermal insulation properties and appropriate fire resistance. The walls after plastering are dense and smooth, and the indoor humidity can be adjusted. Therefore, plastering gypsum is a wall plastering and leveling material with good material properties, construction performance and use functions, and is widely used in industrial and civil buildings.
  • plastering plaster instead of lime mortar and cement mortar plastering is a development trend in building wall decoration.
  • Plastering gypsum for machine-jet surface layer has become a new bright spot in the development of plastering materials for interior walls of buildings.
  • the use of machine-sprayed plastering plaster for plastering works can effectively save the total cost of the project, save labor costs, and accelerate the construction progress of the project, which has become an urgent need for large construction sites.
  • the surface plaster plaster with purification function is prepared, and the large area of the wall is used to purify the air.
  • Phosphogypsum is an industrial by-product of the process of preparing phosphoric acid by wet process. About 5 tons of phosphogypsum are produced for every 1 ton of phosphoric acid produced. At present, the accumulated stock of phosphogypsum in my country has exceeded 300 million tons. In particular, since 2018, China has begun to levy a solid waste environmental protection tax of 25 yuan/ton from sewage companies, so the utilization of phosphogypsum, a regenerated gypsum resource, cannot be delayed.
  • the inventor of the present application found that the harmless pretreatment of phosphogypsum so that the harmful impurities in the phosphogypsum can be solidified during the phosphogypsum cementing process, showing chemical inertness, is a realization An effective way to reuse phosphogypsum.
  • the phosphogypsum is pretreated.
  • the curing agent is used to solidify the impurity ions without diffusion and migration, so that the phosphogypsum meets the requirements of ordinary building gypsum.
  • the preparation technology and construction technology of mechanical plastering gypsum products are not mature at this stage.
  • the use of phosphogypsum, an industrial solid waste, to produce plastering gypsum that is suitable for mechanical spraying and has a purification function is even blank.
  • this application prepares a surface plaster plaster product that meets the requirements of mechanical spraying performance and product quality through the coordination of retarder and water retention agent.
  • the flow of the surface plaster plaster It has excellent properties, cohesion and water retention, and is suitable for mechanical spraying.
  • the surface plaster also has the ability to purify formaldehyde. It is a machine spray surface plaster that can purify air and meets the requirements of China's national and industry standards.
  • the raw material of the surface plaster plaster includes the following components: pretreated phosphogypsum powder, curing agent, water, retarder, water retention agent And purifiers.
  • the mass ratio of the pretreated phosphogypsum powder, the curing agent, the water, the retarder, the water-retaining agent, and the purifying agent may be 100: (1.5 to 5 ):(200 to 300):(2 to 5):(5 to 25):(0.5 to 2).
  • the pretreated phosphogypsum powder can be obtained by adjusting the pH value of the phosphogypsum to neutral or weakly alkaline, and undergoing calcination, aging, grinding and sieving treatments.
  • the pH value of phosphogypsum can be adjusted to 6.5 to 8.
  • the pH of phosphogypsum can be adjusted to 6.5 to 8 with quicklime.
  • the quicklime CaO reacts with the soluble P 2 O 5 and F - in the phosphogypsum to generate inert substances, which can eliminate the harm of soluble phosphorus and fluorine.
  • the added amount of quicklime may be 0.2% to 1.0% by mass of the amount of phosphogypsum.
  • the calcination temperature may be in the range of 150°C to 200°C.
  • the calcination time may be in the range of 1.5 hours to 4 hours.
  • the aging time may be in the range of 24 hours to 72 hours.
  • the grinding time may be in the range of 3 minutes to 10 minutes.
  • the sieving may include passing the ground phosphogypsum powder through a 50 to 200 mesh sieve.
  • the phosphogypsum can be calcined at 150°C to 200°C for 1.5 hours to 4 hours, after aging for 24 hours to 72 hours, pulverized for 3 minutes to 10 minutes, and passed through a 50 mesh to 200 mesh sieve to obtain The pretreated phosphogypsum powder.
  • the phosphogypsum after adjusting the pH to neutral or weakly alkaline can be calcined at 160°C for 2 hours, aged for 48 hours, and ground for 5 minutes.
  • the phosphogypsum after adjusting the pH to neutral or weakly alkaline can be calcined at 180°C for 2 hours, aged for 48 hours, and ground for 5 minutes.
  • the pretreated phosphogypsum powder can be obtained after passing through an 80-mesh sieve.
  • the content of powder that can pass a 200-mesh sieve is not less than 30% by mass.
  • the curing agent may be selected from any one or more of inorganic curing agents (such as fluorosilicate curing agents) and organic curing agents (such as amine curing agents).
  • inorganic curing agents such as fluorosilicate curing agents
  • organic curing agents such as amine curing agents
  • the plastering gypsum may also include an accelerator.
  • the mass ratio of the amine curing agent to the accelerator may be 1: (0.5 to 1)
  • the fluorosilicate curing agent may be selected from any one or more of magnesium fluorosilicate, zinc fluorosilicate, calcium fluorosilicate, and sodium fluorosilicate.
  • the amine curing agent can be selected from 4,4'-diaminodiphenylmethane, triethylenetetramine, diethylenetriamine, N-methylolacrylamide, polyacrylaniline, and Any one or more of phenylenediamine and tetraethylamine bromide.
  • the accelerator may be selected from any one or more of salicylic acid, formaldehyde, benzaldehyde, methanol, ethanol, n-propanol, tert-butanol, isobutanol, and cyclohexanol.
  • the inventor of the present application found that the calcination treatment in the pretreatment process of phosphogypsum can eliminate the organic matter in the phosphogypsum.
  • the quicklime CaO adjusts the pH while reacting with the soluble P 2 O 5 and F - in the phosphogypsum to generate inert substances. It can eliminate the harm of soluble phosphorus and fluorine.
  • the curing agent After the curing agent is used on the phosphogypsum, it can effectively prevent impurity ions (including soluble P 2 O 5 , F - and metal ions) from destroying and damaging the electric double layer structure between gypsum particles, and restrict the exchange activity of impurity ions. After research, the reason is that the chemical force generated by the curing agent can close the diffusion path of impurity ions, and enhance the cohesion of the phosphogypsum particles. When the phosphogypsum is cured and hardened with water, it will no longer penetrate and diffuse out of the phosphogypsum.
  • impurity ions including soluble P 2 O 5 , F - and metal ions
  • the retarder may be selected from any one or more of citric acid, sodium citrate, sodium hexametaphosphate, borax, and protein retarders.
  • the protein-based retarder may be selected from any one or more of bone glue protein retarder and protein-based gypsum retarder formed by calcium salting of degraded polyamide.
  • the water retaining agent may be selected from any one or more of hydroxypropyl methylcellulose, sodium polyacrylate and polyacrylamide.
  • the hydroxypropyl methyl cellulose may include slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 40,000 Pa.s to 200,000 Pa.s.
  • the hydroxypropyl methyl cellulose may include slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 60000 Pa.s to 100000 Pa.s.
  • the purifying agent may be selected from nano-titanium dioxide (TiO 2 ), titanium dioxide phosphate, zinc oxide (ZnO), tin oxide (SnO 2 ), zirconium dioxide (ZrO 2 ), and cadmium sulfide (CdS) Any one or more of them.
  • the application also provides a preparation method of the machine-sprayed surface layer plaster plaster, the preparation method includes:
  • the plastering gypsum powder and water are evenly mixed at the construction site to obtain the machine-sprayed surface layer plastering gypsum.
  • the mass ratio of the pretreated phosphogypsum powder: the curing agent: the water: the retarder: the water retaining agent: the purifying agent may be 100:( 1.5 to 5): (200 to 300): (2 to 5): (5 to 25): (0.5 to 2).
  • the curing agent may be selected from any one or more of inorganic curing agents (for example, fluorosilicate curing agents) and organic curing agents (for example, amine curing agents), When the curing agent is an amine curing agent, an accelerator may also be included.
  • inorganic curing agents for example, fluorosilicate curing agents
  • organic curing agents for example, amine curing agents
  • the mass ratio of the amine curing agent to the accelerator may be 1: (0.5 to 1).
  • the fluorosilicate curing agent may be selected from any one or more selected from magnesium fluorosilicate, zinc fluorosilicate, calcium fluorosilicate, and sodium fluorosilicate. Kind.
  • the amine curing agent may be selected from 4,4-diaminodiphenylmethane, triethylenetetramine, diethylenetriamine, N-methylolacrylamide, polyacrylaniline , Any one or more of m-phenylenediamine and tetraethylamine bromide.
  • the accelerator may be selected from any one or more of salicylic acid, formaldehyde, benzaldehyde, methanol, ethanol, n-propanol, tert-butanol, isobutanol, and cyclohexanol. Many kinds.
  • the retarder may be selected from any one or more of citric acid, sodium citrate, sodium hexametaphosphate, borax and protein retarders.
  • the protein-based retarder can be selected from any one or more of bone gel protein retarder and protein-based gypsum retarder formed by calcium salting of degraded polyamide .
  • the water retaining agent may be selected from any one or more of hydroxypropyl methylcellulose, sodium polyacrylate, and polyacrylamide.
  • the hydroxypropyl methyl cellulose may include slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 40,000 Pa.s to 200,000 Pa.s.
  • the hydroxypropyl methyl cellulose may include slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 60000 Pa.s to 100000 Pa.s.
  • the purifying agent may be selected from nano titanium dioxide (TiO 2 ), titanium dioxide phosphate, zinc oxide (ZnO), tin oxide (SnO 2 ), zirconium dioxide (ZrO 2 ), and cadmium sulfide ( Any one or more of CdS), in an exemplary embodiment, the purification agent may be nano titanium dioxide.
  • the curing agent, retarder, water-retaining agent, purifying agent and accelerator used in the plastering gypsum raw materials are not limited to the specific materials listed above, and materials that can achieve the effects of various reagents can be used in this application In the preparation of plastering gypsum, the specific materials listed above do not limit the application in any form or substance.
