WO2018086277A1 - 一种自保温砌块 - Google Patents

一种自保温砌块 Download PDF

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Publication number
WO2018086277A1
WO2018086277A1 PCT/CN2017/075152 CN2017075152W WO2018086277A1 WO 2018086277 A1 WO2018086277 A1 WO 2018086277A1 CN 2017075152 W CN2017075152 W CN 2017075152W WO 2018086277 A1 WO2018086277 A1 WO 2018086277A1
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wheat straw
mass
acrylic acid
self
mixed solution
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PCT/CN2017/075152
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English (en)
French (fr)
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张建国
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张建国
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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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/1321—Waste slurries, e.g. harbour sludge, industrial muds
    • 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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/1305—Organic additives
    • 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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/131—Inorganic additives
    • 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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/448—Sulphates or sulphites
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Definitions

  • the invention relates to the technical field of materials, in particular to a self-insulating block.
  • the advantage of the external wall self-insulation thermal insulation block is that it is accompanied by the theme construction.
  • the overall construction time of the project is high, the masonry is convenient, the complicated process of secondary insulation is eliminated, the construction cost is reduced, and the price is relatively low.
  • the use of river wall lake sludge sintering new wall materials and composite blocks produced by using fly ash, slag, coal gangue and other materials have been fully utilized in China.
  • Standard bricks are used for load-bearing walls and perforated bricks for frame structure infill walls.
  • the problem is that the wall does not reach 50% of the public construction required by the state, and 65% of the energy-saving insulation effect is built. It is necessary to make insulation on the external wall, costing materials, long construction period, low fire performance, poor sound insulation effect, and external wall insulation still have quality problems such as short service life, easy water seepage and falling off.
  • the self-heavy building has a small earthquake force and is good for earthquake resistance. Compared with the brick-concrete building, the same building, under the same earthquake conditions, the degree of earthquake damage is different.
  • a seismic design fortification level such as brick-concrete building at 7 degrees, It will be destroyed, and at this time the aerated concrete building will only be protected by 6 degrees and will not be destroyed.
  • more than 30 porous concrete buildings showed minor damage, while the adjacent brick-concrete buildings were seriously damaged.
  • a five-story aerated concrete bearing building in Baijiazhuang, Beijing The self-weight is only 700kg/m2.
  • China is a large agricultural country.
  • the annual output of crop straw is as high as 842 million tons, and it is still increasing at a rate of 1.3%. It is a large number of renewable resources in nature, and has the advantages of wide source and low price.
  • this resource has not been fully utilized. More than 95% of straw resources are dissipated into other forms through different utilization channels each year, and resources are wasted.
  • China's crop straw resources are large and wide.
  • its use can be roughly divided into four aspects: as industrial raw materials, mainly used for industrial papermaking; as animal feed; as fertilizer, fertilization and returning to the field; as fuel, rural living energy although In this way, resources have not been properly developed for a long time, and most of them have been burned. This is a waste of natural resources, and it also causes serious environmental pollution. With the concern and reflection of environmental pollution problems in various countries around the world, the application benefits of straw Received the attention of people.
  • an embodiment of the present invention provides a self-insulating block.
  • the present invention provides a self-insulating block comprising the following materials: 45-52 parts by mass of yellow river cement, 37-41 parts by mass of nisanite, and 1.5-polyphenylene sulfide powder. 3.8 parts by mass, glass beads 0.1-2.3 parts by mass, mixture three 1.0-1.3 parts by mass, mixed solution-30-45 parts by mass, additive 2-3wt% of the mixed solution, and a mixed solution of a mass of 0.025- 0.035 wt% of additive two; the mixed solution one includes acrylic acid, polyvinyl alcohol PVA, modified wheat straw and water.
  • the mixture 3 includes: polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate, nano-calcium carbonate, wherein polypropylene: 2,2-methylene - Sodium bis(4,6-di-tert-butylphenyl)phosphate: mass ratio of nano-calcium carbonate is 100:0.6-1.1:0.08-0.12
  • the mixed solution one wherein the acrylic acid is partially neutralized with acrylic acid, and the degree of neutralization of the acrylic acid is 60-70%.
  • the acrylic acid polyvinyl alcohol
  • PVA modified wheat straw: water mass ratio is 20-30:4-5:6-8:60-70, based on the unneutralized acrylic acid.
  • the Nishan stone is a Nishan stone that has passed through a 100 mesh sieve after being pulverized.
  • the additive one is ammonium hydrogencarbonate
  • the additive 2 includes potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 11.5-16.5:1.
  • the preparation method of the modified wheat straw is: drying the wheat straw, crushing with a pulverizer, taking 120 The wheat straw powder of the mesh sieve is added with a sodium hydroxide solution of 15-20 times the mass of the wheat straw powder, and the mixture is soaked for 18-20 hours, suction filtered, the filtrate is discarded, and the remaining solid is washed with water until neutral, after Drying at 50-60 ° C, (the concentration of the sodium hydroxide solution is 6-10 wt%), the wheat straw powder is pretreated, and N, N-di is added in an amount of 40-45 times that of the pretreated wheat straw powder. After methyleneformamide DMF, after stirring for 30-40 min, stirring is continued and maleic anhydride MA is added.
  • the maleic anhydride MA: pretreated wheat straw powder mass ratio is 0.75-0.8:1, and then the temperature is raised to 100-110 ° C.
  • the reaction is carried out, the reaction process is kept stirring, and after 2-6 hours of reaction, the product is cooled to room temperature, the filtrate is removed by filtration, and the solid remaining after filtration is washed 3-4 times, and then dried in an oven at 60 ° C to be modified. Sex wheat straw.
  • the present invention also provides a method for preparing a self-insulating block, and the method for preparing the self-insulating block comprises the following steps:
  • the mass ratio of polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate and nano-calcium carbonate are uniformly mixed and then granulated by 36 twin-screw extrusion processing.
  • the temperature is 205-210 ° C
  • the screw rotation speed is 220-230 r/min
  • the mixture 3 is obtained.
  • the particle size of the mixture 3 is ⁇ 0.8 mm, and is reserved;
  • the wheat straw is dried, crushed with a pulverizer, and the wheat straw powder of 120 mesh sieve is taken, and the sodium hydroxide solution of 15-20 times of the mass of the wheat straw powder is added, and the mixture is soaked for 18-20 hours, and suction-filtered. The filtrate is discarded, and the remaining solid is washed with water to neutrality, and then dried at 50-60 ° C.
  • the sodium hydroxide solution has a mass concentration of 6-10 wt%, and the pretreated wheat straw powder is added, and the pretreated wheat is added.
  • the straw powder is 40-45 times times of N,N-dimethyleneformamide DMF. After stirring for 30-40 min, stirring is continued and maleic anhydride MA is added.
  • the mass ratio of the maleic anhydride MA:pretreated wheat straw powder is 0.75-0.8:1, then the temperature is raised to 100-110 ° C to carry out the reaction, the reaction process is kept stirring, after 2-6 hours of reaction, the product is cooled to room temperature, the solid after filtration is removed by filtration, washed 3-4 times with water, put After being dried in an oven at 60 ° C, the modified wheat straw is obtained, and used;
  • the first stage calcination temperature is 360-380 ° C, calcined 3-4 h, then heated to 1300 ° C ⁇ 1350 ° C in 30 min, the second stage of calcination, calcination time 5 ⁇ 8min; Then, the temperature is lowered to 300-340 ° C in 30 min, the third stage is calcined, the calcination time is 3-5 h; finally, the temperature is raised to 850-880 ° C in 30 min, the calcination is completed for 24-30 h, and the cooling is 24-48 hours, and the self-insulation is obtained. Piece.
  • the additive one is ammonium hydrogencarbonate
  • the additive 2 includes potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 11.5-16.5:1.
  • the additive-added amount is 2-3 wt% of one mass of the mixed solution, and the additive two is added in an amount of 0.025-0.035 wt% of one mass of the mixed solution.
  • the beneficial effects of the invention are: the raw materials are yellow river cement, wheat straw, turning waste into treasure, comprehensive utilization of resources, obvious land-saving effect, and the heat preservation effect can reach the national energy requirement of 50% of the public construction of more than 65% of the energy-saving requirements, masonry
  • the wall does not need to be insulated by the external wall. Compared with the traditional hollow brick masonry, the strength is significantly increased, the weight is reduced by more than 50%, the thermal resistance of the composite wall is increased, the energy consumption is significantly reduced, the self-insulation effect is excellent, and the outer wall is not required.
  • the construction period can be 1/3 in advance, and the same life span of buildings is more than 70 years.
  • the blocks do not need to be dried to save time, and can be dried by using the residual heat of baking, and the calcination energy is low compared to other self-insulating blocks which are currently dried.
  • the obtained thermal insulation block has excellent thermal performance, low water absorption rate of the product, less than 7%, light weight, high strength and good heat preservation effect.
  • the thermal insulation block does not produce secondary by-products, which is environmentally friendly.
  • the self-insulating block has high early strength and can be improved by natural conditions for 7d strength to reach 7.1-7.4 MPa, which greatly shortens the factory cycle of the block.
  • the present invention provides a self-insulating block, the raw materials are yellow river cement, wheat straw, turning waste into treasure, comprehensive utilization of resources, prohibition of real and land-saving effects, and the heat preservation effect can reach the national public construction.
  • 50% of the building is more than 65% energy-saving requirements
  • the wall of the masonry does not need to be insulated by the external wall.
  • the compressive strength is high, but the density is small, the quality is light, the seismic capacity is good, and the sound insulation effect is good.
  • the product has reached the national A1 fire protection standard and has the same life span of more than 70 years.
  • the middle and upper reaches of the Yellow River are mainly mountainous, and the middle part flows through the Loess Plateau of China. It carries a large amount of sediment to the downstream every year. According to the data of the Yellow River River Department, 1.6 billion tons of sediment will be produced each year, up to 3.9 billion tons.
