WO2023241542A1 - 一种磷石膏基生态水泥泡沫轻质土及其制备方法 - Google Patents

一种磷石膏基生态水泥泡沫轻质土及其制备方法 Download PDF

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WO2023241542A1
WO2023241542A1 PCT/CN2023/099835 CN2023099835W WO2023241542A1 WO 2023241542 A1 WO2023241542 A1 WO 2023241542A1 CN 2023099835 W CN2023099835 W CN 2023099835W WO 2023241542 A1 WO2023241542 A1 WO 2023241542A1
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phosphogypsum
foam
parts
lightweight soil
cement
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PCT/CN2023/099835
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English (en)
French (fr)
Inventor
张琨
王开强
陈波
姜维
杨帆
徐方
许劲
刘亚美
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中建三局集团有限公司
中国地质大学（武汉）
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Publication of WO2023241542A1 publication Critical patent/WO2023241542A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
    • C04B28/143—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/0445—Synthetic gypsum, e.g. 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/40—Porous or lightweight materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention belongs to the technical field of building materials, and specifically relates to a phosphogypsum-based ecological cement foam lightweight soil and a preparation method thereof.
  • Phosphogypsum is a by-product produced during the wet phosphorus production process. Different production processes make it mainly composed of phosphorus-containing dihydrate gypsum or hemihydrate gypsum, and it also contains inorganic residual impurities, making it acidic. Because it directly or indirectly causes encroachment and pollution on environmental resources, it can usually only be treated as a waste residue. At present, a large amount of phosphogypsum in our country can only be stacked in the open air. The random discharge and accumulation of phosphogypsum not only takes up a lot of land, but also causes pollution to the atmospheric environment, soil, water resources, etc. where we live. The problem of processing and utilization of phosphogypsum is urgent.
  • Foamed lightweight soil is a common roadbed material. Preparing phosphogypsum into foamed lightweight soil can not only broaden the utilization of phosphogypsum, but also enable large-scale, high-value utilization of phosphogypsum. At present, research in this area is still in its infancy.
  • patent CN112062529A discloses a gypsum-based foam concrete with a large amount of phosphogypsum, which is composed of phosphogypsum, cement, fiber, retarder, foaming agent, foam stabilizer, and catalyst. It is prepared with water as raw materials; the phosphogypsum used in this plan needs to be dried in an oven with a constant temperature of 130°C for 60 minutes.
  • the phosphogypsum has air-hardening gelling properties through high-temperature pretreatment, and chemical foaming is used to prepare foam concrete. ;
  • the high-temperature pretreatment method used will increase energy consumption, is uneconomical and environmentally friendly, and the amount of phosphogypsum is limited;
  • Patent CN112811858A discloses a kind of all-solid waste foam concrete, which is made by wet grinding ultra-fine slag, phosphogypsum, and steel slag , iron tailings and other solid wastes are used as the main raw materials, and a lightweight and high-strength all-solid waste foam concrete is prepared under the action of a compound activator (a mixture of phosphogypsum, steel slag, and sodium carbonate) and a compound foam stabilizer; in this plan
  • the compound activator accounts for 4 to 10% of the raw material composition, of which the phosphogypsum content accounts for about 50%.
  • the main purpose of the present invention is to provide a phosphogypsum-based ecological cement foam lightweight soil in view of the problems and shortcomings of the existing technology.
  • phosphogypsum-based ecological cement foam lightweight soil On the basis of realizing the resource utilization of large-volume phosphogypsum-based industrial waste, It can effectively take into account good mechanical properties, working performance and stable performance; at the same time, it can effectively simplify the preparation process and reduce energy consumption. It has important economic and environmental benefits and is suitable for popularization and application.