  • the phosphogypsum used can meet the Chinese national standards for building gypsum. It does not penetrate harmful elements and replaces the traditional natural gypsum and desulfurized gypsum. It is the use of phosphogypsum to replace desulfurized gypsum and The construction gypsum production machine sprays plaster gypsum to open up a new way to realize the reuse of solid waste;
  • curing agent can effectively solidify harmful impurity ions in phosphogypsum, enhance the cohesion of phosphogypsum particles, and prevent harmful impurity ions from penetrating and diffusing out of phosphogypsum;
  • the retarder and the water-retaining agent cooperate with each other, and the prepared plaster plaster has excellent fluidity, cohesion and water retention, and can be suitable for mechanical spraying. It solves the problem that ordinary plastering gypsum cannot be mechanized and replaced by mechanized plastering. Manual plastering can greatly improve construction efficiency, shorten construction period, and simplify construction procedures;
  • the plastering gypsum of the present application can form an inorganic acid amorphous polymer film after spraying on the surface of the object, and form a nano-sized micro-pore structure after drying, which can be exposed to light (ultraviolet light and visible light) Under the action of ), the irradiation takes place catalysis and produces strong oxidizing hydroxyl radicals (-OH), which can effectively degrade toxic and harmful gases in the air.
  • -OH oxidizing hydroxyl radicals
  • the raw materials used in the following examples are all common commercial products.
  • Step 1 Adjust the pH value of the phosphogypsum powder to 6.8 by using 0.3% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
  • Step 2 Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 5 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh
  • the powder content of the sieve was 32% by mass.
  • Step 3 Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 2 parts by weight of magnesium fluorosilicate curing agent, 220 parts by weight of water, 2.3 parts by weight of bone gel protein retarder, and hydroxyl with a viscosity of 60000 Pa.s 20 parts by weight of propyl methyl cellulose (HPMC) water retaining agent and 0.6 parts by weight of nano titanium dioxide scavenger.
  • HPMC propyl methyl cellulose
  • Step 4 Mix the pretreated phosphogypsum powder, curing agent, retarder, water-retaining agent, and purifying agent uniformly to obtain plastering gypsum powder.
  • Step 5 Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
  • Step 1 Adjust the pH value of the phosphogypsum powder to 7.2 with 0.5% by mass quicklime in the amount of phosphogypsum to obtain neutralized phosphogypsum powder.
  • Step 2 The neutralized phosphogypsum powder is calcined in a muffle furnace at 180°C for 2 hours. After aging for 48 hours, it is ground for 5 minutes and passed through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 meshes. The powder content of the sieve was 30% by mass.
  • Step 3 Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 4 parts by weight of sodium fluorosilicate curing agent, 250 parts by weight of water, and protein-based gypsum retarded by calcium salting of degraded polyamide 4.6 parts by weight of hydroxypropyl methylcellulose (HPMC) water-retaining agent with a viscosity of 80,000 Pa.s and 1.0 parts by weight of nano-titanium dioxide scavenger.
  • HPMC hydroxypropyl methylcellulose
  • Step 4 Mix the pretreated phosphogypsum powder, curing agent, retarder, water-retaining agent, and purifying agent uniformly to obtain plastering gypsum powder.
  • Step 5 Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
  • Step 1 Adjust the pH value of the phosphogypsum powder to 7.8 by using 0.8% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
  • Step 2 Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 5 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh
  • the content of the powder in the sieve was 33% by mass.
  • Step 3 Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 4.6 parts by weight of N-methylolacrylamide curing agent, 3.0 parts by weight of salicylic acid accelerator, 280 parts by weight of water, and degraded polyamide 4.0 parts by weight of protein gypsum retarder, 10 parts by weight of hydroxypropyl methylcellulose (HPMC) water-retaining agent with a viscosity of 100000 Pa.s, and 1.8 parts by weight of nano-titanium dioxide scavenger.
  • HPMC hydroxypropyl methylcellulose
  • Step 4 Mix the pretreated phosphogypsum powder, curing agent, accelerator, retarder, water retention agent, and purifier uniformly to obtain plastering gypsum powder.
  • Step 5 Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
  • Step 1 Adjust the pH value of the phosphogypsum powder to 6.9 with 0.35% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
  • Step 2 Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 4 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh
  • the powder content of the sieve was 32% by mass.
  • Step 3 Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 2 parts by weight of magnesium fluorosilicate curing agent, 220 parts by weight of water, 2.3 parts by weight of bone gel protein retarder, and hydroxyl with a viscosity of 60000 Pa.s 20 parts by weight of propyl methyl cellulose (HPMC) water retaining agent and 0.62 parts by weight of nano titanium dioxide scavenger.
  • HPMC propyl methyl cellulose
  • Step 4 Mix the pretreated phosphogypsum powder, curing agent, retarder, water-retaining agent, and purifying agent uniformly to obtain plastering gypsum powder.
  • Step 5 Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
  • Step 1 Adjust the pH value of the phosphogypsum powder to 7.2 with 0.5% by mass quicklime in the amount of phosphogypsum to obtain neutralized phosphogypsum powder.
  • Step 2 The neutralized phosphogypsum powder is calcined in a muffle furnace at 180°C for 2 hours. After aging for 48 hours, it is ground for 5 minutes and passed through a 100 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 meshes. The powder content of the sieve was 34% by mass.
  • Step 3 Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 4.5 parts by weight of sodium fluorosilicate curing agent, 250 parts by weight of water, and protein-based gypsum retarded by calcium salting of degraded polyamide 4.6 parts by weight of hydroxypropyl methylcellulose (HPMC) water retaining agent with a viscosity of 80,000 Pa.s and 1.0 parts by weight of cadmium sulfide scavenger.
  • HPMC hydroxypropyl methylcellulose
  • Step 4 Mix the pretreated phosphogypsum powder, curing agent, retarder, water-retaining agent, and purifying agent uniformly to obtain plastering gypsum powder.
  • Step 5 Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
  • Step 1 Adjust the pH value of the phosphogypsum powder to 7.8 by using 0.8% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
  • Step 2 The neutralized phosphogypsum powder is calcined in a muffle furnace at 160°C for 2 hours. After aging for 48 hours, it is ground for 5 minutes and passed through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 meshes. The content of the powder in the sieve was 33% by mass.
  • Step 3 Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 4.8 parts by weight of N-methylol acrylamide curing agent, 3.0 parts by weight of salicylic acid accelerator, 288 parts by weight of water, and degraded polyamide 4.2 parts by weight of protein gypsum retarder, 11 parts by weight of hydroxypropyl methylcellulose (HPMC) water-retaining agent with a viscosity of 100000 Pa.s, and 1.9 parts by weight of zinc oxide scavenger made by calcium salting.
  • HPMC hydroxypropyl methylcellulose
  • Step 4 Mix the pretreated phosphogypsum powder, curing agent, accelerator, retarder, water retention agent, and purifier uniformly to obtain plastering gypsum powder.
  • Step 5 Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
  • Step 1 Weigh the components: 100 parts by weight of unpretreated phosphogypsum, 280 parts by weight of water, 4.0 parts by weight of protein-based gypsum retarder made by calcium salting of degraded polyamide, and hydroxyl with a viscosity of 100000 Pa.s 10 parts by weight of propyl methyl cellulose (HPMC) water retention agent.
  • HPMC propyl methyl cellulose
  • Step 2 Mix the unpretreated phosphogypsum powder, retarder and water retaining agent uniformly to obtain plastering gypsum powder.
  • Step 3 Mix the mixed plastering gypsum powder with water at the construction site to obtain plastering gypsum products.
  • Pretreated phosphogypsum powder is used to prepare plaster plaster, but no purifying agent is added to plaster plaster
  • Step 1 Adjust the pH value of the phosphogypsum powder to 6.8 by using 0.3% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
  • Step 2 Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 5 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh
  • the powder content of the sieve was 32% by mass.
  • Step 3 Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 2 parts by weight of magnesium fluorosilicate curing agent, 220 parts by weight of water, 2.3 parts by weight of bone glue protein retarder, and hydroxyl with a viscosity of 60000 Pa.s 20 parts by weight of propyl methyl cellulose (HPMC) water retaining agent.
  • HPMC propyl methyl cellulose
  • Step 4 Mix the pretreated phosphogypsum powder, curing agent, retarder, and water retention agent uniformly to obtain plastering gypsum powder.
  • Step 5 Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster that can be mechanized.
  • the pretreated phosphogypsum powder is used to prepare plastering gypsum, but no purifying agent is added to the plastering gypsum.
  • Step 1 Adjust the pH value of the phosphogypsum powder to 6.9 with 0.35% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
  • Step 2 Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 4 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh
  • the powder content of the sieve was 32% by mass.
  • Step 3 Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 2 parts by weight of magnesium fluorosilicate curing agent, 220 parts by weight of water, 2.3 parts by weight of bone gel protein retarder, and hydroxyl with a viscosity of 60000 Pa.s 20 parts by weight of propyl methyl cellulose (HPMC) water retaining agent.
  • HPMC propyl methyl cellulose
  • Step 4 Mix the pretreated phosphogypsum powder, curing agent, retarder, and water retention agent uniformly to obtain plastering gypsum powder.
  • Step 5 Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster that can be mechanized.
  • Example 1 the machine-sprayed surface plastering gypsum slurry obtained in Example 1 to Example 6 has an initial setting time of more than 1 hour, a final setting time of much less than 8 hours, and a water retention rate of more than 97%.
  • the strength, compressive strength, tensile bonding strength, and purification efficiency all meet the requirements of national standards and industry standards, and all indicators are higher than those of commercially available products.
  • Comparative Example 1 shows that the unpretreated phosphogypsum powder does not use a curing agent, and the indexes of the obtained plaster gypsum cannot meet the requirements of national standards.
  • Example 1 and Comparative Example 2 and Example 4 and Comparative Example 3 shows that the plaster gypsum added with nano-titanium dioxide purifying agent has the purification function and the purification effect is good.
  • the consistency of the plastering gypsum of Examples 1 to 6 is significantly higher than that of the commercial products of Comparative Examples 4 and 5, indicating that the plastering gypsum slurry of Examples 1 to 6 has high fluidity and good workability. Suitable for mechanical spraying. In addition, the slurry has high water retention rate, almost no bleeding, high tensile bonding strength, and good slurry cohesion, indicating that the construction effect of plastering gypsum is better than that of commercially available products.

Abstract

A machine-spraying surface gypsum plaster having a purification function, comprising pre-treatment phosphogypsum powder, a curing agent, water, a retarder, a water retaining agent, and a cleaning agent, optionally further comprising an accelerator. The mass ratio of the pre-treatment phosphogypsum powder, the curing agent, water, the retarder, the water retaining agent, and the cleaning agent is 100:(1.5-5):(200-300):(2-5):(5-25):(0.5-2), and provided is a preparation method of the gypsum plaster. The machine-spraying surface gypsum plaster eliminates the harm of soluble phosphorus and fluorine in phosphogypsum, solidifies harmful ions in the phosphogypsum, and implements the reuse of the phosphogypsum.