  • the main components are; hydrated silicate, alumina, and contains quartz, feldspar, mica, and sulfate.
  • the Yellow River cement has the characteristics of large viscosity and good plasticity. It can improve the comprehensive performance of the product by combining with other materials such as Nishan stone, polyphenylene sulfide powder and glass microbeads.
  • Nishan Stone It is the mountain rock of Shandong Qufu.
  • the invention provides a self-insulating block, characterized in that the self-insulating block comprises the following raw materials: 45-52 parts by mass of yellow river cement, 37-41 parts by mass of nisanite, and 1.5-3.8 parts by mass of polyphenylene sulfide powder. , glass microbeads 2.1-2.3 parts by mass, mixture three 1.0-1.3 parts by mass, mixed solution-30-45 parts by mass, additive 1-3wt% of the mixed solution, and the mixed solution a mass of 0.025-0.035wt% Additive 2; the mixed solution 1 includes acrylic acid, polyvinyl alcohol PVA, modified wheat straw and water.
  • the mixture 3 includes: polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate, nano-calcium carbonate, wherein polypropylene: 2,2-methylene - Sodium bis(4,6-di-tert-butylphenyl)phosphate: mass ratio of nano-calcium carbonate is 100:0.6-1.1:0.08-0.12
  • the mixed solution one wherein the acrylic acid is partially neutralized with acrylic acid, and the degree of neutralization of the acrylic acid is 60-70%.
  • the acrylic acid polyvinyl alcohol
  • PVA modified wheat straw: water mass ratio is 20-30:4-5:6-8:60-70, based on the unneutralized acrylic acid.
  • the Nishan stone is a Nishan stone that has passed through a 100 mesh sieve after being pulverized.
  • the additive one is ammonium hydrogencarbonate
  • the additive 2 includes potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 11.5-16.5:1.
  • the preparation method of the modified wheat straw is: drying the wheat straw, pulverizing with a pulverizer, taking the wheat straw powder of the 120 mesh sieve, adding a sodium hydroxide solution of 15-20 times the mass of the wheat straw powder, Quiet Soak for 18-20 hours, suction filtration, discard the filtrate, the remaining solid is washed with water to neutral, and then dried at 50-60 ° C.
  • the sodium hydroxide solution has a mass concentration of 6-10 wt%, which is pretreated.
  • the preparation method of the self-insulating block comprises the following steps:
  • the mass ratio of polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate and nano-calcium carbonate are uniformly mixed and then granulated by twin-screw extrusion, and the processing temperature is obtained.
  • the wheat straw is dried, crushed with a pulverizer, and the wheat straw powder of 120 mesh sieve is taken, and the sodium hydroxide solution of 15-20 times of the mass of the wheat straw powder is added, and the mixture is soaked for 18-20 hours, and suction-filtered. The filtrate is discarded, and the remaining solid is washed with water to neutrality, and then dried at 50-60 ° C.
  • the sodium hydroxide solution has a mass concentration of 6-10 wt%, and the pretreated wheat straw powder is added, and the pretreated wheat is added.
  • the straw powder is 40-45 times times of N,N-dimethyleneformamide DMF. After stirring for 30-40 min, stirring is continued and maleic anhydride MA is added.
  • the mass ratio of the maleic anhydride MA:pretreated wheat straw powder is 0.75-0.8:1, then the temperature is raised to 100-110 ° C to carry out the reaction, the reaction process is kept stirring, after 2-6 hours of reaction, the product is cooled to room temperature, the solid after filtration is removed by filtration, washed 3-4 times with water, put After being dried in an oven at 60 ° C, the modified wheat straw is obtained, and used;
  • the first stage calcination temperature is 360-380 ° C, calcined 3-4 h, then heated to 1300 ° C ⁇ 1350 ° C in 30 min, the second stage of calcination, calcination time 5 ⁇ 8min; Then, the temperature is lowered to 300-340 ° C in 30 min, the third stage is calcined, the calcination time is 3-5 h; finally, the temperature is raised to 850-880 ° C in 30 min, the calcination is completed for 24-30 h, and the cooling is 24-48 hours, and the self-insulation is obtained. Piece.
  • the temperatures are all degrees Celsius.
  • the percentages not specified are all by mass.
  • Embodiment 1 Self-insulating block of the present invention
  • Self-insulating block including the following raw materials: 48 parts by weight of Yellow River cement, 37 parts by weight of Nishan stone, 1.5 parts by weight of polyphenylene sulfide powder (Dongguan Shenhua Industrial Investment Co., Ltd.), 2.2 parts by weight of glass beads (Yongqing County Haiyu Glass Beads Co., Ltd.), mixture of 1.0 parts by mass, 35 parts by mass of mixed solution, 2.6 wt% of additive of mixed solution, and additive 2 of 0.030 wt% of mixed solution; mixed solution Among them, acrylic acid, polyvinyl alcohol PVA (CAS No. 9002-89-5, model 1799), modified wheat straw and water are included. Wherein acrylic acid is partially neutralized with acrylic acid, and the degree of neutralization of acrylic acid is 70%.
  • Wheat straw is wheat straw in Dezhou, Shandong.
  • the mixture 3 includes: polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate, nano-calcium carbonate, wherein polypropylene: 2,2-methylene - Sodium bis(4,6-di-tert-butylphenyl)phosphate: nano-calcium carbonate mass ratio 100:1:0.08. 2,2-methylene-bis(4,6-di-tert-butylphenyl) Sodium phosphate (CAS No. 85209-91-2, Luoyang Zhongda Chemical Co., Ltd.).
  • acrylic acid polyvinyl alcohol PVA: modified wheat straw: water mass ratio is 30:4:7:62 (in which partially neutralized acrylic acid is converted into equimolar un-neutralized acrylic acid, according to And acrylic acid mass,); wherein the amount of polyvinyl alcohol PVA is the net content of polyvinyl alcohol, not the content of polyvinyl alcohol PVA solution;
  • Nishan Stone is a Nishan Stone that has been crushed and passed through a 100 mesh sieve.
  • the additive one is ammonium hydrogencarbonate
  • the additive 2 includes potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 14:1. (N-methylol acrylamide CAS No.924-42-5)
  • the preparation method comprises the following steps:
  • the mass ratio of polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate and nano-calcium carbonate are uniformly mixed and then granulated by 36 twin-screw extrusion processing. Temperature 205 ⁇ 210 ° C, screw speed 220r / min, to obtain a mixture of three, the particle size of the mixture three ⁇ 1mm, spare; the polypropylene grade used is T30S;
  • the wheat straw is dried, crushed with a pulverizer, and the wheat straw powder of 120 mesh sieve is taken, and the sodium hydroxide solution 20 times of the mass of the wheat straw powder is added, and the mixture is soaked for 20 hours, filtered, and the filtrate is discarded. After the residual solid is washed with water to neutrality, and dried at 60 ° C, the sodium hydroxide solution has a mass concentration of 6 wt%, and the pretreated wheat straw powder is obtained, and 40 times of N is added relative to the pretreated wheat straw powder.
  • N-Dimethyleneformamide DMF (CAS No. 68-12-2)
  • maleic anhydride MA CAS No.
  • the maleic anhydride MA The pretreatment wheat straw powder mass ratio is 0.75:1, then the temperature is raised to 110 ° C to carry out the reaction, the reaction process is kept stirring, after the reaction for 6 hours, the product is cooled to room temperature, the filtrate is removed by filtration, and the remaining solid after filtration is washed 3 times with water. After being dried in an oven at 60 ° C, the modified wheat straw is obtained and used;
  • the first stage calcination temperature is 360 ° C, calcination for 4 h, then heating to 1350 ° C in 30 min, the second stage calcination, calcination time 5 min; and then cooling to 340 ° C in 30 min,
  • the third stage is calcined, the calcination time is 4 h; finally, the temperature is raised to 880 ° C in 30 min, the calcination is completed for 24 h, and the natural cooling is carried out for 24 hours to obtain a self-insulating block.
  • a self-insulating block comprises the following materials: 52 parts by weight of yellow river cement, 39 parts by weight of nisanite, 2.0 parts by mass of polyphenylene sulfide powder, 2.3 parts of glass beads, 1.2 parts by mass of mixture, mixed solution a 45 parts by mass of the additive 1 in an amount of 2.8 wt% of the mixed solution and an additive 2 in an amount of 0.025 wt% of the mixed solution;
  • the mixed solution 1 comprises acrylic acid, polyvinyl alcohol PVA, modified wheat straw and water .
  • the mixture 3 includes: polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate, nano-calcium carbonate, wherein polypropylene: 2,2-methylene - Sodium bis(4,6-di-tert-butylphenyl)phosphate: The mass ratio of nano-calcium carbonate is 100:0.6:0.12.
  • the solution one was mixed, wherein acrylic acid was partially neutralized with acrylic acid, and the degree of neutralization of acrylic acid was 60%.
  • acrylic acid polyvinyl alcohol
  • PVA modified wheat straw: water mass ratio of 25:4.5:7:70, based on the unneutralized acrylic acid.
  • Nishan stone is a Nishan stone that has been crushed and passed through a 100 mesh sieve.
  • the additive one is ammonium hydrogencarbonate
  • the additive 2 includes potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 11.5:1.
  • the preparation method of the self-insulating block comprises the following steps:
  • the mass ratio of polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate and nano-calcium carbonate are uniformly mixed and then granulated by twin-screw extrusion, and the processing temperature is obtained. 205 ⁇ 210 ° C, screw speed 230r / min, to obtain a mixture of three, the particle size of the mixture three ⁇ 1mm, spare; the polypropylene grade used is T30S;
  • the wheat straw is dried, crushed with a pulverizer, and the wheat straw powder of 120 mesh sieve is taken, and the sodium hydroxide solution of 15 times the mass of the wheat straw powder is added, and the mixture is soaked for 18 hours, filtered, and the filtrate is discarded. Remaining After the residual solid is washed with water to neutrality, and dried at 50 ° C, the sodium hydroxide solution has a mass concentration of 10 wt%, and the wheat straw powder is pretreated, and N is added 45 times times the pretreated wheat straw powder. After stirring for 30 minutes, N-dimethylideneformamide DMF was stirred and added with maleic anhydride MA.