  • a phosphogypsum-based ecological cement foam lightweight earth material which uses phosphogypsum-based ecological cement, phosphogypsum fine aggregate, prefabricated composite foam, composite admixtures and water as main raw materials, in which phosphogypsum-based ecological cement is used as a cementing material , composed of the first phosphogypsum, slag powder, and Portland cement; the phosphogypsum fine aggregate uses the second phosphogypsum; the composite admixture consists of a coagulant, a water reducing agent and a rheology additive; each component and its The parts by weight include: 40 to 70 parts of the first phosphogypsum, 60 to 180 parts of the second phosphogypsum, 40 to 70 parts of slag powder, 2 to 5 parts of Portland cement, 1.5 to 7.5 parts of composite admixtures, and prefabricated composite 2 to 20 parts of foam and 40 to 95 parts of water.
  • each component in the composite admixture and its mass fraction are: 0 to 0.5 parts of rheology aid, 0.5 to 2 parts of water reducing agent, and 1 to 5 parts of coagulant.
  • the mass ratio of the rheology aid, water reducing agent and coagulant is 1:(5-20):(20-80).
  • the mass ratio of the rheology aid, water reducing agent and coagulant is 1: (8-15): (30-50).
  • the SiO 2 /Al 2 O 3 molar ratio of the phosphogypsum-based ecological cement foam lightweight soil raw material is controlled to be 2.3 to 2.6, and the CaO/SO 3 molar ratio is controlled to be 1.5 to 1.8.
  • the first phosphogypsum is produced by drying and crushing undisturbed phosphogypsum at low temperature, with a particle size of no more than 0.08mm, and a specific surface area of 250 to 450 m 2 /kg; the second phosphogypsum is produced by using undisturbed phosphogypsum. Obtained after low-temperature drying and sieving, the particle size is not greater than 2.36mm; among them, the moisture content of the original phosphogypsum is not greater than 25%, the mass fraction of CaSO 4 ⁇ 2H 2 O is not less than 75%, and the mass fraction of water-soluble P 2 O 5 Not more than 0.8%, water-soluble F - mass fraction not more than 0.5%.
  • the drying temperature used in the low-temperature drying is 45-55°C and the time is 18-36 hours.
  • the slag powder is granulated blast furnace slag powder not lower than S95 grade.
  • the main components are CaO, Al 2 O 3 and SiO 2 , and the specific surface area is not less than 400m 2 /kg.
  • the cement is Portland cement or ordinary Portland cement, and the strength grade is not lower than P.O 42.5.
  • the coagulant is one or more of sodium hydroxide, quicklime, fast-hardening sulfoaluminate cement, and the like.
  • the water-reducing agent is a polycarboxylic acid high-performance water-reducing agent with a solid content of 10-25% and a water-reducing rate of 20-30%.
  • the rheology additive is hydroxypropyl methylcellulose (HPMC), carboxymethyl cellulose One or more of sodium (CMC), etc.; the purity of HPMC and CMC is not less than 98%.
  • the prefabricated foam is made by dissolving a foaming agent and a foam stabilizer in water through physical foaming.
  • the foaming agent is sodium ⁇ -alkenyl sulfonate (AOS), and its purity is not less than 96%.
  • the foam stabilizer is xanthan gum, and its purity is not less than 96%; by weight, the prefabricated foam components and dosage are: 2.0 to 5.0g of foaming agent, 0.5 to 2.5g of foam stabilizer, and 1000ml of water.
  • the half-life of the obtained prefabricated foam is not less than 200 minutes, and the average Feret diameter is 0.10 ⁇ 0.60mm.
  • the ratio of the half-life of the obtained preformed foam (unit: min) to the setting time (unit: min) of the phosphogypsum slurry is controlled at 1: (1 ⁇ 1.5); the ultimate shear force of the phosphogypsum slurry (unit: min) is Pa) and the ratio of the average Feret diameter (unit: mm) of the prefabricated foam is controlled at (100 ⁇ 300):1, the ultimate shear stress of the phosphogypsum slurry is 35 ⁇ 85Pa; the phosphogypsum slurry is made of phosphogypsum-based ecological
  • the cement, phosphogypsum fine aggregate, composite admixture and water are uniformly mixed (obtained in step S2).