Description

一种具有净化功能的机喷面层抹灰石膏及其制备方法Plastering gypsum for machine-sprayed surface layer with purification function and preparation method thereof 技术领域Technical field
本申请涉及但不限于建筑材料领域，具体地，涉及但不限于一种具有净化功能的机喷面层抹灰石膏及其制备方法。This application relates to but not limited to the field of building materials, in particular, to but not limited to a machine spray surface plaster plaster with purification function and a preparation method thereof.
背景技术Background technique
抹灰石膏是近年来发展迅速的新型找平材料，其主要是以石膏为主要胶凝材料，加入掺合料、外加剂等制成的抹灰材料，广泛应用于内墙及顶板的找平及装饰。在建筑工程中，抹灰石膏具有良好的和易性、流动性、保水性、保温隔热性能和适当的防火性能。采用抹灰石膏涂抹后的墙面致密平整，且能够调节室内湿度。因此，抹灰石膏是一种材料性能、施工性能和使用功能良好的墙体抹灰找平材料，广泛应用于工业与民用建筑。Plastering gypsum is a new leveling material that has developed rapidly in recent years. It is mainly made of gypsum as the main cementing material, adding admixtures, admixtures, etc., and is widely used in the leveling and decoration of interior walls and ceilings. . In construction projects, plastering gypsum has good workability, fluidity, water retention, thermal insulation properties and appropriate fire resistance. The walls after plastering are dense and smooth, and the indoor humidity can be adjusted. Therefore, plastering gypsum is a wall plastering and leveling material with good material properties, construction performance and use functions, and is widely used in industrial and civil buildings.
近年来，抹灰石膏代替石灰砂浆和水泥砂浆抹灰是建筑墙面装饰装修的一个发展趋势。机喷面层抹灰石膏成为建筑内墙抹灰材料发展的新亮点。利用机喷面层抹灰石膏进行抹面工程，可有效实现节约工程总造价、节约人工费，加快工程施工进度，成为大型建筑工地的迫切需求。制备具有净化功能的面层抹灰石膏，利用了墙体的面积大的特点从而起到净化空气的作用。In recent years, plastering plaster instead of lime mortar and cement mortar plastering is a development trend in building wall decoration. Plastering gypsum for machine-jet surface layer has become a new bright spot in the development of plastering materials for interior walls of buildings. The use of machine-sprayed plastering plaster for plastering works can effectively save the total cost of the project, save labor costs, and accelerate the construction progress of the project, which has become an urgent need for large construction sites. The surface plaster plaster with purification function is prepared, and the large area of the wall is used to purify the air.
磷石膏是湿法制取磷酸过程的工业副产品，每生产1吨磷酸约产生5吨的磷石膏，目前我国磷石膏累计堆存量已超3亿吨。特别地，自2018年起，中国已开始向排污企业征收25元/吨的固废环境保护税，因此磷石膏这种再生石膏资源的利用刻不容缓。Phosphogypsum is an industrial by-product of the process of preparing phosphoric acid by wet process. About 5 tons of phosphogypsum are produced for every 1 ton of phosphoric acid produced. At present, the accumulated stock of phosphogypsum in my country has exceeded 300 million tons. In particular, since 2018, China has begun to levy a solid waste environmental protection tax of 25 yuan/ton from sewage companies, so the utilization of phosphogypsum, a regenerated gypsum resource, cannot be delayed.
发明概述Summary of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics detailed in this article. This summary is not intended to limit the scope of protection of the claims.
目前的抹灰石膏以脱硫石膏和建筑石膏为石膏来源的较多，采用磷石膏制备抹灰石膏的研究鲜有报道。因为磷石膏酸度大、杂质含量高、使用效果 不稳定，直接用来替代天然石膏或脱硫石膏制备抹灰石膏，产品凝结时间快、工作性能不好，粘聚性差、机械喷涂后面层易脱落，施工的整体效果不好。Currently, most plastering gypsum uses desulphurization gypsum and construction gypsum as gypsum sources, and there are few reports on the use of phosphogypsum to prepare plaster gypsum. Because phosphogypsum has high acidity, high impurity content, and unstable use effect, it is directly used to replace natural gypsum or desulfurized gypsum to prepare plastering gypsum. The product has fast setting time, poor working performance, poor cohesion, and the layer after mechanical spraying is easy to fall off. The overall effect of construction is not good.
在对现有技术进行悉心研究的基础上，本申请的发明人发现，将磷石膏进行无害化预处理，让其中的有害杂质在磷石膏胶结过程中固化，呈现化学惰性，是一种实现磷石膏再利用的有效方式。本申请对磷石膏进行预处理，在石膏胶结固化过程中利用固化剂使杂质离子固化，不扩散迁移，使得磷石膏满足普通建筑石膏的使用要求。On the basis of careful research on the prior art, the inventor of the present application found that the harmless pretreatment of phosphogypsum so that the harmful impurities in the phosphogypsum can be solidified during the phosphogypsum cementing process, showing chemical inertness, is a realization An effective way to reuse phosphogypsum. In this application, the phosphogypsum is pretreated. During the gypsum cementation and curing process, the curing agent is used to solidify the impurity ions without diffusion and migration, so that the phosphogypsum meets the requirements of ordinary building gypsum.
此外，现阶段机械抹灰石膏产品的制备技术和施工技术并不成熟，利用磷石膏这种工业固废生产适合机械喷涂且具有净化功能的抹灰石膏技术更是空白。本申请在对磷石膏进行预处理的基础上，通过缓凝剂与保水剂相互配合，制备得到满足机械喷涂工作性能和产品质量要求的面层抹灰石膏产品，该面层抹灰石膏的流动性、粘聚性、保水性优良，适合机械喷涂，另外该面层抹灰石膏还兼具净化甲醛的能力，是符合中国国家和行业标准要求的能净化空气的机喷面层抹灰石膏。In addition, the preparation technology and construction technology of mechanical plastering gypsum products are not mature at this stage. The use of phosphogypsum, an industrial solid waste, to produce plastering gypsum that is suitable for mechanical spraying and has a purification function is even blank. Based on the pretreatment of phosphogypsum, this application prepares a surface plaster plaster product that meets the requirements of mechanical spraying performance and product quality through the coordination of retarder and water retention agent. The flow of the surface plaster plaster It has excellent properties, cohesion and water retention, and is suitable for mechanical spraying. In addition, the surface plaster also has the ability to purify formaldehyde. It is a machine spray surface plaster that can purify air and meets the requirements of China's national and industry standards.
本申请提供了一种具有净化功能的机喷面层抹灰石膏，所述面层抹灰石膏的原料包括如下组分：预处理的磷石膏粉、固化剂、水、缓凝剂、保水剂和净化剂。This application provides a machine-jet surface plaster plaster with purification function. The raw material of the surface plaster plaster includes the following components: pretreated phosphogypsum powder, curing agent, water, retarder, water retention agent And purifiers.
在一些实施方式中，所述预处理的磷石膏粉、所述固化剂、所述水、所述缓凝剂、所述保水剂、所述净化剂的质量比可以为100:(1.5至5):(200至300):(2至5):(5至25):(0.5至2)。In some embodiments, the mass ratio of the pretreated phosphogypsum powder, the curing agent, the water, the retarder, the water-retaining agent, and the purifying agent may be 100: (1.5 to 5 ):(200 to 300):(2 to 5):(5 to 25):(0.5 to 2).
在一些实施方式中，所述预处理的磷石膏粉可以通过调节磷石膏的pH值至中性或弱碱性，并经过煅烧、陈化、粉磨以及过筛处理得到。In some embodiments, the pretreated phosphogypsum powder can be obtained by adjusting the pH value of the phosphogypsum to neutral or weakly alkaline, and undergoing calcination, aging, grinding and sieving treatments.
在一些实施方式中，可以将磷石膏的pH值调节至6.5至8。In some embodiments, the pH value of phosphogypsum can be adjusted to 6.5 to 8.
在一些实施方式中，可以用生石灰将磷石膏的pH值调节至6.5至8。生石灰CaO与磷石膏中的可溶性P 2O 5、F -发生反应生成惰性物质，可消除可溶磷和氟的危害。 In some embodiments, the pH of phosphogypsum can be adjusted to 6.5 to 8 with quicklime. The quicklime CaO reacts with the soluble P 2 O 5 and F - in the phosphogypsum to generate inert substances, which can eliminate the harm of soluble phosphorus and fluorine.
在一些实施方式中，生石灰掺加量可以为磷石膏用量的0.2质量％至1.0质量％。In some embodiments, the added amount of quicklime may be 0.2% to 1.0% by mass of the amount of phosphogypsum.
在一些实施方式中，所述煅烧的温度可以在150℃至200℃范围内。In some embodiments, the calcination temperature may be in the range of 150°C to 200°C.
在一些实施方式中，所述煅烧的时间可以在1.5小时至4小时范围内。In some embodiments, the calcination time may be in the range of 1.5 hours to 4 hours.
在一些实施方式中，所述陈化的时间可以在24小时至72小时范围内。In some embodiments, the aging time may be in the range of 24 hours to 72 hours.
在一些实施方式中，所述粉磨的时间可以在3分钟至10分钟范围内。In some embodiments, the grinding time may be in the range of 3 minutes to 10 minutes.
在一些实施方式中，所述过筛可以包括将粉磨后的磷石膏粉过50目至200目筛。In some embodiments, the sieving may include passing the ground phosphogypsum powder through a 50 to 200 mesh sieve.
在一些实施方式中，可以将磷石膏在150℃至200℃下煅烧1.5小时至4小时，陈化24小时至72小时后，粉磨3分钟至10分钟，过50目至200目筛，得到所述预处理的磷石膏粉。In some embodiments, the phosphogypsum can be calcined at 150°C to 200°C for 1.5 hours to 4 hours, after aging for 24 hours to 72 hours, pulverized for 3 minutes to 10 minutes, and passed through a 50 mesh to 200 mesh sieve to obtain The pretreated phosphogypsum powder.
在一些实施方式中，可以将调节pH值至中性或弱碱性后的磷石膏在160℃煅烧2小时，陈化48小时后粉磨5分钟。In some embodiments, the phosphogypsum after adjusting the pH to neutral or weakly alkaline can be calcined at 160°C for 2 hours, aged for 48 hours, and ground for 5 minutes.