  • the maleic anhydride MA:pretreated wheat straw powder mass ratio was 0.8:1, and then the temperature was raised to 100 ° C to carry out the reaction.
  • the reaction process was kept stirring. After reacting for 2 hours, the product was cooled to room temperature, and the filtrate was removed by filtration. The remaining solid in the upper layer of the filter paper after filtration was washed four times with water, and then dried in an oven at 60 ° C to obtain modified wheat straw. ,spare;
  • the first stage calcination temperature is 380 ° C, calcination for 3 h, then heating to 1300 ° C in 30 min, the second stage calcination, calcination time 8 min; and then cooling to 300 ° C in 30 min, The third stage calcination, calcination time 5h; finally heated to 850 ° C in 30min, calcined for 30h sintering, natural cooling for 24 hours, to obtain self-insulating blocks.
  • a self-insulating block comprises the following materials: 45 parts by weight of yellow river cement, 41 parts by mass of nisanite, 3.5 parts by mass of polyphenylene sulfide powder, 2.1 parts by mass of glass microbeads, 1.3 parts by mass of mixture, and mixing 39 parts by mass of the solution, an additive of 2.1% by weight of the mixed solution, and an additive 2 of 0.035 wt% of the mixed solution;
  • the mixed solution 1 comprises acrylic acid, polyvinyl alcohol PVA, modified wheat straw and water.
  • the mixture 3 includes: polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate, nano-calcium carbonate, wherein polypropylene: 2,2-methylene - Sodium bis(4,6-di-tert-butylphenyl)phosphate: The mass ratio of nano-calcium carbonate is 100:1.1:0.1.
  • acrylic acid polyvinyl alcohol
  • PVA modified wheat straw: water mass ratio of 20:5:8:65, based on the unneutralized acrylic acid.
  • Nishan stone is a Nishan stone that has been crushed and passed through a 100 mesh sieve.
  • the additive one is ammonium hydrogencarbonate
  • the additive 2 includes potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 16.5:1.
  • the preparation method of the self-insulating block comprises the following steps:
  • the mass ratio of polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate and nano-calcium carbonate are uniformly mixed and then granulated by twin-screw extrusion, and the processing temperature is obtained. 205 ⁇ 210 ° C, screw speed 225r / min, to obtain a mixture of three, the particle size of the mixture three ⁇ 1mm, spare; the polypropylene grade used is T30S;
  • the wheat straw was dried, crushed with a universal grinder, and the wheat straw powder of 120 mesh sieve was taken, and a sodium hydroxide solution having a mass concentration of 8 wt% relative to the mass of the wheat straw powder was added, and the mixture was allowed to stand for 19 hours. After suction filtration, the filtrate was discarded, and the remaining solid was washed with water until neutral, and then dried at 55 ° C to obtain pretreated wheat straw powder, and added N, N-dimethylidene which was 42 times times the pretreated wheat straw powder. After the formic acid DMF was stirred for 35 min, stirring was continued and maleic anhydride MA was added.
  • the maleic anhydride MA: pretreated wheat straw powder mass ratio was 0.78:1, and then the temperature was raised to 100 ° C to carry out the reaction, and the reaction was kept stirring. After 4 hours, the product was cooled to room temperature, and the filtrate was removed by filtration. The remaining solid of the upper layer of the filter paper after filtration was washed three times with water, and then dried in an oven at 60 ° C to obtain modified wheat straw, which was used;
  • Additive 2 then continue stirring for 4 minutes, then stop stirring, then heat up to 245 ° C in 10 min, after constant temperature at 245 ° C for 15 min, cool down to 60 ° C, hold at 60 ° C for 9 hours to solidify, then release the blank Drying at 60 ° C for 30 h;
  • the first stage calcination temperature is 370 ° C, calcination for 4 h, then heating to 1320 ° C in 30 min, the second stage calcination, calcination time 7 min; and then cooling to 320 ° C in 30 min, The third stage calcination, calcination time 3h; finally heated to 860 ° C in 30min, calcined 26h after sintering, natural cooling for 30 hours, to obtain self-insulating blocks.
  • a self-insulating block comprises the following materials: 50 parts by weight of yellow river cement, 38 parts by weight of Nishan stone, 3 parts by mass of polyphenylene sulfide powder, 2.3 parts of glass beads, and 1.1 parts by mass of mixture, mixed solution 30 parts by mass, an additive of 2.5% by weight of the mixed solution, and an additive 2 of 0.028% by weight of the mixed solution;
  • the mixed solution includes acrylic acid, polyvinyl alcohol PVA, modified wheat straw and water .
  • the mixture 3 includes: polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate, nano-calcium carbonate, wherein polypropylene: 2,2-methylene - Sodium bis(4,6-di-tert-butylphenyl)phosphate: The mass ratio of nano-calcium carbonate is 100:0.9:0.12.
  • the solution one was mixed, wherein acrylic acid was partially neutralized with acrylic acid, and the degree of neutralization of acrylic acid was 62%.
  • acrylic acid polyvinyl alcohol
  • PVA modified wheat straw: water mass ratio of 25:5:8:60, based on the unneutralized acrylic acid.
  • Nishan stone is a Nishan stone that has been crushed and passed through a 100 mesh sieve.
  • the additive one is ammonium hydrogencarbonate
  • the additive two is potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 13:1.
  • the preparation method of the self-insulating block comprises the following steps:
  • the mass ratio of polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate and nano-calcium carbonate are uniformly mixed and then granulated by twin-screw extrusion, and the processing temperature is obtained. 205 ⁇ 210 ° C, screw speed 220r / min, to obtain a mixture of three, the particle size of the mixture three ⁇ 1mm, spare; the polypropylene grade used is T30S;
  • the wheat straw is dried, crushed with a pulverizer, and the wheat straw powder of 120 mesh sieve is taken, and a sodium hydroxide solution having a mass concentration of 7 wt% relative to the mass of the wheat straw powder is added, and the mixture is soaked for 18 hours. Filtration, the filtrate was discarded, and the remaining solid was washed with water until neutral, and then dried at 60 ° C to obtain pretreated wheat straw powder, and added N, N-dimethylene A relative to the pretreated wheat straw powder 45 times times. After stirring for 40 minutes, the amide DMF was stirred and added with maleic anhydride MA.
  • the maleic anhydride MA: pretreated wheat straw powder mass ratio was 0.75:1, and then the temperature was raised to 110 ° C to carry out the reaction, and the reaction was kept stirring, and the reaction 2 After -6 hours, the product was cooled to room temperature, the filtrate was removed by filtration, and the remaining solid in the upper layer of the filter paper was taken, washed 4 times with water, and dried in an oven at 60 ° C to obtain modified wheat straw, which was used;
  • the first stage calcination temperature is 375 ° C, calcination for 3 h, then heating to 1330 ° C in 30 min, the second stage calcination, calcination time 6 min; and then cooling to 310 ° C in 30 min, The third stage of calcination, calcination time 4h; finally heated to 870 ° C within 30min, calcined for 24h After sintering, it was naturally cooled for 48 hours to obtain a self-insulating block.
  • a self-insulating block comprises the following materials: 49 parts by weight of yellow river cement, 40 parts by weight of nisanite, 3.8 parts by mass of polyphenylene sulfide powder, 2.2 parts of glass beads, 1.0 parts by mass of mixture, mixed solution a 38 parts by mass, an additive 1 of 3% by weight of the mixed solution, and an additive 2 of 0.032% by weight of the mixed solution;
  • the mixed solution 1 comprises acrylic acid, polyvinyl alcohol PVA, modified wheat straw and water .
  • the mixture 3 includes: polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate, nano-calcium carbonate, wherein polypropylene: 2,2-methylene - Sodium bis(4,6-di-tert-butylphenyl)phosphate: The mass ratio of nano-calcium carbonate is 100:0.8:0.09.
  • the acrylic acid polyvinyl alcohol
  • PVA modified wheat straw: water mass ratio was 30:4:6:70 based on the unneutralized acrylic acid.
  • Nishan stone is a Nishan stone that has been crushed and passed through a 100 mesh sieve.
  • the additive one is ammonium hydrogencarbonate
  • the additive two is potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 15:1.
  • the preparation method of the self-insulating block comprises the following steps:
  • the mass ratio of polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate and nano-calcium carbonate are uniformly mixed and then granulated by twin-screw extrusion, and the processing temperature is obtained. 205 ⁇ 210 ° C, screw speed 230r / min, to obtain a mixture of three, the particle size of the mixture three ⁇ 1mm, spare; the polypropylene grade used is T30S;
  • the wheat straw is dried, crushed with a pulverizer, and the wheat straw powder of 120 mesh sieve is taken, and a sodium hydroxide solution having a mass concentration of 10 wt% relative to the mass of the wheat straw powder is added, and the mixture is soaked for 20 hours, and pumped. Filtration, the filtrate was discarded, and the remaining solid was washed with water until neutral, and then dried at 50 ° C to obtain pretreated wheat straw powder, and added N, N-dimethylene A relative to the pretreated wheat straw powder 45 times times. After stirring for 40 min, the amide DMF was stirred and added with maleic anhydride MA.