  • the dry density of the foamed lightweight soil is 800-1400kg/m 3
  • the fluidity is 160-210mm
  • the 7-day compressive strength is 0.5-3.0MPa
  • the 28-day compressive strength is 1.5-8.0MPa.
  • the above-mentioned phosphogypsum-based ecological cement foam lightweight soil and its preparation method include the following steps:
  • Step S3 Prepare foamed lightweight soil: Add the prefabricated foam prepared in step S1 to the slurry prepared in step S2, and stir until the prefabricated foam and the slurry are evenly mixed to obtain a foamed lightweight soil mixture;
  • the temperature used in the curing step is 18-22°C
  • the humidity is above 95%
  • the curing period is no less than 7 days.
  • step S1 specifically includes:
  • step S1.2 Place the mixed solution in step S1.1 into a foam device.
  • the foam device is connected to an air compressor through a hose; the air compressor is used for foaming to obtain prefabricated foam.
  • the present invention uses phosphogypsum-based ecological cement instead of ordinary silicon cement as the cementing material, which greatly reduces the use of cement; and uses phosphogypsum as fine aggregate to prepare; while achieving a large dosage (phosphogypsum content can be as high as 80% Above), the purpose of large-scale and high-value consumption of phosphogypsum; phosphogypsum has the dual functions of cementing material raw material and fine aggregate skeleton filling; in order to make the composition system take into account good mechanical properties, working performance, durability and Environmental protection performance, further through optimized composition design, precise control of hydration products, effective solidification of soluble phosphorus, fluorine and other pollutants in phosphogypsum, achieving the dual purpose of excellent performance and environmental protection standards, while achieving large dosage, large-scale, and high value
  • the purpose of absorbing phosphogypsum suitable for engineering fillers and other fields;
  • the proportional relationship between the ultimate shear force and the average Feret diameter of the prefabricated foam achieves the simultaneous improvement of multiple effects such as the working performance, water retention performance, early strength, uniform slurry structure, and compactness of the phosphogypsum-based ecological cement foam lightweight soil. ;
  • the phosphogypsum-based ecological cement foam lightweight soil obtained by the present invention has significant advantages in energy conservation and environmental protection, and reduces CO2 emissions by more than 90% compared with general cement; it does not need to resort to conventional high-temperature calcination, autoclaved curing and other means, and can effectively take both good and
  • the mechanical properties, working performance and stability performance can provide a new idea for the high value-added application of industrial waste such as phosphogypsum.
  • Figure 1 is a schematic diagram of the production process of phosphogypsum-based ecological cement foam lightweight soil.
  • the main chemical composition of the original phosphogypsum used is CaO and SO 3 , the main component is CaSO 4 ⁇ 2H 2 O, the mass fraction of attached water is not more than 25%, and the mass fraction of CaSO 4 ⁇ 2H 2 O is 81% , The mass fraction of water-soluble P 2 O 5 is 0.04%, and the mass fraction of water-soluble F- is 0.1%.
  • the first phosphogypsum is obtained by drying the original phosphogypsum at low temperature (45°C, 36h), grinding and crushing. The particle size is not greater than 0.08mm, and its specific surface area is 415m 2 /kg; the second phosphogypsum is in its original form. Phosphogypsum is obtained by low-temperature drying (45°C, 36h) and sieving. The particle size is no more than 2.36mm, and its specific surface area is 86m 2 /kg.
  • the slag powder used is S95 grade granulated blast furnace slag powder, whose main components are CaO, Al 2 O 3 and SiO 2.
  • the measured specific surface area of the slag powder is 424m 2 /kg.
  • the cement used is ordinary Portland cement with a strength grade of P.O 42.5.
  • the setting accelerator used is fast-hardening sulfoaluminate cement.
  • the water-reducing agent used is polycarboxylic acid high-performance water-reducing agent with a solid content of 20% and a water-reducing rate of 28%.
  • the rheology additive used is hydroxypropyl methylcellulose (HPMC).