在一些实施方式中，可以将调节pH值至中性或弱碱性后的磷石膏在180℃煅烧2小时，陈化48小时后粉磨5分钟。In some embodiments, the phosphogypsum after adjusting the pH to neutral or weakly alkaline can be calcined at 180°C for 2 hours, aged for 48 hours, and ground for 5 minutes.
在一些实施方式中，可以在过80目筛后得到所述预处理的磷石膏粉。In some embodiments, the pretreated phosphogypsum powder can be obtained after passing through an 80-mesh sieve.
在一些实施方式中，在所述预处理的磷石膏粉中，能通过200目筛的粉体含量不低于30质量％。In some embodiments, in the pretreated phosphogypsum powder, the content of powder that can pass a 200-mesh sieve is not less than 30% by mass.
在一些实施方式中，所述固化剂可以选自无机固化剂(例如氟硅酸盐类固化剂)以及有机固化剂(例如胺类固化剂)中的任意一种或更多种，当所述固化剂为胺类固化剂时，所述抹灰石膏还可以包括促进剂。In some embodiments, the curing agent may be selected from any one or more of inorganic curing agents (such as fluorosilicate curing agents) and organic curing agents (such as amine curing agents). When the curing agent is an amine curing agent, the plastering gypsum may also include an accelerator.
在一些实施方式中，所述胺类固化剂与所述促进剂的质量比可以为1:(0.5至1)In some embodiments, the mass ratio of the amine curing agent to the accelerator may be 1: (0.5 to 1)
在一些实施方式中，所述氟硅酸盐类固化剂可以选自氟硅酸镁、氟硅酸锌、氟硅酸钙和氟硅酸钠中的任意一种或更多种。In some embodiments, the fluorosilicate curing agent may be selected from any one or more of magnesium fluorosilicate, zinc fluorosilicate, calcium fluorosilicate, and sodium fluorosilicate.
在一些实施方式中，所述胺类固化剂可以选自4,4’-二氨基二苯基甲烷、三乙烯四胺、二乙烯三胺、N-羟甲基丙烯酰胺、聚丙稀苯胺、间苯二胺和四乙基溴化胺中的任意一种或更多种。In some embodiments, the amine curing agent can be selected from 4,4'-diaminodiphenylmethane, triethylenetetramine, diethylenetriamine, N-methylolacrylamide, polyacrylaniline, and Any one or more of phenylenediamine and tetraethylamine bromide.
在一些实施方式中，所述促进剂可以选自水杨酸、甲醛、苯甲醛、甲醇、 乙醇、正丙醇、叔丁醇、异丁醇和环己醇中的任意一种或更多种。In some embodiments, the accelerator may be selected from any one or more of salicylic acid, formaldehyde, benzaldehyde, methanol, ethanol, n-propanol, tert-butanol, isobutanol, and cyclohexanol.
本申请的发明人发现，预处理磷石膏工艺过程中的煅烧处理可消除磷石膏中的有机物，生石灰CaO调节pH的同时与磷石膏中的可溶性P 2O 5、F -发生反应生成惰性物质，可消除可溶磷和氟的危害。 The inventor of the present application found that the calcination treatment in the pretreatment process of phosphogypsum can eliminate the organic matter in the phosphogypsum. The quicklime CaO adjusts the pH while reacting with the soluble P 2 O 5 and F - in the phosphogypsum to generate inert substances. It can eliminate the harm of soluble phosphorus and fluorine.
采用上述固化剂作用于磷石膏后，能有效阻止杂质离子(包括可溶性P 2O 5、F -和金属离子等)对石膏颗粒间双电层结构的破坏和损伤，限制杂质离子的交换活动。经研究，其原因在于，固化剂产生的化学力能封闭杂质离子的扩散路径，使磷石膏颗粒凝聚力增强，在磷石膏遇水凝结硬化的过程中胶结固化，不再渗透扩散出磷石膏。 After the curing agent is used on the phosphogypsum, it can effectively prevent impurity ions (including soluble P 2 O 5 , F - and metal ions) from destroying and damaging the electric double layer structure between gypsum particles, and restrict the exchange activity of impurity ions. After research, the reason is that the chemical force generated by the curing agent can close the diffusion path of impurity ions, and enhance the cohesion of the phosphogypsum particles. When the phosphogypsum is cured and hardened with water, it will no longer penetrate and diffuse out of the phosphogypsum.
在一些实施方式中，所述缓凝剂可以选自柠檬酸、柠檬酸钠、六偏磷酸钠、硼砂和蛋白质类缓凝剂中的任意一种或更多种。In some embodiments, the retarder may be selected from any one or more of citric acid, sodium citrate, sodium hexametaphosphate, borax, and protein retarders.
在一些实施方式中，所述蛋白质类缓凝剂可以选自骨胶蛋白质缓凝剂和降解聚酰胺经钙盐化而成的蛋白质类石膏缓凝剂中的任意一种或更多种。In some embodiments, the protein-based retarder may be selected from any one or more of bone glue protein retarder and protein-based gypsum retarder formed by calcium salting of degraded polyamide.
在一些实施方式中，所述保水剂可以选自羟丙基甲基纤维素、聚丙烯酸钠和聚丙烯酰胺中的任意一种或更多种。In some embodiments, the water retaining agent may be selected from any one or more of hydroxypropyl methylcellulose, sodium polyacrylate and polyacrylamide.
在一些实施方式中，所述羟丙基甲基纤维素可以包括粘度等级在40000Pa.s至200000Pa.s范围内的缓溶性羟丙基甲基纤维素。In some embodiments, the hydroxypropyl methyl cellulose may include slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 40,000 Pa.s to 200,000 Pa.s.
在一些实施方式中，所述羟丙基甲基纤维素可以包括粘度等级在60000Pa.s至100000Pa.s范围内的缓溶性羟丙基甲基纤维素。In some embodiments, the hydroxypropyl methyl cellulose may include slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 60000 Pa.s to 100000 Pa.s.
在一些实施方式中，所述净化剂可以选自纳米二氧化钛(TiO 2)、磷酸二氧化钛、氧化锌(ZnO)、氧化锡(SnO 2)、二氧化锆(ZrO 2)、和硫化镉(CdS)中的任意一种或更多种。 In some embodiments, the purifying agent may be selected from nano-titanium dioxide (TiO 2 ), titanium dioxide phosphate, zinc oxide (ZnO), tin oxide (SnO 2 ), zirconium dioxide (ZrO 2 ), and cadmium sulfide (CdS) Any one or more of them.
本申请还提供了所述机喷面层抹灰石膏的制备方法，所述制备方法包括：The application also provides a preparation method of the machine-sprayed surface layer plaster plaster, the preparation method includes:
将所述预处理的磷石膏粉、所述固化剂、所述缓凝剂、所述保水剂、所述净化剂以及任选地促进剂混合均匀，得到抹灰石膏粉；Mixing the pretreated phosphogypsum powder, the curing agent, the retarder, the water-retaining agent, the purifying agent, and optionally the accelerator uniformly to obtain plastering gypsum powder;
在施工现场将所述抹灰石膏粉与水混合均匀，得到所述机喷面层抹灰石膏。The plastering gypsum powder and water are evenly mixed at the construction site to obtain the machine-sprayed surface layer plastering gypsum.
在制备方法的一些实施方式中，所述预处理的磷石膏粉:所述固化剂:所述水:所述缓凝剂:所述保水剂：所述净化剂的质量比可以为100:(1.5至5):(200至300):(2至5):(5至25):(0.5至2)。In some embodiments of the preparation method, the mass ratio of the pretreated phosphogypsum powder: the curing agent: the water: the retarder: the water retaining agent: the purifying agent may be 100:( 1.5 to 5): (200 to 300): (2 to 5): (5 to 25): (0.5 to 2).
在制备方法的一些实施方式中，所述固化剂可以选自无机固化剂(例如氟硅酸盐类固化剂)以及有机固化剂(例如胺类固化剂)中的任意一种或更多种，当所述固化剂为胺类固化剂时，还可以包括促进剂。In some embodiments of the preparation method, the curing agent may be selected from any one or more of inorganic curing agents (for example, fluorosilicate curing agents) and organic curing agents (for example, amine curing agents), When the curing agent is an amine curing agent, an accelerator may also be included.
在制备方法的一些实施方式中，所述胺类固化剂与所述促进剂的质量比可以为1:(0.5至1)。In some embodiments of the preparation method, the mass ratio of the amine curing agent to the accelerator may be 1: (0.5 to 1).
在制备方法的一些实施方式中，所述氟硅酸盐类固化剂可以选自选自氟硅酸镁、氟硅酸锌、氟硅酸钙和氟硅酸钠中的任意一种或更多种。In some embodiments of the preparation method, the fluorosilicate curing agent may be selected from any one or more selected from magnesium fluorosilicate, zinc fluorosilicate, calcium fluorosilicate, and sodium fluorosilicate. Kind.
在制备方法的一些实施方式中，所述胺类固化剂可以选自4,4-二氨基二苯基甲烷、三乙烯四胺，二乙烯三胺、N-羟甲基丙烯酰胺、聚丙稀苯胺、间苯二胺和四乙基溴化胺中的任意一种或更多种。In some embodiments of the preparation method, the amine curing agent may be selected from 4,4-diaminodiphenylmethane, triethylenetetramine, diethylenetriamine, N-methylolacrylamide, polyacrylaniline , Any one or more of m-phenylenediamine and tetraethylamine bromide.
在制备方法的一些实施方式中，所述促进剂可以选自水杨酸、甲醛、苯甲醛、甲醇、乙醇、正丙醇、叔丁醇、异丁醇和环己醇中的任意一种或更多种。In some embodiments of the preparation method, the accelerator may be selected from any one or more of salicylic acid, formaldehyde, benzaldehyde, methanol, ethanol, n-propanol, tert-butanol, isobutanol, and cyclohexanol. Many kinds.
在制备方法的一些实施方式中，所述缓凝剂可以选自柠檬酸、柠檬酸钠、六偏磷酸钠、硼砂和蛋白质类缓凝剂中的任意一种或更多种。In some embodiments of the preparation method, the retarder may be selected from any one or more of citric acid, sodium citrate, sodium hexametaphosphate, borax and protein retarders.
在制备方法的一些实施方式中，所述蛋白质类缓凝剂可以选自骨胶蛋白质缓凝剂和降解聚酰胺经钙盐化而成的蛋白质类石膏缓凝剂中的任意一种或更多种。In some embodiments of the preparation method, the protein-based retarder can be selected from any one or more of bone gel protein retarder and protein-based gypsum retarder formed by calcium salting of degraded polyamide .