  • the maleic anhydride MA: pretreated wheat straw powder mass ratio was 0.8:1, and then the temperature was raised to ° C to carry out the reaction, and the reaction was kept stirring for 3 hours. After that, the product was cooled to room temperature, and the filtrate was removed by filtration, and the remaining solid after filtration was washed with water. After that, it is dried in an oven at 60 ° C to obtain modified wheat straw, and used;
  • the amount of additive 1 is 3% by weight of the mixed solution, and the additive is added in an amount of 0.032% by weight of the additive solution, and then stirring is continued for 5 minutes, then the stirring is stopped, and then the temperature is raised to 240 ° C in 10 minutes, and the temperature is raised at 240 ° C. After 15 minutes, the temperature was lowered to 70 ° C, and the film was solidified at 70 ° C for 9 hours, and then the mold release body was dried at 60 ° C for 28 hours;
  • the first stage calcination temperature is 360 ° C, calcination for 4 h, then heating to 1310 ° C in 30 min, the second stage calcination, calcination time 6 min; and then cooling to 340 ° C in 30 min, The third stage calcination, calcination time 4h; finally heated to 880 ° C in 30min, calcined 24h sintering, natural cooling for 36 hours, to obtain self-insulating blocks.
  • a self-insulating block comprises the following raw materials: 46 parts by weight of yellow river cement, 39 parts by weight of nisanite, 2.9 parts by mass of polyphenylene sulfide powder, 2.1 parts of glass microbeads, 1.1 parts by mass of mixture, mixed solution One 30 parts by mass of the additive 1 in an amount of 2% by weight of the mixed solution and the additive 2 in an amount of 0.034% by weight of the mixed solution; the mixed solution one comprises acrylic acid, polyvinyl alcohol PVA, modified wheat straw and water.
  • the mixture 3 includes: polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate, nano-calcium carbonate, wherein polypropylene: 2,2-methylene - Sodium bis(4,6-di-tert-butylphenyl)phosphate: The mass ratio of nano-calcium carbonate is 100:0.9:0.11.
  • acrylic acid polyvinyl alcohol
  • PVA modified wheat straw: water mass ratio of 23:5:7:66, based on the unneutralized acrylic acid.
  • Nishan stone is a Nishan stone that has been crushed and passed through a 100 mesh sieve.
  • the additive one is ammonium hydrogencarbonate
  • the additive two is potassium persulfate and N-methylol acrylamide, wherein the mass ratio of potassium persulfate: N-methylol acrylamide is 16:1.
  • the preparation method of the self-insulating block comprises the following steps:
  • the mass ratio of polypropylene, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphate and nano-calcium carbonate are uniformly mixed and then granulated by twin-screw extrusion, and the processing temperature is obtained. 205 ⁇ 210 ° C, screw speed 228r / min, to obtain a mixture of three, the particle size of the mixture three ⁇ 1mm, spare; the polypropylene grade used is T30S;
  • the wheat straw was dried, crushed with a pulverizer, and the wheat straw powder of 120 mesh sieve was taken, and a sodium hydroxide solution of 17 times the mass of the wheat straw powder was added, and the mixture was allowed to stand for 19 hours, suction filtered, and the filtrate was discarded. After the remaining solid is washed with water to neutrality, and dried at 55 ° C, the sodium hydroxide solution has a mass concentration of 6 wt%, and the wheat straw powder is pretreated, and N is added in an amount of 43 times that of the pretreated wheat straw powder. N-Dimethyleneformamide DMF, after stirring for 36 min, stirring was continued and maleic anhydride MA was added.
  • the maleic anhydride MA: pretreated wheat straw powder mass ratio was 0.76:1, and then the temperature was raised to 104 ° C for reaction.
  • the reaction process was kept stirring. After reacting for 4 hours, the product was cooled to room temperature, and the filtrate was removed by filtration. The remaining solid of the upper layer of the filter paper after filtration was washed three times with water, and then dried in an oven at 60 ° C to obtain modified wheat straw. ,spare;
  • the first stage calcination temperature is 380 ° C, calcination for 3 h, then heating to 1330 ° C in 30 min, the second stage calcination, calcination time 6 min; and then cooling to 340 ° C in 30 min, The third stage calcination, calcination time 3h; finally heated to 870 ° C in 30min, calcined 26h after sintering, natural cooling for 26 hours, to obtain self-insulating blocks.
  • Yellow River silt standard brick (porous brick), 70% of Yellow River cement, 30% coal gangue, single block weight 2.4kg, compressive strength 15MPa or more, used for building load-bearing walls, masonry must be used for external wall insulation, labor, cost High, long construction period, poor insulation effect.
  • Concrete brick 240*115*53, single block weight 3.5kg, main raw material cement 15%, stone nitrate 10%, stone powder 45%, fly ash 30%, compressive strength greater than 15MPa, used for building load-bearing walls, itself Since it is significant, the wall must be insulated by external walls. Workers are labor intensive, labor-intensive, costly, and have poor thermal insulation.
  • Preparation method cloth ⁇ mixing ⁇ conveying ⁇ forming ⁇ falling board ⁇ finished product maintenance ⁇ finished product.
  • Example 1 On the basis of Example 1, the Yellow River cement and Nishan stone were replaced with ordinary Portland cement and sand, and other conditions were unchanged.
  • the density is 752kg/m 3 , the compressive strength is 7.1Mpa, the water absorption rate is 13%, and the weathering resistance is 0.68. External insulation is required.
  • Example 1 On the basis of Example 1, no other polyphenylene sulfide powder and glass microbeads were added.