  • test methods for the relevant macroscopic properties and prefabricated foam cell structure parameters of the obtained phosphogypsum-based ecological cement foam lightweight soil are as follows:
  • Fluidity Slowly pour the freshly mixed phosphogypsum-based ecological cement foam lightweight soil slurry (foam lightweight soil mixture) into a cylindrical mold.
  • the size of the cylindrical mold is: 80mm in diameter, Height is 80mm;
  • test mold (2) Setting time: Pour the freshly mixed phosphogypsum-based ecological cement foam lightweight soil slurry into the test mold.
  • the size of the test mold is: the depth of the test mold is 40mm ⁇ 0.2mm, and the inner diameter of the top is ⁇ 65mm ⁇ 0.5mm. , a truncated cone with a bottom inner diameter of ⁇ 75mm ⁇ 0.5mm; each test mold should be equipped with a flat glass bottom plate larger than the test mold and with a thickness of ⁇ 2.5mm for measurement of the setting time;
  • Compressive strength Prepare a phosphogypsum-based ecological cement foam lightweight soil test block with a side length of 100mm. After demoulding with reference to the curing method described in the embodiment, measure the compressive strength at different ages;
  • Dry density Prepare a cubic foam concrete test block with a side length of 100mm, place it in an environment with a temperature of 20 ⁇ 2°C and a relative humidity of more than 95%, and measure its dry density;
  • F is the measured value of the tensile gauge (N); b is the width of the sheet (m); h is the embedded material of the sheet The depth of the slurry (m); ⁇ m is the ultimate shear stress (Pa) of the geopolymer pure slurry;
  • a kind of phosphogypsum-based ecological cement foam lightweight soil material the raw materials are weighed according to the following mass parts: 45 parts of the first phosphogypsum, 50 parts of slag powder, 5 parts of ordinary Portland cement, phosphogypsum fine aggregate (the second 60 parts of phosphogypsum), 2.55 parts of composite admixtures (0.5 parts of water-reducing agent, 2 parts of coagulant, 0.05 part of rheological additive, the mass ratio of rheological additive, water-reducing agent and coagulant is 1: 10:40), 10 parts of prefabricated foam, 50 parts of water, where the SiO 2 /Al 2 O 3 ratio is 2.3, and the CaO/SO 3 ratio is 1.8;
  • Preparation of prefabricated foam Mix the foaming agent, foam stabilizer and water, and foam through an air compressor to obtain prefabricated foam; the components and dosage (the mass added per 1000ml of water) are: 4.0g ⁇ -alkenyl sulfon Sodium sulfate (AOS) foaming agent, 1.5g xanthan gum foam stabilizer; the half-life of the obtained prefabricated foam is 260min, and the average Feret diameter is 0.227mm;
  • AOS ⁇ -alkenyl sulfon Sodium sulfate
  • Step S3 Prepare foamed lightweight soil: Add the prefabricated foam prepared in step S1 to the phosphogypsum slurry prepared in step S2, and stir until the prefabricated foam and the slurry are evenly mixed to obtain a foamed lightweight soil mixture;
  • the main performance indicators of the phosphogypsum-based ecological cement foam lightweight soil test block obtained in this example are: fluidity is 180mm, initial setting time is 3h40min, final setting time is 5h15min, 7d compressive strength is 2.42MPa, 14d The compressive strength is 3.36MPa, the 28d compressive strength is 4.18MPa, the dry density is 850kg/m 3 , the ratio of the half-life of the prefabricated foam to the final setting time of the slurry is 1:1.2, and the ratio of the ultimate shear force to the average Feret diameter is 264:1.