在制备方法的一些实施方式中，所述保水剂可以选自羟丙基甲基纤维素、聚丙烯酸钠和聚丙烯酰胺中的任意一种或更多种。In some embodiments of the preparation method, the water retaining agent may be selected from any one or more of hydroxypropyl methylcellulose, sodium polyacrylate, and polyacrylamide.
在制备方法的一些实施方式中，所述羟丙基甲基纤维素可以包括粘度等级在40000Pa.s至200000Pa.s范围内的缓溶性羟丙基甲基纤维素。In some embodiments of the preparation method, the hydroxypropyl methyl cellulose may include slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 40,000 Pa.s to 200,000 Pa.s.
在制备方法的一些实施方式中，所述羟丙基甲基纤维素可以包括粘度等级在60000Pa.s至100000Pa.s范围内的缓溶性羟丙基甲基纤维素。In some embodiments of the preparation method, the hydroxypropyl methyl cellulose may include slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 60000 Pa.s to 100000 Pa.s.
在制备方法的一些实施方式中，所述净化剂可以选自纳米二氧化钛 (TiO 2)、磷酸二氧化钛、氧化锌(ZnO)、氧化锡(SnO 2)、二氧化锆(ZrO 2)和硫化镉(CdS)中的任意一种或更多种，在示例性实施方式中，所述净化剂可以为纳米二氧化钛。 In some embodiments of the preparation method, the purifying agent may be selected from nano titanium dioxide (TiO 2 ), titanium dioxide phosphate, zinc oxide (ZnO), tin oxide (SnO 2 ), zirconium dioxide (ZrO 2 ), and cadmium sulfide ( Any one or more of CdS), in an exemplary embodiment, the purification agent may be nano titanium dioxide.
应理解，抹灰石膏原料中使用的固化剂、缓凝剂、保水剂、净化剂和促进剂，并不限于上述所列举的具体材料，能够实现各种试剂的作用的材料均可用于本申请的抹灰石膏的制备中，上述所列举的具体材料并非对本申请作出任何形式上或实质上的限定。It should be understood that the curing agent, retarder, water-retaining agent, purifying agent and accelerator used in the plastering gypsum raw materials are not limited to the specific materials listed above, and materials that can achieve the effects of various reagents can be used in this application In the preparation of plastering gypsum, the specific materials listed above do not limit the application in any form or substance.
本申请具有的有益效果在于：The beneficial effects of this application are:
1、采用的磷石膏经中和、煅烧、陈化、固化之后，能够达到建筑石膏的中国国家标准，有害元素不渗透，替代了传统的天然石膏与脱硫石膏，为利用磷石膏替代脱硫石膏和建筑石膏生产机喷抹灰石膏开辟了新路子，实现固体废弃物的再利用；1. After being neutralized, calcined, aged, and solidified, the phosphogypsum used can meet the Chinese national standards for building gypsum. It does not penetrate harmful elements and replaces the traditional natural gypsum and desulfurized gypsum. It is the use of phosphogypsum to replace desulfurized gypsum and The construction gypsum production machine sprays plaster gypsum to open up a new way to realize the reuse of solid waste;
2、采用固化剂，能有效固化磷石膏中的有害杂质离子，增强磷石膏颗粒的凝聚力，使有害杂质离子不再渗透扩散出磷石膏；2. The use of curing agent can effectively solidify harmful impurity ions in phosphogypsum, enhance the cohesion of phosphogypsum particles, and prevent harmful impurity ions from penetrating and diffusing out of phosphogypsum;
3、缓凝剂与保水剂相互配合，制备得到的抹灰石膏的流动性、粘聚性、保水性优良，能够适合机械喷涂，解决了普通抹灰石膏无法机械化施工的难题，机械化抹灰代替人工抹灰，可以大大提高施工效率，缩短工期，简化施工工序；3. The retarder and the water-retaining agent cooperate with each other, and the prepared plaster plaster has excellent fluidity, cohesion and water retention, and can be suitable for mechanical spraying. It solves the problem that ordinary plastering gypsum cannot be mechanized and replaced by mechanized plastering. Manual plastering can greatly improve construction efficiency, shorten construction period, and simplify construction procedures;
4、净化剂与抹灰石膏结合，大面积、充分接触室内空气，净化效果良好。4. Combination of purifying agent and plastering gypsum, large area, full contact with indoor air, good purification effect.
5、制备得到的机喷面层抹灰石膏的各项力学性能均满足要求；5. The mechanical properties of the machine-sprayed plastering plaster prepared meet the requirements;
6、当采用生石灰对磷石膏进行中和处理时，可消除磷石膏中的可溶磷和氟的危害，工艺简单，成本低廉；6. When phosphogypsum is neutralized with quicklime, the harm of soluble phosphorus and fluorine in phosphogypsum can be eliminated, the process is simple and the cost is low;
7、当净化剂采用纳米二氧化钛时，本申请的抹灰石膏喷涂到物体表面后能够形成无机酸非晶体聚合物薄膜，干燥后形成纳米尺寸的微细孔结构，在光(紫外光与可见光均可)的作用下照射发生催化作用，产生具有强氧化作用的氢氧自由基(-OH)，能够有效降解空气中的有毒害气体。7. When the purifier adopts nano-titanium dioxide, the plastering gypsum of the present application can form an inorganic acid amorphous polymer film after spraying on the surface of the object, and form a nano-sized micro-pore structure after drying, which can be exposed to light (ultraviolet light and visible light) Under the action of ), the irradiation takes place catalysis and produces strong oxidizing hydroxyl radicals (-OH), which can effectively degrade toxic and harmful gases in the air.
本申请的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本申请而了解。本申请的目的和其他优 点可通过在说明书、权利要求书所特别指出的结构来实现和获得。Other features and advantages of the present application will be described in the following description, and partly become obvious from the description, or understood by implementing the present application. The purpose and other advantages of this application can be realized and obtained through the structures specifically pointed out in the specification and claims.
详述Detail
为使本申请的目的、技术方案和优点更加清楚明白，下文中将对本申请的实施例进行详细说明。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互任意组合。In order to make the purpose, technical solutions, and advantages of the present application clearer, the embodiments of the present application will be described in detail below. It should be noted that the embodiments in this application and the features in the embodiments can be combined with each other arbitrarily if there is no conflict.
以下实施例中所使用的原料均为普通市售产品。The raw materials used in the following examples are all common commercial products.
实施例1Example 1
步骤1：以磷石膏用量的0.3质量％的生石灰调节磷石膏粉的pH值至6.8，得到中和处理的磷石膏粉。Step 1: Adjust the pH value of the phosphogypsum powder to 6.8 by using 0.3% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
步骤2：将中和处理的磷石膏粉在马弗炉中160℃煅烧2小时，陈化48小时后粉磨5分钟，过80目筛，得到预处理的磷石膏粉，其中能通过200目筛的粉体的含量为32质量％。Step 2: Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 5 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh The powder content of the sieve was 32% by mass.
步骤3：称量各组分：其中预处理的磷石膏粉100重量份、氟硅酸镁固化剂2重量份、水220重量份、骨胶蛋白质缓凝剂2.3重量份、粘度60000Pa.s的羟丙基甲基纤维素(HPMC)保水剂20重量份、纳米二氧化钛净化剂0.6重量份。Step 3: Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 2 parts by weight of magnesium fluorosilicate curing agent, 220 parts by weight of water, 2.3 parts by weight of bone gel protein retarder, and hydroxyl with a viscosity of 60000 Pa.s 20 parts by weight of propyl methyl cellulose (HPMC) water retaining agent and 0.6 parts by weight of nano titanium dioxide scavenger.
步骤4：将预处理的磷石膏粉、固化剂、缓凝剂、保水剂、净化剂混合均匀，得到抹灰石膏粉。Step 4: Mix the pretreated phosphogypsum powder, curing agent, retarder, water-retaining agent, and purifying agent uniformly to obtain plastering gypsum powder.
步骤5：在施工现场将混合好的抹灰石膏粉与水混合，即可得到具有净化功能且可以机械化施工的机喷面层抹灰石膏。Step 5: Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
实施例2Example 2
步骤1：以磷石膏用量的0.5质量％的生石灰调节磷石膏粉的pH值至7.2，得到中和处理的磷石膏粉。Step 1: Adjust the pH value of the phosphogypsum powder to 7.2 with 0.5% by mass quicklime in the amount of phosphogypsum to obtain neutralized phosphogypsum powder.
步骤2：将中和处理的磷石膏粉在马弗炉中180℃煅烧2小时，陈化48小时后粉磨5分钟，过80目筛，得到预处理的磷石膏粉，其中能通过200目筛的粉体的含量为30质量％。Step 2: The neutralized phosphogypsum powder is calcined in a muffle furnace at 180°C for 2 hours. After aging for 48 hours, it is ground for 5 minutes and passed through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 meshes. The powder content of the sieve was 30% by mass.
步骤3：称量各组分：其中预处理的磷石膏粉100重量份、氟硅酸钠固化剂4重量份、水250重量份、降解聚酰胺经钙盐化而成的蛋白质类石膏缓凝剂4.6重量份、粘度80000Pa.s的羟丙基甲基纤维素(HPMC)保水剂15重量份、纳米二氧化钛净化剂1.0重量份。Step 3: Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 4 parts by weight of sodium fluorosilicate curing agent, 250 parts by weight of water, and protein-based gypsum retarded by calcium salting of degraded polyamide 4.6 parts by weight of hydroxypropyl methylcellulose (HPMC) water-retaining agent with a viscosity of 80,000 Pa.s and 1.0 parts by weight of nano-titanium dioxide scavenger.
步骤4：将预处理的磷石膏粉、固化剂、缓凝剂、保水剂、净化剂混合均匀，得到抹灰石膏粉。Step 4: Mix the pretreated phosphogypsum powder, curing agent, retarder, water-retaining agent, and purifying agent uniformly to obtain plastering gypsum powder.
步骤5：在施工现场将混合好的抹灰石膏粉与水混合，即可得到具有净化功能且可以机械化施工的机喷面层抹灰石膏。Step 5: Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
实施例3Example 3
步骤1：以磷石膏用量的0.8质量％的生石灰调节磷石膏粉的pH值至7.8，得到中和处理的磷石膏粉。Step 1: Adjust the pH value of the phosphogypsum powder to 7.8 by using 0.8% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
步骤2：将中和处理的磷石膏粉在马弗炉中160℃煅烧2小时，陈化48小时后粉磨5分钟，过80目筛，得到预处理的磷石膏粉，其中能通过200目筛的粉体的含量为33质量％。Step 2: Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 5 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh The content of the powder in the sieve was 33% by mass.