  • the density is 740kg/m 3 , the compressive strength is 7.0Mpa, the water absorption rate is 14%, and the weathering resistance is 0.65. External insulation is required.
  • Example 1 On the basis of Example 1, no mixed solution and additives were added, and only the moisture in the mixed solution was retained, and other conditions were unchanged.
  • the calcination of the body requires heating to 950-1250 ° C, calcination for 36-48 h, density of 822 kg / m 3 , compressive strength of 7.0 Mpa, water absorption of 13%, and weathering resistance of 0.64.
  • Example 1 On the basis of Example 1, no modified wheat straw was added to the mixed solution, and other conditions were unchanged.
  • the density is 751kg/m 3 , the compressive strength is 7.1Mpa, the water absorption rate is 15%, and the weathering resistance is 0.69.
  • the density is 760kg/m 3
  • the compressive strength is 7.5Mpa
  • the water absorption rate is 15%
  • the weathering resistance is 0.67. External insulation is required.
  • the density is 591kg/m 3 , the compressive strength is 7.6Mpa, the water absorption rate is 11%, and the weathering resistance is 0.63.
  • Light-weight buildings have small earthquakes and are good for earthquakes. Compared with brick-concrete buildings, the same buildings, under the same earthquake conditions, have different seismic damage levels. A seismic design fortification level, under the same foundation conditions, light-weight buildings The number of layers can be increased and economically advantageous.
  • the density of the self-insulating block is less than 50% of the block of the same strength grade, the stability is high, the comprehensive performance is good, and the construction cost is comprehensively reduced by more than 20%.

Abstract

一种自保温砌块，包括以下原料：黄河胶泥45-52质量份、尼山石37-41质量份、聚苯硫醚粉1.5-3.8质量份、玻璃微珠2.1-2.3质量份、混合物三1.0-1.3质量份、混合溶液一30-45质量份、占混合溶液一质量2-3wt％的添加剂一和占混合溶液一质量0.025-0.035wt％的添加剂二；该混合溶液一中，包括丙烯酸、聚乙烯醇、改性小麦秸秆和水。

Description

一种自保温砌块 技术领域
本发明涉及材料技术领域，特别涉及一种自保温砌块。
背景技术
外墙自保温保温砌块优点是伴随主题施工，项目整体施工时效性高，砌筑方便，免去二次做保温的繁琐工序，降低了建筑成本，价格相对较低。利用江河湖泊淤泥烧结新型墙材及利用粉煤灰、矿渣、煤矸石等材料生产的复合砌块在我国已得到充分的利用。标砖用于承重墙、多孔砖用于框架结构填充墙。存在的问题为墙体达不到国家规定的公建50％，居建65％的节能保温效果。需在外墙做保温，费工费料、工期长、防火性能低、隔音效果差、外墙保温还存在着使用寿命短、易渗水、脱落等质量问题。
自重轻的建筑地震力就小，对抗震有利，和砖混建筑相比，同样的建筑，同样的地震条件下，震害程度相差一个地震设计设防级别，如砖混建筑在达7度设防，它会受破坏，而此时加气混凝土建筑只达6度设防，就不会破坏。1975年海城地震时，30余幢多孔混凝土建筑展害轻微，而邻近的砖混建筑则震害严重；1976年唐山地震时，北京市白家庄的一栋五层加气混凝土承重楼，自重仅700kg/m2，当时处于地震烈度为6度强的情况下，震后没有出现新的裂缝，而在50m处的四层混合结构的住宅，下部却产生大斜裂缝。在相同地基条件下，自重轻的建筑的层数可以增多，经济上有利。
另外我国是农业大国,每年农作物秸秆的产量高达8.42亿吨,且还在以1.3％的速度增加,是自然界中数量庞大的可再生资源,且具有来源广泛、价格低廉的优点。但是,这一资源并未得到充分利用,每年有95％以上秸秆资源通过不同的利用途径转化成其他形式而被耗散,资源浪费严重。中国农作物秸秆资源量大面广,现阶段其用途大致可分为4个方面:作为工业原料,主要用于工业造纸；作为畜牧饲料；作为肥料,造肥还田；作为燃料,农村生活能源虽然如此,资源仍然长期未得到合理的开发,大部分都被焚烧,这是对天然资源的浪费,同时还造成了严重的环境污染随着世界各国对环境污染问题的关注和反思,秸秆的应用益受到人们的重视。
因此合理利用现有资源开发符合国家节能保温标准的自重轻，强度高的墙体材料是目前研发的方向。
发明内容
为了满足国家公建50％居建65％的节能保温标准需求，充分利用现有资源，节能降耗，降低自保温砌块的自重，，同时解决砌体材料强度和导热系数不能同时保证的巨大矛盾,本发明实施例提供了一种自保温砌块。利用我国江河湖泊大量的淤泥资源及小麦秸秆为原料，资源综合利用，生产能耗低，保温效果好，防火阻燃抗老化，耐久性高，寿命长，性能稳定，质量轻抗震能力好，安全稳固性好的产品，外墙不再做保温，即可达到国家公建50％居建65％的节能保温标准。因外墙不需再做外墙保温，建设成本与传统的做法相比较每平方米造价可降低20％以上，工期可提前30％以上，一项技术同时支持国家禁实、节地、环保、防火、资源综合利用多项基本国策。
为了实现上述发明目的，本发明提供了一种自保温砌块，所述自保温砌块包括以下原料：黄河胶泥45-52质量份、尼山石37-41质量份，聚苯硫醚粉1.5-3.8质量份、玻璃微珠2.1-2.3质量份、混合物三1.0-1.3质量份、混合溶液一30-45质量份、占混合溶液一质量2-3wt％的添加剂一和占混合溶液一质量0.025-0.035wt％的添加剂二；所述混合溶液一中，包括丙烯酸、聚乙烯醇PVA、改性小麦秸秆和水。
所述混合物三中包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:0.6-1.1:0.08-0.12
所述混合溶液一，其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为60-70％。
所述混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为20-30：4-5:6-8：60-70。
所述尼山石为粉碎后过100目筛的尼山石。
所述添加剂一为碳酸氢铵；
所述添加剂二包括过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为11.5-16.5:1。
所述改性小麦秸秆的制备方法为：将小麦秸秆晾干,用粉碎机粉碎,取过120 目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15-20倍的氢氧化钠溶液一，静置浸泡18-20小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在50-60℃下烘干，(所述氢氧化钠溶液一浓度为6-10wt％),得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉40-45质量倍的N,N-二亚甲基甲酰胺DMF，搅拌30-40min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.75-0.8:1，然后升温至100-110℃进行反应，反应过程保持搅拌，反应2-6小时后，将产物冷却至室温，过滤去除滤液，取过滤后剩余固体，洗涤3-4次后，放入烘箱60℃下烘干，便得到改性小麦秸秆。
为了更好地实现发明目的，本发明还提供一种自保温砌块的制备方法，所述自保温砌块的制备方法包括以下步骤：
(1)用质量浓度为30wt％的氢氧化钠溶液二中和丙烯酸至中和度60-70％，得中和后丙烯酸，备用；
将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过36双螺杆挤出造粒，加工温度205～210℃，螺杆转速220～230r/min，得混合物三，所述混合物三的粒径≤0.8mm，备用；
将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15-20倍的氢氧化钠溶液一，静置浸泡18-20小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在50-60℃下烘干，所述氢氧化钠溶液一质量浓度为6-10wt％,得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉40-45质量倍的N,N-二亚甲基甲酰胺DMF，搅拌30-40min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.75-0.8:1，然后升温至100-110℃进行反应，反应过程保持搅拌，反应2-6小时后，将产物冷却至室温，过滤去除滤液后的固体，用水洗涤3-4次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用；
向聚乙烯醇PVA中加入相对于聚乙烯醇质量6-7倍的蒸馏水，搅拌并加热至85-90℃使聚乙烯醇PVA完全溶解后,停止加热,冷却至15℃-25℃,得到聚乙烯醇PVA溶液备用；
(2)将中和后丙烯酸、聚乙烯醇PVA溶液、改性小麦秸秆和水,搅拌混合均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为20-30：4-5:6-8：60-70；在模具中将黄河胶泥、尼 山石、聚苯硫醚粉、玻璃微珠、混合物三、与所述混合溶液一按重量百分比45-52：37-41：1.5-3.8：2.1-2.3：1.0-1.3:30～45充分混合后，制成浆料混合物二；向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至60-80℃，充分搅拌后向浆料混合物二中依次加入添加量占混合溶液一质量2-3wt％的添加剂一，添加量占混合溶液一质量0.025-0.035wt％的添加剂二，然后继续搅拌3-5分钟后停止搅拌，然后在10min中内升温至240-250℃,在240-250℃下恒温15min后，降温至60-80℃，在60-80℃下保温8-10小时固化成型，然后脱模坯体在60℃干燥24-30h；
(3)将干燥后的坯体煅烧，第一阶段煅烧温度为360-380℃，煅烧3-4h,随后在30min内升温至1300℃～1350℃，第二阶段煅烧，煅烧时间5～8min；而后在30min内降温至300-340℃，第三阶段煅烧，煅烧时间3-5h；最后在30min内升温至850-880℃，煅烧24-30h烧结完毕,冷却24-48小时，得到自保温砌块。
所述自保温砌块的制备方法中所述添加剂一为碳酸氢铵；
所述添加剂二包括过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为11.5-16.5:1。
所述添加剂一添加量为占混合溶液一质量的2-3wt％，添加剂二添加量为占混合溶液一质量的0.025-0.035wt％。