步骤3：称量各组分：其中预处理的磷石膏粉100重量份、N-羟甲基丙烯酰胺固化剂4.6重量份、水杨酸促进剂3.0重量份、水280重量份、降解聚酰胺经钙盐化而成的蛋白质类石膏缓凝剂4.0重量份、粘度100000Pa.s的羟丙基甲基纤维素(HPMC)保水剂10重量份、纳米二氧化钛净化剂1.8重量份。Step 3: Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 4.6 parts by weight of N-methylolacrylamide curing agent, 3.0 parts by weight of salicylic acid accelerator, 280 parts by weight of water, and degraded polyamide 4.0 parts by weight of protein gypsum retarder, 10 parts by weight of hydroxypropyl methylcellulose (HPMC) water-retaining agent with a viscosity of 100000 Pa.s, and 1.8 parts by weight of nano-titanium dioxide scavenger.
步骤4：将预处理的磷石膏粉、固化剂、促进剂、缓凝剂、保水剂、净化剂混合均匀，得到抹灰石膏粉。Step 4: Mix the pretreated phosphogypsum powder, curing agent, accelerator, retarder, water retention agent, and purifier uniformly to obtain plastering gypsum powder.
步骤5：在施工现场将混合好的抹灰石膏粉与水混合，即可得到具有净化功能且可以机械化施工的机喷面层抹灰石膏。Step 5: Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
实施例4Example 4
步骤1：以磷石膏用量的0.35质量％的生石灰调节磷石膏粉的pH值至6.9，得到中和处理的磷石膏粉。Step 1: Adjust the pH value of the phosphogypsum powder to 6.9 with 0.35% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
步骤2：将中和处理的磷石膏粉在马弗炉中160℃煅烧2小时，陈化48小时后粉磨4分钟，过80目筛，得到预处理的磷石膏粉，其中能通过200 目筛的粉体的含量为32质量％。Step 2: Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 4 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh The powder content of the sieve was 32% by mass.
步骤3：称量各组分：其中预处理的磷石膏粉100重量份、氟硅酸镁固化剂2重量份、水220重量份、骨胶蛋白质缓凝剂2.3重量份、粘度60000Pa.s的羟丙基甲基纤维素(HPMC)保水剂20重量份、纳米二氧化钛净化剂0.62重量份。Step 3: Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 2 parts by weight of magnesium fluorosilicate curing agent, 220 parts by weight of water, 2.3 parts by weight of bone gel protein retarder, and hydroxyl with a viscosity of 60000 Pa.s 20 parts by weight of propyl methyl cellulose (HPMC) water retaining agent and 0.62 parts by weight of nano titanium dioxide scavenger.
步骤4：将预处理的磷石膏粉、固化剂、缓凝剂、保水剂、净化剂混合均匀，得到抹灰石膏粉。Step 4: Mix the pretreated phosphogypsum powder, curing agent, retarder, water-retaining agent, and purifying agent uniformly to obtain plastering gypsum powder.
步骤5：在施工现场将混合好的抹灰石膏粉与水混合，即可得到具有净化功能且可以机械化施工的机喷面层抹灰石膏。Step 5: Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
实施例5Example 5
步骤1：以磷石膏用量的0.5质量％的生石灰调节磷石膏粉的pH值至7.2，得到中和处理的磷石膏粉。Step 1: Adjust the pH value of the phosphogypsum powder to 7.2 with 0.5% by mass quicklime in the amount of phosphogypsum to obtain neutralized phosphogypsum powder.
步骤2：将中和处理的磷石膏粉在马弗炉中180℃煅烧2小时，陈化48小时后粉磨5分钟，过100目筛，得到预处理的磷石膏粉，其中能通过200目筛的粉体的含量为34质量％。Step 2: The neutralized phosphogypsum powder is calcined in a muffle furnace at 180°C for 2 hours. After aging for 48 hours, it is ground for 5 minutes and passed through a 100 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 meshes. The powder content of the sieve was 34% by mass.
步骤3：称量各组分：其中预处理的磷石膏粉100重量份、氟硅酸钠固化剂4.5重量份、水250重量份、降解聚酰胺经钙盐化而成的蛋白质类石膏缓凝剂4.6重量份、粘度80000Pa.s的羟丙基甲基纤维素(HPMC)保水剂15重量份、硫化镉净化剂1.0重量份。Step 3: Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 4.5 parts by weight of sodium fluorosilicate curing agent, 250 parts by weight of water, and protein-based gypsum retarded by calcium salting of degraded polyamide 4.6 parts by weight of hydroxypropyl methylcellulose (HPMC) water retaining agent with a viscosity of 80,000 Pa.s and 1.0 parts by weight of cadmium sulfide scavenger.
步骤4：将预处理的磷石膏粉、固化剂、缓凝剂、保水剂、净化剂混合均匀，得到抹灰石膏粉。Step 4: Mix the pretreated phosphogypsum powder, curing agent, retarder, water-retaining agent, and purifying agent uniformly to obtain plastering gypsum powder.
步骤5：在施工现场将混合好的抹灰石膏粉与水混合，即可得到具有净化功能且可以机械化施工的机喷面层抹灰石膏。Step 5: Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
实施例6Example 6
步骤1：以磷石膏用量的0.8质量％的生石灰调节磷石膏粉的pH值至7.8，得到中和处理的磷石膏粉。Step 1: Adjust the pH value of the phosphogypsum powder to 7.8 by using 0.8% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
步骤2：将中和处理的磷石膏粉在马弗炉中160℃煅烧2小时，陈化48 小时后粉磨5分钟，过80目筛，得到预处理的磷石膏粉，其中能通过200目筛的粉体的含量为33质量％。Step 2: The neutralized phosphogypsum powder is calcined in a muffle furnace at 160°C for 2 hours. After aging for 48 hours, it is ground for 5 minutes and passed through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 meshes. The content of the powder in the sieve was 33% by mass.
步骤3：称量各组分：其中预处理的磷石膏粉100重量份、N-羟甲基丙烯酰胺固化剂4.8重量份、水杨酸促进剂3.0重量份、水288重量份、降解聚酰胺经钙盐化而成的蛋白质类石膏缓凝剂4.2重量份、粘度100000Pa.s的羟丙基甲基纤维素(HPMC)保水剂11重量份、氧化锌净化剂1.9重量份。Step 3: Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 4.8 parts by weight of N-methylol acrylamide curing agent, 3.0 parts by weight of salicylic acid accelerator, 288 parts by weight of water, and degraded polyamide 4.2 parts by weight of protein gypsum retarder, 11 parts by weight of hydroxypropyl methylcellulose (HPMC) water-retaining agent with a viscosity of 100000 Pa.s, and 1.9 parts by weight of zinc oxide scavenger made by calcium salting.
步骤4：将预处理的磷石膏粉、固化剂、促进剂、缓凝剂、保水剂、净化剂混合均匀，得到抹灰石膏粉。Step 4: Mix the pretreated phosphogypsum powder, curing agent, accelerator, retarder, water retention agent, and purifier uniformly to obtain plastering gypsum powder.
步骤5：在施工现场将混合好的抹灰石膏粉与水混合，即可得到具有净化功能且可以机械化施工的机喷面层抹灰石膏。Step 5: Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster with purification function and mechanized construction.
对比例1Comparative example 1
步骤1：称量各组分：未预处理的磷石膏100重量份、水280重量份、降解聚酰胺经钙盐化而成的蛋白质类石膏缓凝剂4.0重量份、粘度100000Pa.s的羟丙基甲基纤维素(HPMC)的保水剂10重量份。Step 1: Weigh the components: 100 parts by weight of unpretreated phosphogypsum, 280 parts by weight of water, 4.0 parts by weight of protein-based gypsum retarder made by calcium salting of degraded polyamide, and hydroxyl with a viscosity of 100000 Pa.s 10 parts by weight of propyl methyl cellulose (HPMC) water retention agent.
步骤2：将未预处理的磷石膏粉、缓凝剂、保水剂混合均匀，得到抹灰石膏粉。Step 2: Mix the unpretreated phosphogypsum powder, retarder and water retaining agent uniformly to obtain plastering gypsum powder.
步骤3：在施工现场将混合好的抹灰石膏粉与水混合，得到抹灰石膏产品。Step 3: Mix the mixed plastering gypsum powder with water at the construction site to obtain plastering gypsum products.
对比例2Comparative example 2
采用预处理的磷石膏粉制备抹灰石膏，但抹灰石膏中不添加净化剂Pretreated phosphogypsum powder is used to prepare plaster plaster, but no purifying agent is added to plaster plaster
步骤1：以磷石膏用量的0.3质量％的生石灰调节磷石膏粉的pH值至6.8，得到中和处理的磷石膏粉。Step 1: Adjust the pH value of the phosphogypsum powder to 6.8 by using 0.3% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
步骤2：将中和处理的磷石膏粉在马弗炉中160℃煅烧2小时，陈化48小时后粉磨5分钟，过80目筛，得到预处理的磷石膏粉，其中能通过200目筛的粉体的含量为32质量％。Step 2: Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 5 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh The powder content of the sieve was 32% by mass.
步骤3：称量各组分：其中预处理的磷石膏粉100重量份、氟硅酸镁固化剂2重量份、水220重量份、骨胶蛋白质缓凝剂2.3重量份、粘度60000Pa.s 的羟丙基甲基纤维素(HPMC)保水剂20重量份。Step 3: Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 2 parts by weight of magnesium fluorosilicate curing agent, 220 parts by weight of water, 2.3 parts by weight of bone glue protein retarder, and hydroxyl with a viscosity of 60000 Pa.s 20 parts by weight of propyl methyl cellulose (HPMC) water retaining agent.
步骤4：将预处理的磷石膏粉、固化剂、缓凝剂、保水剂混合均匀，得到抹灰石膏粉。Step 4: Mix the pretreated phosphogypsum powder, curing agent, retarder, and water retention agent uniformly to obtain plastering gypsum powder.
步骤5：在施工现场将混合好的抹灰石膏粉与水混合，即可得到可以机械化施工的机喷面层抹灰石膏。Step 5: Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster that can be mechanized.
对比例3Comparative example 3
采用预处理的磷石膏粉制备抹灰石膏，但抹灰石膏中不添加净化剂。The pretreated phosphogypsum powder is used to prepare plastering gypsum, but no purifying agent is added to the plastering gypsum.
步骤1：以磷石膏用量的0.35质量％的生石灰调节磷石膏粉的pH值至6.9，得到中和处理的磷石膏粉。Step 1: Adjust the pH value of the phosphogypsum powder to 6.9 with 0.35% by mass quicklime in the amount of the phosphogypsum to obtain neutralized phosphogypsum powder.
步骤2：将中和处理的磷石膏粉在马弗炉中160℃煅烧2小时，陈化48小时后粉磨4分钟，过80目筛，得到预处理的磷石膏粉，其中能通过200目筛的粉体的含量为32质量％。Step 2: Calcinate the neutralized phosphogypsum powder in a muffle furnace at 160°C for 2 hours, grind for 4 minutes after aging for 48 hours, and pass through an 80 mesh sieve to obtain pretreated phosphogypsum powder, which can pass 200 mesh The powder content of the sieve was 32% by mass.
步骤3：称量各组分：其中预处理的磷石膏粉100重量份、氟硅酸镁固化剂2重量份、水220重量份、骨胶蛋白质缓凝剂2.3重量份、粘度60000Pa.s的羟丙基甲基纤维素(HPMC)保水剂20重量份。Step 3: Weigh the components: 100 parts by weight of pretreated phosphogypsum powder, 2 parts by weight of magnesium fluorosilicate curing agent, 220 parts by weight of water, 2.3 parts by weight of bone gel protein retarder, and hydroxyl with a viscosity of 60000 Pa.s 20 parts by weight of propyl methyl cellulose (HPMC) water retaining agent.
步骤4：将预处理的磷石膏粉、固化剂、缓凝剂、保水剂混合均匀，得到抹灰石膏粉。Step 4: Mix the pretreated phosphogypsum powder, curing agent, retarder, and water retention agent uniformly to obtain plastering gypsum powder.
步骤5：在施工现场将混合好的抹灰石膏粉与水混合，即可得到可以机械化施工的机喷面层抹灰石膏。Step 5: Mix the mixed plastering gypsum powder with water at the construction site to obtain machine-sprayed surface plastering plaster that can be mechanized.
对比例4Comparative example 4
市售普通机喷面层抹灰石膏，购买自芜湖和业建材科技有限公司，由天然石膏制成。Commercially available ordinary machine spray surface plaster plaster, purchased from Wuhu Heye Building Material Technology Co., Ltd., made of natural gypsum.
对比例5Comparative example 5
市售普通机喷面层抹灰石膏，购买自无锡轩亚建筑材料有限公司，由脱硫石膏制成。Commercially available ordinary machine spray surface plaster plaster, purchased from Wuxi Xuanya Building Materials Co., Ltd., made of desulfurized gypsum.
依据中国国家标准GB/T28627-2012《抹灰石膏》，对实施例和对比例得到的抹灰石膏的基本性能进行检测，结果如表1所示。抹灰石膏属于不具有 装饰功能的喷涂材料，因此参照JCT-1074-2008-《室内空气净化功能涂覆材料净化性能》中II类产品标准进行判定其净化性能和净化效果持久性，结果如表2所示。According to the Chinese national standard GB/T28627-2012 "Plaster Gypsum", the basic properties of the plaster gypsum obtained in the Examples and Comparative Examples were tested, and the results are shown in Table 1. Plastering gypsum is a spraying material that does not have decorative functions. Therefore, refer to JCT-1074-2008-"Purification Performance of Indoor Air Purification Function Coating Material" to determine its purification performance and purification effect durability. The results are shown in the table 2 shown.
表1 面层抹灰石膏的基本性能Table 1 Basic performance of surface plastering plaster
Figure PCTCN2019094250-appb-000001
Figure PCTCN2019094250-appb-000001
表2 面层抹灰石膏的净化效果Table 2 Purification effect of surface plaster plaster
Figure PCTCN2019094250-appb-000002
Figure PCTCN2019094250-appb-000002
Figure PCTCN2019094250-appb-000003
Figure PCTCN2019094250-appb-000003
从表1可以看出，实施例1至实施例6得到的机喷面层抹灰石膏浆，初凝时间大于1小时，终凝时间远远小于8小时，保水率在97％以上，抗折强度、抗压强度、拉伸粘结强度、净化效率均满足国家标准及行业标准要求，且各项指标均高于市售产品。It can be seen from Table 1 that the machine-sprayed surface plastering gypsum slurry obtained in Example 1 to Example 6 has an initial setting time of more than 1 hour, a final setting time of much less than 8 hours, and a water retention rate of more than 97%. The strength, compressive strength, tensile bonding strength, and purification efficiency all meet the requirements of national standards and industry standards, and all indicators are higher than those of commercially available products.
对比例1与实施例1至至实施例6相比，说明未预处理的磷石膏粉，不使用固化剂、得到的抹灰石膏的指标均不能满足国家标准要求。Compared with Examples 1 to 6, Comparative Example 1 shows that the unpretreated phosphogypsum powder does not use a curing agent, and the indexes of the obtained plaster gypsum cannot meet the requirements of national standards.
实施例1与对比例2对比，实施例4与对比例3对比，说明添加纳米二氧化钛净化剂的抹灰石膏具备净化功能，净化效果良好。The comparison between Example 1 and Comparative Example 2 and Example 4 and Comparative Example 3 shows that the plaster gypsum added with nano-titanium dioxide purifying agent has the purification function and the purification effect is good.
实施例1至至实施例6的抹灰石膏稠度明显高于对比例4、5的市售产品，说明实施例1至至实施例6的抹灰石膏浆体的流动性大、工作性好，适合机械喷涂。另外浆体保水率高、几乎无泌水，拉伸粘结强度大、浆体粘聚性好，说明抹灰石膏的施工效果好于市售产品。The consistency of the plastering gypsum of Examples 1 to 6 is significantly higher than that of the commercial products of Comparative Examples 4 and 5, indicating that the plastering gypsum slurry of Examples 1 to 6 has high fluidity and good workability. Suitable for mechanical spraying. In addition, the slurry has high water retention rate, almost no bleeding, high tensile bonding strength, and good slurry cohesion, indicating that the construction effect of plastering gypsum is better than that of commercially available products.
本公开内容是本申请实施例的原则的示例，并非对本申请作出任何形式上或实质上的限定，或将本申请限定到具体的实施方案。对本领域的技术人员而言，很显然本申请实施例的技术方案的要素、方法和***等，可以进行变动、改变、改动、演变，而不背离如上所述的本申请的实施例、技术方案的，如权利要求中所定义的原理、精神和范围。这些变动、改变、改动、演变的实施方案均包括在本申请的等同实施例内，这些等同实施例均包括在本申请的由权利要求界定的范围内。虽然可以许多不同形式来使本申请实施例具体化，但此处详细描述的是本申请的一些实施方案。此外，本申请的实施例包括此处所述的各种实施方案的一些或全部的任意可能的组合，也包括在本申请的由权利要求界定的范围内。在本申请中或在任一个引用的专利、引用的专利申请或其它引用的资料中任何地方所提及的所有专利、专利申请和 其它引用资料据此通过引用以其整体并入。The present disclosure is an example of the principles of the embodiments of the application, and does not limit the application in any form or substance, or limit the application to specific embodiments. For those skilled in the art, it is obvious that the elements, methods, and systems of the technical solutions of the embodiments of the application can be changed, changed, modified, and evolved without departing from the embodiments and technical solutions of the application as described above. , As defined in the claims, the principle, spirit and scope. The implementation schemes of these changes, changes, modifications, and evolutions are all included in the equivalent embodiments of the present application, and these equivalent embodiments are all included in the scope defined by the claims of the present application. Although the embodiments of the present application can be embodied in many different forms, some embodiments of the present application are described in detail here. In addition, the examples of the present application include any possible combination of some or all of the various embodiments described herein, and are also included in the scope of the present application defined by the claims. All patents, patent applications and other cited materials mentioned in this application or anywhere in any cited patent, cited patent application or other cited materials are hereby incorporated by reference in their entirety.
以上公开内容规定为说明性的而不是穷尽性的。对于本领域技术人员来说，本说明书会暗示许多变化和可选择方案。所有这些可选择方案和变化旨在被包括在本权利要求的范围内，其中术语“包括”意思是“包括，但不限于”。The above disclosure is provided as illustrative rather than exhaustive. For those skilled in the art, this description will suggest many changes and alternatives. All these alternatives and variations are intended to be included within the scope of the claims, where the term "including" means "including, but not limited to."
在此完成了对本申请可选择的实施方案的描述。本领域技术人员可认识到此处所述的实施方案的其它等效变换，这些等效变换也为由附于本文的权利要求所包括。This completes the description of the alternative embodiments of the application. Those skilled in the art may recognize other equivalent transformations of the embodiments described herein, and these equivalent transformations are also encompassed by the claims attached herein.

Claims (15)

  1. 一种具有净化功能的机喷面层抹灰石膏，所述机喷面层抹灰石膏包括预处理的磷石膏粉、固化剂、水、缓凝剂、保水剂以及净化剂，任选地，还包括促进剂。A machine-sprayed surface layer plastering gypsum with purification function. The machine-sprayed surface layer plastering gypsum includes pretreated phosphogypsum powder, curing agent, water, retarder, water retaining agent and purifying agent, optionally, Also includes accelerators.
  2. 根据权利要求1所述的具有净化功能的机喷面层抹灰石膏，其中，所述预处理的磷石膏粉、所述固化剂、所述水、所述缓凝剂、所述保水剂、所述净化剂的质量比为100:(1.5至5):(200至300):(2至5):(5至25):(0.5至2)。The machine spray surface plaster plaster with purification function according to claim 1, wherein the pretreated phosphogypsum powder, the curing agent, the water, the retarder, the water retaining agent, The mass ratio of the purifying agent is 100: (1.5 to 5): (200 to 300): (2 to 5): (5 to 25): (0.5 to 2).
  3. 根据权利要求1或2所述的具有净化功能的机喷面层抹灰石膏，其中，所述预处理的磷石膏粉通过以下方法来制备：The machine-jet surface plaster plaster with purification function according to claim 1 or 2, wherein the pretreated phosphogypsum powder is prepared by the following method:
    调节磷石膏的pH，煅烧，陈化，粉磨以及过筛。Adjust the pH of phosphogypsum, calcining, aging, grinding and sieving.