本发明的有益效果是：原材料为黄河胶泥、小麦秸秆，变废为宝，资源综合利用，节地效果明显，保温效果可达到国家规定公建50％居建65％以上节能要求，砌筑的墙体不需再做外墙保温，与传统空心砖砌筑体相比较强度显著增加，重量降低50％以上，复合墙体热阻增大，显著降低能耗，自保温效果优异，外墙不需要另外做保温，工期可提前1/3，与建筑物同寿命达70年以上。砌块不需要晾干，节约时间，利用焙烧余热即可干燥，而且相对于目前进行干燥的其他自保温砌块，焙烧的耗能低。制得的保温砌块热工性能优良，产品吸水率低，低于7％，重量轻，强度高，保温效果好。该保温砌块不产生二次副产品，利废环保。该自保温砌块，早期强度高，经自然条件养护7d强度即可达到7.1-7.4兆帕，大大缩短砌块的出厂周期。
具体实施方式
针对现有技术的问题，本发明提供一种自保温砌块，原材料有黄河胶泥、小麦秸秆，变废为宝，资源综合利用，禁实、节地效果明显，保温效果可达到国家规定公建50％居建65％以上节能要求，砌筑的墙体不需再做外墙保温，与传统空心砖砌筑体相比较，抗压强度高，但是密度小质量轻，抗震能力好，隔音保温效果极好，产品达到国家A1级防火标准，与建筑物同寿命达70年以上。
黄河中上游以山地为主，中段流经中国黄土高原，每年夹带大量泥沙流向下游，具黄河河务部门数据显示，每年会产生16亿吨泥沙，最多年份可达39亿吨。带有粘性的细颗粒粒径小于0.01mm时沉积较慢，形成黄河胶泥层。主要成分有；水合硅酸盐、氧化铝、并含有石英、长石、云母、及硫酸盐等。黄河胶泥具有粘性大、塑性好的特点，与尼山石、聚苯硫醚粉、玻璃微珠等其他材料结合可以提高制品的综合性能。尼山石：为山东曲阜尼山石。
本发明提供一种自保温砌块，其特征在于，所述自保温砌块包括以下原料：黄河胶泥45-52质量份、尼山石37-41质量份，聚苯硫醚粉1.5-3.8质量份、玻璃微珠2.1-2.3质量份、混合物三1.0-1.3质量份、混合溶液一30-45质量份、占混合溶液一质量2-3wt％的添加剂一和占混合溶液一质量0.025-0.035wt％的添加剂二；所述混合溶液一中，包括丙烯酸、聚乙烯醇PVA、改性小麦秸秆和水。
所述混合物三中包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:0.6-1.1:0.08-0.12
所述混合溶液一，其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为60-70％。
所述混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为20-30：4-5:6-8：60-70。
所述尼山石为粉碎后过100目筛的尼山石。
所述添加剂一为碳酸氢铵；
所述添加剂二包括过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为11.5-16.5:1。
所述改性小麦秸秆的制备方法为：将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15-20倍的氢氧化钠溶液一，静 置浸泡18-20小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在50-60℃下烘干，所述氢氧化钠溶液一质量浓度为6-10wt％,得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉40-45质量倍的N,N-二亚甲基甲酰胺DMF，搅拌30-40min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.75-0.8:1，然后升温至100-110℃进行反应，反应过程保持搅拌，反应2-6小时后，将产物冷却至室温，过滤去除滤液，取过滤后剩余固体，用水洗涤3-4次后，放入烘箱60℃下烘干，便得到改性小麦秸秆。
自保温砌块的制备方法包括以下步骤：
(1)用质量浓度为30wt％的氢氧化钠溶液二中和丙烯酸至中和度60-70％，得中和后丙烯酸，备用；
将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过双螺杆挤出造粒，加工温度205～210℃，螺杆转速220～230r/min，得混合物三，所述混合物三的粒径≤0.8mm，备用；
将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15-20倍的氢氧化钠溶液一，静置浸泡18-20小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在50-60℃下烘干，所述氢氧化钠溶液一质量浓度为6-10wt％,得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉40-45质量倍的N,N-二亚甲基甲酰胺DMF，搅拌30-40min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.75-0.8:1，然后升温至100-110℃进行反应，反应过程保持搅拌，反应2-6小时后，将产物冷却至室温，过滤去除滤液后的固体，用水洗涤3-4次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用；
向聚乙烯醇PVA中加入相对于聚乙烯醇质量6-7倍的蒸馏水，搅拌并加热至85-90℃使聚乙烯醇PVA完全溶解后,停止加热,冷却至15℃-25℃,得到聚乙烯醇PVA溶液备用；
(2)将中和后丙烯酸、聚乙烯醇PVA溶液、改性小麦秸秆和水,搅拌混合均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为20-30：4-5:6-8：60-70；在模具中将黄河胶泥、尼山石、聚苯硫醚粉、玻璃微珠、混合物三、与所述混合溶液一按重量百分比45-52：37-41：1.5-3.8：2.1-2.3：1.0-1.3：30～45充分混合后，制成浆料混合物二； 向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至60-80℃，充分搅拌后向浆料混合物二中依次加入添加量占混合溶液一质量2-3wt％的添加剂一，添加量占混合溶液一质量0.025-0.035wt％的添加剂二，然后继续搅拌3-5分钟后停止搅拌，然后在10min中内升温至240-250℃,在240-250℃下恒温15min后，降温至60-80℃，在60-80℃下保温8-10小时固化成型，然后脱模坯体在60℃干燥24-30h；
(3)将干燥后的坯体煅烧，第一阶段煅烧温度为360-380℃，煅烧3-4h,随后在30min内升温至1300℃～1350℃，第二阶段煅烧，煅烧时间5～8min；而后在30min内降温至300-340℃，第三阶段煅烧，煅烧时间3-5h；最后在30min内升温至850-880℃，煅烧24-30h烧结完毕,冷却24-48小时，得到自保温砌块。
实施例中温度均为摄氏度。未指明的百分含量均为质量百分含量。
实施例1本发明自保温砌块
一种自保温砌块，包括以下原料：黄河胶泥48质量份、尼山石37质量份，聚苯硫醚粉1.5质量份(东莞市神化实业投资有限公司)、玻璃微珠2.2质量份(永清县海宇玻璃微珠有限公司)、混合物三1.0质量份、混合溶液一35质量份、占混合溶液一质量2.6wt％的添加剂一和占混合溶液一质量0.030wt％的添加剂二；混合溶液一中，包括丙烯酸、聚乙烯醇PVA(CAS No.9002-89-5，型号1799)、改性小麦秸秆和水。其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为70％。
小麦秸秆为山东德州的小麦秸秆。
所述混合物三中包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:1:0.08。2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠(CAS No.85209-91-2，洛阳市中达化工有限公司)。
混合溶液一中，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为30：4:7：62(其中部分中和的丙烯酸换算成等摩尔的未中和的丙烯酸后，按照未中和丙烯酸质量计，)；其中聚乙烯醇PVA的量为聚乙烯醇的净含量，不是聚乙烯醇PVA溶液的含量；
尼山石为粉碎后过100目筛的尼山石，
所述添加剂一为碳酸氢铵；
所述添加剂二包括过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为14:1。(N-羟甲基丙烯酰胺CAS No.924-42-5)
制备方法包括以下步骤：
(1)用质量浓度为30％的氢氧化钠溶液二中和丙烯酸至中和度70％，得中和后丙烯酸，备用；
将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过36双螺杆挤出造粒，加工温度205～210℃，螺杆转速220r/min，得混合物三，所述混合物三的粒径≤1mm，备用；所用聚丙烯牌号为T30S；
将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量20倍的氢氧化钠溶液一，静置浸泡20小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在60℃下烘干，所述氢氧化钠溶液一质量浓度为6wt％,得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉40质量倍的N,N-二亚甲基甲酰胺DMF(CAS No.68-12-2)，搅拌40min后,继续搅拌并加入马来酸酐MA(CAS No.108-31-6)，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.75:1，然后升温至110℃进行反应，反应过程保持搅拌，反应6小时后，将产物冷却至室温，过滤去除滤液，取过滤后剩余固体，用水洗涤3次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用；
向聚乙烯醇PVA中加入相对于聚乙烯醇质量7倍的蒸馏水，搅拌并加热至85℃使聚乙烯醇PVA完全溶解后,停止加热,冷却至20℃,得到聚乙烯醇PVA溶液备用；
(2)将中和后丙烯酸、聚乙烯醇PVA溶液、改性小麦秸秆和水,搅拌混合均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为30：4：7：62；在模具中将黄河胶泥、尼山石、聚苯硫醚粉、玻璃微珠、混合物三、与所述混合溶液一按质量比充分混合后，制成浆料混合物二；向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至70℃，充分搅拌后向浆料混合物二中依次加入添加量占混合溶液一质量2.6wt％的添加剂一，添加量占混合溶液一质量0.030wt％的添加剂二，然后继续搅拌5分钟后停止搅拌，然后在10min中内升温至250℃,在250℃下恒温15min后，降温至80℃，在80℃下保温8小时固化成型，然 后脱模坯体在60℃干燥24h；
(3)将干燥后的坯体煅烧，第一阶段煅烧温度为360℃，煅烧4h,随后在30min内升温至1350℃，第二阶段煅烧，煅烧时间5min；而后在30min内降温至340℃，第三阶段煅烧，煅烧时间4h；最后在30min内升温至880℃，煅烧24h烧结完毕,自然冷却24小时，得到自保温砌块。
实施例2
一种自保温砌块，自保温砌块包括以下原料：黄河胶泥52质量份、尼山石39质量份，聚苯硫醚粉2.0质量份、玻璃微珠2.3份、混合物三1.2质量份、混合溶液一45质量份、占混合溶液一质量2.8wt％的添加剂一和占混合溶液一质量0.025wt％的添加剂二；所述混合溶液一中，包括丙烯酸、聚乙烯醇PVA、改性小麦秸秆和水。
所述混合物三中包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:0.6:0.12。
混合溶液一，其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为60％。
混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为25：4.5:7：70。
尼山石为粉碎后过100目筛的尼山石。
所述添加剂一为碳酸氢铵；
所述添加剂二包括过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为11.5:1。
自保温砌块的制备方法包括以下步骤：
(1)用质量浓度为30wt％的氢氧化钠溶液二中和丙烯酸至中和度60％，得中和后丙烯酸，备用；
将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过双螺杆挤出造粒，加工温度205～210℃，螺杆转速230r/min，得混合物三，所述混合物三的粒径≤1mm，备用；所用聚丙烯牌号为T30S；
将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15倍的氢氧化钠溶液一，静置浸泡18小时,抽滤，舍去滤液，剩 余固体用水洗涤至中性后，在50℃下烘干，所述氢氧化钠溶液一质量浓度为10wt％,得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉45质量倍的N,N-二亚甲基甲酰胺DMF，搅拌30min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.8:1，然后升温至100℃进行反应，反应过程保持搅拌，反应2小时后，将产物冷却至室温，过滤去除滤液，取过滤后滤纸上层的剩余固体，用水洗涤4次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用；