  4. 根据权利要求3所述的具有净化功能的机喷面层抹灰石膏，其中，The machine-sprayed surface plaster plaster with purification function according to claim 3, wherein:
    用生石灰将所述磷石膏的pH调节至6.5-8，Adjust the pH of the phosphogypsum to 6.5-8 with quicklime,
    生石灰掺加量为所述磷石膏用量的0.2质量％-1.0质量％，The added amount of quicklime is 0.2%-1.0% by mass of the amount of phosphogypsum,
    将调节pH后的磷石膏在150℃至200℃下煅烧1.5小时至4小时，陈化24小时至72小时，粉磨3分钟至10分钟，过50目至200目筛。The pH-adjusted phosphogypsum is calcined at 150°C to 200°C for 1.5 hours to 4 hours, aged for 24 hours to 72 hours, ground for 3 minutes to 10 minutes, and passed through a sieve of 50 mesh to 200 mesh.
  5. 根据权利要求1至4中任一项所述的具有净化功能的机喷面层抹灰石膏，其中，所述固化剂选自无机固化剂和有机固化剂中的任意一种或更多种。The machine-jet surface plaster plaster with purification function according to any one of claims 1 to 4, wherein the curing agent is selected from any one or more of inorganic curing agents and organic curing agents.
  6. 根据权利要求5所述的具有净化功能的机喷面层抹灰石膏，其中，所述无机固化剂包括氟硅酸盐类固化剂，所述有机固化剂包括胺类固化剂。The machine-sprayed surface plaster plaster with purification function according to claim 5, wherein the inorganic curing agent comprises a fluorosilicate curing agent, and the organic curing agent comprises an amine curing agent.
  7. 根据权利要求6所述的具有净化功能的机喷面层抹灰石膏，其中，所述氟硅酸盐类固化剂选自氟硅酸镁、氟硅酸锌、氟硅酸钙和氟硅酸钠中的任意一种或更多种。The machine-sprayed surface plaster plaster with purifying function according to claim 6, wherein the fluorosilicate curing agent is selected from magnesium fluorosilicate, zinc fluorosilicate, calcium fluorosilicate and fluorosilicic acid Any one or more of sodium.
  8. 根据权利要求6或7所述的具有净化功能的机喷面层抹灰石膏，其中，所述胺类固化剂选自4,4’-二氨基二苯基甲烷、三乙烯四胺，二乙烯三胺、N-羟甲基丙烯酰胺、聚丙稀苯胺、间苯二胺和四乙基溴化胺中的任意一种或更多种。The machine-jet surface plaster plaster with purification function according to claim 6 or 7, wherein the amine curing agent is selected from 4,4'-diaminodiphenylmethane, triethylenetetramine, diethylene Any one or more of triamine, N-methylolacrylamide, polypropylene aniline, m-phenylenediamine, and tetraethyl amine bromide.
  9. 根据权利要求6至8中任一项所述的具有净化功能的机喷面层抹灰石膏，其中，当所述固化剂为胺类固化剂时，所述机喷面层抹灰石膏包括促进剂，所述胺类固化剂与所述促进剂的质量比为1:(0.5至1)。The machine-sprayed surface layer plastering gypsum with purification function according to any one of claims 6 to 8, wherein, when the curing agent is an amine curing agent, the machine-sprayed surface layer plastering gypsum includes accelerating The mass ratio of the amine curing agent to the accelerator is 1: (0.5 to 1).
  10. 根据权利要求1至9中任一项所述的具有净化功能的机喷面层抹灰石膏，其中，所述促进剂选自水杨酸、甲醛、苯甲醛、甲醇、乙醇、正丙醇、叔丁醇、异丁醇和环己醇中的任意一种或更多种。The machine spray surface plaster plaster with purification function according to any one of claims 1 to 9, wherein the accelerator is selected from salicylic acid, formaldehyde, benzaldehyde, methanol, ethanol, n-propanol, Any one or more of tert-butanol, isobutanol, and cyclohexanol.
  11. 根据权利要求1至10中任一项所述的具有净化功能的机喷面层抹灰石膏，其中，所述缓凝剂选自柠檬酸、柠檬酸钠、六偏磷酸钠、硼砂和蛋白质类缓凝剂中的任意一种或更多种。The machine-sprayed surface plaster plaster with purification function according to any one of claims 1 to 10, wherein the retarder is selected from citric acid, sodium citrate, sodium hexametaphosphate, borax and protein Any one or more of retarders.
  12. 根据权利要求1至11中任一项所述的具有净化功能的机喷面层抹灰石膏，其中，所述保水剂选自羟丙基甲基纤维素、聚丙烯酸钠和聚丙烯酰胺中的任意一种或更多种，The machine spray surface plaster plaster with purification function according to any one of claims 1 to 11, wherein the water retaining agent is selected from the group consisting of hydroxypropyl methylcellulose, sodium polyacrylate and polyacrylamide Any one or more,
    任选地，所述羟丙基甲基纤维素为粘度等级在40000Pa.s至200000Pa.s范围内的缓溶性羟丙基甲基纤维素。Optionally, the hydroxypropyl methyl cellulose is a slow-dissolving hydroxypropyl methyl cellulose with a viscosity grade ranging from 40,000 Pa.s to 200,000 Pa.s.
  13. 根据权利要求1至12中任一项所述的具有净化功能的机喷面层抹灰石膏，其中，所述净化剂选自纳米二氧化钛、磷酸二氧化钛、氧化锌、氧化锡、二氧化锆和硫化镉中的任意一种或更多种。The machine-jet surface plaster plaster with purification function according to any one of claims 1 to 12, wherein the purification agent is selected from the group consisting of nano-titanium dioxide, titanium dioxide phosphate, zinc oxide, tin oxide, zirconium dioxide and sulfide Any one or more of cadmium.
  14. 根据权利要求1至13中任一项所述的具有净化功能的机喷面层抹灰石膏，其中，所述缓凝剂选自骨胶蛋白质缓凝剂和降解聚酰胺经钙盐化而成的蛋白质类石膏缓凝剂中的任意一种或更多种。The machine-sprayed surface plaster plaster with purifying function according to any one of claims 1 to 13, wherein the retarder is selected from the group consisting of bone glue protein retarder and degraded polyamide which is formed by calcium salting Any one or more of protein gypsum retarders.
  15. 权利要求1至14中任一项所述的具有净化功能的机喷面层抹灰石膏的制备方法，所述制备方法包括：The preparation method of machine-sprayed surface layer plaster plaster with purification function according to any one of claims 1 to 14, the preparation method comprising:
    将所述预处理的磷石膏粉、所述固化剂、所述缓凝剂、所述保水剂、所述净化剂以及任选地所述促进剂混合均匀，得到抹灰石膏粉；Mixing the pretreated phosphogypsum powder, the curing agent, the retarder, the water retaining agent, the purifying agent, and optionally the accelerator uniformly to obtain plastering gypsum powder;
    在施工现场将所述抹灰石膏粉与所述水混合均匀，得到所述具有净化功能的机喷面层抹灰石膏。The plastering gypsum powder and the water are uniformly mixed at the construction site to obtain the machine-sprayed surface plastering plaster with purification function.
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Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
CN113968720A (en) * 2021-11-11 2022-01-25 北新集团建材股份有限公司 Gypsum-based dry-mixed mortar and preparation method thereof
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2484399A1 (en) * 1980-06-11 1981-12-18 Viazzi Pierre Building material made from moist gypsum obtd. from phosphate ores - where calcium oxide is added to gypsum to absorb water, thus providing powder used in plaster mouldings
CN101456686A (en) * 2007-12-10 2009-06-17 尹小林 Novel industrial waste gypsum self forming energy-saving process
CN105130355A (en) * 2015-07-19 2015-12-09 北京工业大学 Mechanical-spraying light-weight base layer plastering gypsum and preparation method
CN106431034A (en) * 2016-08-31 2017-02-22 贵州川恒化工股份有限公司 Method for producing building gypsum powder from semi-hydrate phosphogypsum
WO2017198930A1 (en) * 2016-05-18 2017-11-23 Saint-Gobain Weber Binder based on calcium aluminosilicate derivatives for construction materials.
CN108793920A (en) * 2018-07-20 2018-11-13 宁波荣山新型材料有限公司 A kind of ardealite base lightweight plastering gupsum product

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5751186A (en) * 1980-09-08 1982-03-25 Osaka Cement Improvement of gypsum hardened body
CN101597147A (en) * 2009-07-06 2009-12-09 贵州安捷能建筑材料发展有限公司 The processing method of a kind of phosphogypsum, desulphurization gypsum for preparing high strength plaster of Paris
CN103496934B (en) * 2013-09-18 2015-09-30 武汉理工大学 A kind of phosphogypsum foundation base brushing gypsum material and preparation method thereof
FR3021647B1 (en) * 2014-05-28 2021-04-23 Saint Gobain Weber COATING PRODUCT WITH PHOTOCATALYTIC PROPERTIES
CN105688362A (en) * 2016-01-18 2016-06-22 四川大学 Stabilizing agent for phosphogypsum and method for innocent treatment of phosphogypsum

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2484399A1 (en) * 1980-06-11 1981-12-18 Viazzi Pierre Building material made from moist gypsum obtd. from phosphate ores - where calcium oxide is added to gypsum to absorb water, thus providing powder used in plaster mouldings
CN101456686A (en) * 2007-12-10 2009-06-17 尹小林 Novel industrial waste gypsum self forming energy-saving process
CN105130355A (en) * 2015-07-19 2015-12-09 北京工业大学 Mechanical-spraying light-weight base layer plastering gypsum and preparation method
WO2017198930A1 (en) * 2016-05-18 2017-11-23 Saint-Gobain Weber Binder based on calcium aluminosilicate derivatives for construction materials.
CN106431034A (en) * 2016-08-31 2017-02-22 贵州川恒化工股份有限公司 Method for producing building gypsum powder from semi-hydrate phosphogypsum
CN108793920A (en) * 2018-07-20 2018-11-13 宁波荣山新型材料有限公司 A kind of ardealite base lightweight plastering gupsum product

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANG, QIGANG: "Non-official translation: Using Waste Phosphogypsum to Pepare Plastering Gypsum", CHINA RESOURCES COMPREHENSIVE UTILIZATION, no. 1, 25 January 2003 (2003-01-25), DOI: 20191212170858Y *

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