向聚乙烯醇PVA中加入相对于聚乙烯醇质量6倍的蒸馏水，搅拌并加热至85℃使聚乙烯醇PVA完全溶解后,停止加热,冷却至15℃,得到聚乙烯醇PVA溶液备用；
(2)将中和后丙烯酸、聚乙烯醇PVA溶液、改性小麦秸秆和水,搅拌混合均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为25：4.5:7：70；在模具中将黄河胶泥、尼山石、聚苯硫醚粉、玻璃微珠、混合物三、与所述混合溶液一按质量比充分混合后，制成浆料混合物二；向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至80℃，充分搅拌后向浆料混合物二中依次加入添加量占混合溶液一质量2.8wt％的添加剂一，添加量占混合溶液一质量0.025wt％的添加剂二，然后继续搅拌3分钟后停止搅拌，然后在10min中内升温至240℃,在240℃下恒温15min后，降温至60℃，在60℃下保温10小时固化成型，然后脱模坯体在60℃干燥24h；
(3)将干燥后的坯体煅烧，第一阶段煅烧温度为380℃，煅烧3h,随后在30min内升温至1300℃，第二阶段煅烧，煅烧时间8min；而后在30min内降温至300℃，第三阶段煅烧，煅烧时间5h；最后在30min内升温至850℃，煅烧30h烧结完毕,自然冷却24小时，得到自保温砌块。
实施例3
一种自保温砌块，自保温砌块包括以下原料：黄河胶泥45质量份、尼山石41质量份，聚苯硫醚粉3.5质量份、玻璃微珠2.1质量份、混合物三1.3质量份、混合溶液一39质量份、占混合溶液一质量2.1wt％的添加剂一和占混合溶液一质量0.035wt％的添加剂二；所述混合溶液一中，包括丙烯酸、聚乙烯醇PVA、改性小麦秸秆和水。
所述混合物三中包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:1.1:0.1。
混合溶液一，其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为65％。
混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为20：5:8：65。
尼山石为粉碎后过100目筛的尼山石。
所述添加剂一为碳酸氢铵；
所述添加剂二包括过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为16.5:1。
自保温砌块的制备方法包括以下步骤：
(1)用质量浓度为30wt％的氢氧化钠溶液二中和丙烯酸至中和度65％，得中和后丙烯酸，备用；
将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过双螺杆挤出造粒，加工温度205～210℃，螺杆转速225r/min，得混合物三，所述混合物三的粒径≤1mm，备用；所用聚丙烯牌号为T30S；
将小麦秸秆晾干,用万能粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量18倍的质量浓度为8wt％的氢氧化钠溶液一，静置浸泡19小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在55℃下烘干，得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉42质量倍的N,N-二亚甲基甲酰胺DMF，搅拌35min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.78:1，然后升温至100℃进行反应，反应过程保持搅拌，反应4小时后，将产物冷却至室温，过滤去除滤液，取过滤后滤纸上层的剩余固体，用水洗涤3次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用；
向聚乙烯醇PVA中加入相对于聚乙烯醇质量6倍的蒸馏水，搅拌并加热至90℃使聚乙烯醇PVA完全溶解后,停止加热,冷却至25℃,得到聚乙烯醇PVA溶液备用；
(2)将中和后丙烯酸、聚乙烯醇PVA溶液、改性小麦秸秆和水,搅拌混合 均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为20：5:8：65；在模具中将黄河胶泥、尼山石、聚苯硫醚粉、玻璃微珠、混合物三、与所述混合溶液一按质量比充分混合后，制成浆料混合物二；向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至60℃，充分搅拌后向浆料混合物二中依次加入添加量占混合溶液一质量2.1wt％的添加剂一，添加量占混合溶液一质量0.035wt％的添加剂二，然后继续搅拌4分钟后停止搅拌，然后在10min中内升温至245℃,在245℃下恒温15min后，降温至60℃，在60℃下保温9小时固化成型，然后脱模坯体在60℃干燥30h；
(3)将干燥后的坯体煅烧，第一阶段煅烧温度为370℃，煅烧4h,随后在30min内升温至1320℃，第二阶段煅烧，煅烧时间7min；而后在30min内降温至320℃，第三阶段煅烧，煅烧时间3h；最后在30min内升温至860℃，煅烧26h烧结完毕,自然冷却30小时，得到自保温砌块。
实施例4
一种自保温砌块，自保温砌块包括以下原料：黄河胶泥50质量份、尼山石38质量份，聚苯硫醚粉3质量份、玻璃微珠2.3份、混合物三1.1质量份、混合溶液一30质量份、占混合溶液一质量2.5wt％的添加剂一和占混合溶液一质量0.028wt％的添加剂二；所述混合溶液一中，包括丙烯酸、聚乙烯醇PVA、改性小麦秸秆和水。
所述混合物三中包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:0.9：0.12。
混合溶液一，其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为62％。
混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为25：5:8：60。
尼山石为粉碎后过100目筛的尼山石。
添加剂一为碳酸氢铵；
添加剂二为过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为13:1。
自保温砌块的制备方法包括以下步骤：
(1)用质量浓度为30wt％的氢氧化钠溶液二中和丙烯酸至中和度62％，得中和后丙烯酸，备用；
将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过双螺杆挤出造粒，加工温度205～210℃，螺杆转速220r/min，得混合物三，所述混合物三的粒径≤1mm，备用；所用聚丙烯牌号为T30S；
将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15倍的质量浓度为7wt％的氢氧化钠溶液一，静置浸泡18小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在60℃下烘干，得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉45质量倍的N,N-二亚甲基甲酰胺DMF，搅拌40min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.75:1，然后升温至110℃进行反应，反应过程保持搅拌，反应2-6小时后，将产物冷却至室温，过滤去除滤液，取滤纸上层的剩余固体，用水洗涤4次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用；
向聚乙烯醇PVA中加入相对于聚乙烯醇质量6.5倍的蒸馏水，搅拌并加热至88℃使聚乙烯醇PVA完全溶解后,停止加热,冷却至20℃,得到聚乙烯醇PVA溶液备用；
(2)将中和后丙烯酸、聚乙烯醇PVA溶液、改性小麦秸秆和水,搅拌混合均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为25：5:8：60；在模具中将黄河胶泥、尼山石、聚苯硫醚粉、玻璃微珠、混合物三、与所述混合溶液一按质量比充分混合后，制成浆料混合物二；向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至80℃，充分搅拌后向浆料混合物二中依次加入添加量占混合溶液一质量2.5wt％的添加剂一，添加量占混合溶液一质量0.028wt％的添加剂二，然后继续搅拌3分钟后停止搅拌，然后在10min中内升温至250℃,在250℃下恒温15min后，降温至60℃，在60℃下保温8小时固化成型，然后脱模坯体在60℃干燥25h；
(3)将干燥后的坯体煅烧，第一阶段煅烧温度为375℃，煅烧3h,随后在30min内升温至1330℃，第二阶段煅烧，煅烧时间6min；而后在30min内降温至310℃，第三阶段煅烧，煅烧时间4h；最后在30min内升温至870℃，煅烧24h 烧结完毕,自然冷却48小时，得到自保温砌块。
实施例5
一种自保温砌块，自保温砌块包括以下原料：黄河胶泥49质量份、尼山石40质量份，聚苯硫醚粉3.8质量份、玻璃微珠2.2份、混合物三1.0质量份、混合溶液一38质量份、占混合溶液一质量3wt％的添加剂一和占混合溶液一质量0.032wt％的添加剂二；；所述混合溶液一中，包括丙烯酸、聚乙烯醇PVA、改性小麦秸秆和水。
所述混合物三中包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:0.8:0.09。
混合溶液一，其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为69％。
混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为30：4:6：70。尼山石为粉碎后过100目筛的尼山石。
添加剂一为碳酸氢铵；
添加剂二为过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为15:1。
自保温砌块的制备方法包括以下步骤：
(1)用质量浓度为30wt％的氢氧化钠溶液二中和丙烯酸至中和度69％，得中和后丙烯酸，备用；
将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过双螺杆挤出造粒，加工温度205～210℃，螺杆转速230r/min，得混合物三，所述混合物三的粒径≤1mm，备用；所用聚丙烯牌号为T30S；
将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15倍的质量浓度为10wt％的氢氧化钠溶液一，静置浸泡20小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在50℃下烘干，得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉45质量倍的N,N-二亚甲基甲酰胺DMF，搅拌40min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.8:1，然后升温至℃进行反应，反应过程保持搅拌，反应3小时后，将产物冷却至室温，过滤去除滤液，取过滤后的剩余固体，用水洗涤4 次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用；
向聚乙烯醇PVA中加入相对于聚乙烯醇质量6倍的蒸馏水，搅拌并加热至85℃使聚乙烯醇PVA完全溶解后,停止加热,冷却至25℃,得到聚乙烯醇PVA溶液备用；
(2)将中和后丙烯酸、聚乙烯醇PVA溶液、改性小麦秸秆和水,搅拌混合均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为30：4:7：70；在模具中将黄河胶泥、尼山石、聚苯硫醚粉、玻璃微珠、混合物三、与所述混合溶液一按质量比充分混合后，制成浆料混合物二；向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至60℃，充分搅拌后向浆料混合物二中依次加入添加量占混合溶液一质量3wt％的添加剂一，添加量占混合溶液一质量0.032wt％的添加剂二，然后继续搅拌5分钟后停止搅拌，然后在10min中内升温至240℃,在240℃下恒温15min后，降温至70℃，在70℃下保温9小时固化成型，然后脱模坯体在60℃干燥28h；
(3)将干燥后的坯体煅烧，第一阶段煅烧温度为360℃，煅烧4h,随后在30min内升温至1310℃，第二阶段煅烧，煅烧时间6min；而后在30min内降温至340℃，第三阶段煅烧，煅烧时间4h；最后在30min内升温至880℃，煅烧24h烧结完毕,自然冷却36小时，得到自保温砌块。
实施例6
一种自保温砌块，自保温砌块包括以下原料：黄河胶泥46质量份、尼山石39质量份，聚苯硫醚粉2.9质量份、玻璃微珠2.1份、混合物三1.1质量份、混合溶液一30质量份、占混合溶液一质量2wt％的添加剂一和占混合溶液一质量0.034wt％的添加剂二；所述混合溶液一中，包括丙烯酸、聚乙烯醇PVA、改性小麦秸秆和水。
所述混合物三中包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:0.9:0.11。
混合溶液一，其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为65％。
混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为23：5:7：66。
尼山石为粉碎后过100目筛的尼山石。
添加剂一为碳酸氢铵；
添加剂二为过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为16:1。
自保温砌块的制备方法包括以下步骤：
(1)用质量浓度为30wt％的氢氧化钠溶液二中和丙烯酸至中和度65％，得中和后丙烯酸，备用；
将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过双螺杆挤出造粒，加工温度205～210℃，螺杆转速228r/min，得混合物三，所述混合物三的粒径≤1mm，备用；所用聚丙烯牌号为T30S；
将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量17倍的氢氧化钠溶液一，静置浸泡19小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在55℃下烘干，所述氢氧化钠溶液一质量浓度为6wt％,得预处理小麦秸秆粉，加入相对于预处理小麦秸秆粉43质量倍的N,N-二亚甲基甲酰胺DMF，搅拌36min后,继续搅拌并加入马来酸酐MA，所述马来酸酐MA：预处理小麦秸秆粉质量比为0.76:1，然后升温至104℃进行反应，反应过程保持搅拌，反应4小时后，将产物冷却至室温，过滤去除滤液，取过滤后滤纸上层的剩余固体，用水洗涤3次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用；
向聚乙烯醇PVA中加入相对于聚乙烯醇质量7倍的蒸馏水，搅拌并加热至90℃使聚乙烯醇PVA完全溶解后,停止加热,冷却至15℃,得到聚乙烯醇PVA溶液备用；
(2)将中和后丙烯酸、聚乙烯醇PVA溶液、改性小麦秸秆和水,搅拌混合均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇PVA：改性小麦秸秆：水质量比为23：5:7：66；在模具中将黄河胶泥、尼山石、聚苯硫醚粉、玻璃微珠、混合物三、与混合溶液一按质量比充分混合后，制成浆料混合物二；向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至80℃，充分搅拌后向浆料混合物二中依次加入添加量占混合溶液一质量2wt％的添加剂一，添加量占混合溶液一质量0.034wt％的添加 剂二，然后继续搅拌5分钟后停止搅拌，然后在10min中内升温至250℃,在250℃下恒温15min后，降温至70℃，在70℃下保温9小时固化成型，然后脱模坯体在60℃干燥24h；添加剂为碳酸氢铵：硝酸铈铵(NH4)2Ce(N03)6质量比为23:1。
(3)将干燥后的坯体煅烧，第一阶段煅烧温度为380℃，煅烧3h,随后在30min内升温至1330℃，第二阶段煅烧，煅烧时间6min；而后在30min内降温至340℃，第三阶段煅烧，煅烧时间3h；最后在30min内升温至870℃，煅烧26h烧结完毕,自然冷却26小时，得到自保温砌块。
对比例1黄河胶泥标砖(多孔砖)
黄河淤泥标砖(多孔砖)，黄河胶泥70％，煤矸石30％，单块重2.4㎏，抗压强度15MPa以上，用于建筑物承重墙，砌体必须做外墙保温，费工、成本高、工期长、保温效果差。
制备方法：混合料→搅拌→成型→干燥→烧结→出窑码垛。
对比例2混凝土砖
混凝土砖，240*115*53，单块重3.5㎏，主要原料水泥15％，石硝10％，石粉45％，粉煤灰30％，抗压强度大于15MPa，用于建筑物承重墙，本身自重大，墙体必须做外墙保温，工人劳动强度大，费工，成本高，保温效果差。
制备方法：布料→搅拌→输送→成型→落板→成品养护→成品。
对比例3
在实施例1基础上，将黄河胶泥和尼山石替换为普通硅酸盐水泥和沙子，其他条件不变。
密度为752kg/m3，抗压强度7.1Mpa，吸水率13％，抗风化性能0.68，需要做外保温。
对比例4
在实施例1基础上，不加聚苯硫醚粉和玻璃微珠其他条件不变。
密度为740kg/m3，抗压强度7.0Mpa，吸水率14％，抗风化性能0.65，需要做外保温。
对比例5
在实施例1基础上，不加混合溶液一和添加剂，仅保留混合溶液一中的水分，其他条件不变。
坯体煅烧是需要升温到950-1250℃，煅烧36-48h,密度为822kg/m3，抗 压强度7.0Mpa，吸水率13％，抗风化性能0.64。
对比例6
在实施例1基础上，混合溶液一中不加改性小麦秸秆，其他条件不变。
密度为751kg/m3，抗压强度7.1Mpa，吸水率15％，抗风化性能0.69。
对比例7
在实施例1基础上，混合溶液一中不加聚乙烯醇PVA，其他条件不变。
密度为760kg/m3，抗压强度7.5Mpa，吸水率15％，抗风化性能0.67，需要做外保温。
对比例8
在实施例1基础上，不加混合物三，其他条件不变。
密度为591kg/m3，抗压强度7.6Mpa，吸水率11％，抗风化性能0.63。
表1各实施例产品的性能指标
Figure PCTCN2017075152-appb-000001
从表1可以看出利用我国黄河大量的淤泥资源及小麦秸秆固体废料为原料， 资源综合利用，生产能耗低，保温效果好，安全稳固性好的产品，外墙不再做保温，即可达到国家公建50％居建65％的节能保温标准，节约工期30％以上。
自重轻的建筑地震力就小，对抗震有利，和砖混建筑相比，同样的建筑，同样的地震条件下，震害程度相差一个地震设计设防级别，在相同地基条件下，自重轻的建筑的层数可以增多，经济上有利。实施例中自保温砌块密度为相同强度等级砌块的50％以下，稳定性高，综合性能好，综合降低施工成本20％以上。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种自保温砌块，其特征在于，所述自保温砌块包括以下原料：黄河胶泥45-52质量份、尼山石37-41质量份、聚苯硫醚粉1.5-3.8质量份、玻璃微珠2.1-2.3质量份、混合物三1.0-1.3质量份、混合溶液一30-45质量份、占混合溶液一质量2-3wt％的添加剂一和占混合溶液一质量0.025-0.035wt％的添加剂二；所述混合溶液一中，包括丙烯酸、聚乙烯醇、改性小麦秸秆和水。
  2. 根据权利要求1所述的自保温砌块，其特征在于，所述混合物三包括：聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙，其中聚丙烯：2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠：纳米碳酸钙质量比为100:0.6-1.1:0.08-0.12。
  3. 根据权利要求1或2所述的自保温砌块，其特征在于，所述混合溶液一，其中丙烯酸为部分中和丙烯酸，丙烯酸的中和度为60-70％。
  4. 根据权利要求1-3所述的自保温砌块，其特征在于，所述混合溶液一中，其中丙烯酸以未中和的丙烯酸计，丙烯酸：聚乙烯醇：改性小麦秸秆：水质量比为20-30：4-5:6-8：60-70。
  5. 根据权利要求1-4任一所述的自保温砌块，其特征在于，所述尼山石为粉碎后过100目筛的尼山石。
  6. 根据权利要求1-5任一所述的自保温砌块，其特征在于，所述添加剂一为碳酸氢铵；
    所述添加剂二包括过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为11.5-16.5:1。
  7. 根据权利要求1-6任一所述的自保温砌块，其特征在于，所述改性小麦秸秆的制备方法为：将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15-20倍的氢氧化钠溶液一，静置浸泡18-20小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在50-60℃下烘干，得预处理小麦秸秆粉；在预处理小麦秸秆粉中加入相对于预处理小麦秸秆粉40-45质量倍的N,N-二亚甲基甲酰胺，搅拌30-40min后,继续搅拌并加入马来酸酐，所述马来酸酐：预处理小麦秸秆粉质量比为0.75-0.8:1，然后升温至100-110℃进行反应，反应过程保持搅拌，反应2-6小时后，将产物冷却至室温，过滤去除滤 液，取过滤后剩余固体，用水洗涤3-4次后，放入烘箱60℃下烘干，便得到改性小麦秸秆；所述氢氧化钠溶液一质量浓度为6-10wt％。
  8. 根据权利要求1-7任一所述的自保温砌块，其特征在于，所述自保温砌块的制备方法包括以下步骤：
    (1)用质量浓度为30wt％的氢氧化钠溶液二中和丙烯酸至中和度60-70％，得中和后丙烯酸，备用；
    将所述质量比的聚丙烯、2,2-亚甲基-双(4,6-二叔丁基苯基)磷酸酯钠、纳米碳酸钙混合均匀后通过双螺杆挤出造粒，得混合物三，备用；
    将小麦秸秆晾干,用粉碎机粉碎,取过120目筛的小麦秸秆粉,加入相对于小麦秸秆粉质量15-20倍的氢氧化钠溶液一，静置浸泡18-20小时,抽滤，舍去滤液，剩余固体用水洗涤至中性后，在50-60℃下烘干，得预处理小麦秸秆粉，然后向预处理小麦秸秆粉中加入相对于预处理小麦秸秆粉40-45质量倍的N,N-二亚甲基甲酰胺，搅拌30-40min后,继续搅拌并加入马来酸酐，所述马来酸酐：预处理小麦秸秆粉质量比为0.75-0.8:1，然后升温至100-110℃进行反应，反应过程保持搅拌，反应2-6小时后，将产物冷却至室温，过滤去除滤液，取过滤后剩余固体，用水洗涤3-4次后，放入烘箱60℃下烘干，便得到改性小麦秸秆，备用，所述氢氧化钠溶液一质量浓度为6-10wt％；
    向聚乙烯醇中加入相对于聚乙烯醇质量6-7倍的蒸馏水，搅拌并加热至85-90℃使聚乙烯醇完全溶解后,停止加热,冷却至15℃-25℃,得到聚乙烯醇溶液，备用；
    (2)将中和后丙烯酸、聚乙烯醇溶液、改性小麦秸秆和水,搅拌混合均匀得混合溶液一；混合溶液一中，以未中和的丙烯酸计，丙烯酸：聚乙烯醇：改性小麦秸秆：水质量比为20-30：4-5:6-8：60-70；在模具中将黄河胶泥、尼山石、聚苯硫醚粉、玻璃微珠、混合物三、与所述混合溶液一按重量比45-52：37-41：1.5-3.8：2.1-2.3：1.0-1.3：30～45充分混合后，制成浆料混合物二；向浆料混合物二中冲入氮气同时剧烈搅拌置换其中的氧气，随后将浆料混合物二升温至60-80℃，充分搅拌后向浆料混合物二中依次加入添加剂一和添加剂二，然后继续搅拌3-5分钟后停止搅拌,然后在10min中内升温至240-250℃,在240-250℃下恒温15min后，降温至60-80℃，在60-80℃下保温8-10小时固化成型，然后脱模坯体在60℃干燥24-30h；所述添加剂一添加量为占混合溶液一 质量的2-3wt％，添加剂二添加量为占混合溶液一质量的0.025-0.035wt％；
    (3)将干燥后的坯体煅烧，第一阶段煅烧温度为360-380℃，煅烧3-4h,随后在30min内升温至1300℃～1350℃后，进行第二阶段煅烧，煅烧时间5～8min；而后在30min内降温至300-340℃，进行第三阶段煅烧，煅烧时间3-5h；最后在30min内升温至850-880℃，进行第四阶段煅烧，煅烧24-30h烧结完毕,冷却24-48小时，得到自保温砌块。
  9. 根据权利要求1-8任一所述的自保温砌块，其特征在于，所述自保温砌块的制备方法中所述添加剂一为碳酸氢铵；
    所述添加剂二包括过硫酸钾和N-羟甲基丙烯酰胺，其中过硫酸钾：N-羟甲基丙烯酰胺质量比为11.5-16.5:1。
  10. 根据权利要求1-9任一所述的自保温砌块，其特征在于，所述添加剂一添加量为占混合溶液一质量的2-3wt％，添加剂二添加量为占混合溶液一质量的0.025-0.035wt％。
PCT/CN2017/075152 2016-11-14 2017-02-28 一种自保温砌块 WO2018086277A1 (zh)

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CN114538890A (zh) * 2021-12-31 2022-05-27 中国建筑科学研究院有限公司 一种利用工农业废弃物生产可降解砌块的方法
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CN112136643A (zh) * 2020-09-04 2020-12-29 华中农业大学 一种夹芯多孔屋顶基质块及其制备方法
CN112136643B (zh) * 2020-09-04 2021-12-17 华中农业大学 一种夹芯多孔屋顶基质块及其制备方法
CN114538890A (zh) * 2021-12-31 2022-05-27 中国建筑科学研究院有限公司 一种利用工农业废弃物生产可降解砌块的方法
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CN116444287B (zh) * 2023-04-19 2024-05-07 国发环保新材料(江门)有限公司 一种发泡陶瓷生产工艺及设备
CN116903318A (zh) * 2023-09-11 2023-10-20 潍坊市金柏尔新型建材有限公司 一种高强加气混凝土砌块的制备方法
CN116903318B (zh) * 2023-09-11 2023-12-29 潍坊市金柏尔新型建材有限公司 一种高强加气混凝土砌块的制备方法

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