  • a kind of phosphogypsum-based ecological cement foam lightweight soil material the raw materials are weighed according to the following mass parts: 45 parts of the first phosphogypsum, 50 parts of slag powder, 5 parts of ordinary Portland cement, phosphogypsum fine aggregate (the second 100 parts of phosphogypsum, 2.7 parts of composite admixture (0.65 parts of water-reducing agent, 2 parts of coagulant, 0.05 part of rheological additive, the mass ratio of rheological additive, water-reducing agent and coagulant is 1: 13:40) 5 parts of prefabricated foam, 65 parts of water, where the SiO 2 /Al 2 O 3 ratio is 2.4, and the CaO / SO 3 ratio is 1.7; its preparation flow chart refers to Figure 1, and the specific preparation steps are as described in Example 1 ; Among them, the components and dosages used in the preparation process of the prefabricated foam (the mass added per 1000ml of water) are: 3.0g sodium ⁇ -alkenesulfonate (AOS)
  • the main performance indicators of the obtained phosphogypsum-based ecological cement foam lightweight soil test block are: fluidity is 190mm, initial setting time is 4h15min, final setting time is 5h20min, 7d compressive strength is 1.65MPa, 14d compressive strength is 2.58MPa, the 28d compressive strength is 4.86MPa, the dry density is 1230kg/m 3 , the ultimate shear force of the phosphogypsum slurry is 52Pa, the ratio of the half-life of the prefabricated foam to the final setting time of the slurry is 1:1.1, the ultimate The ratio of shear force to average Feret diameter is 212:1.
  • a kind of phosphogypsum-based ecological cement foam lightweight soil material the raw materials are weighed according to the following mass parts: 45 parts of the first phosphogypsum, 50 parts of slag powder, 5 parts of ordinary Portland cement, phosphogypsum fine aggregate (the second 140 parts of phosphogypsum, 3.05 parts of composite admixture (1 part of water-reducing agent, 2 parts of coagulant, 0.05 part of rheological additive, the mass ratio of rheological additive, water-reducing agent and coagulant is 1: 20:40), 15 parts of prefabricated foam, 75 parts of water, where the SiO 2 /Al 2 O 3 ratio is 2.5, and the CaO / SO 3 ratio is 1.6.
  • Figure 1 for its preparation flow chart.
  • Example 1 The specific preparation steps are as shown in Example 1.
  • the components and dosage (the mass added per 1000ml of water) are: 3.5g sodium ⁇ -alkenesulfonate (AOS) foaming agent, 1.5g xanthan gum foam stabilizer, and the resulting prefabricated foam is as follows: The half-life of the foam is 340min, and the average Feret diameter is 0.227mm.
  • AOS sodium ⁇ -alkenesulfonate
  • the main performance indicators of the obtained phosphogypsum-based ecological cement foam lightweight soil test block are: fluidity is 160mm, initial setting time is 5h30min, final setting time is 6h45min, 7d compressive strength is 1.35MPa, 14d compressive strength is 2.26MPa, the 28d compressive strength is 3.60MPa, the ultimate shear force of the phosphogypsum slurry is 45Pa, the ratio of the half-life of the prefabricated foam to the final setting time of the slurry is 1:1.2, the ultimate shear force and the average Feret diameter The ratio is 198:1.
  • a kind of phosphogypsum-based ecological cement foam lightweight soil material the raw materials are weighed according to the following mass parts: 45 parts of the first phosphogypsum, 50 parts of slag powder, 5 parts of ordinary Portland cement, phosphogypsum fine aggregate (the second 180 parts of phosphogypsum, 3.05 parts of composite admixture (1 part of water-reducing agent, 2 parts of coagulant, 0.05 part of rheological additive, the mass ratio of rheological additive, water-reducing agent and coagulant is 1: 20:40), 10 parts of prefabricated foam, 85 parts of water, where the SiO 2 /Al 2 O 3 ratio is 2.6, and the CaO / SO 3 ratio is 1.5.
  • Figure 1 for its preparation flow chart.
  • the main performance indicators of the phosphogypsum-based ecological cement foam lightweight soil test block obtained in this example are: fluidity is 190mm, initial setting time is 5h25min, final setting time is 6h50min, 7d compressive strength is 0.85MPa, 14d The compressive strength is 1.63MPa, the 28d compressive strength is 2.74MPa, and the dry density is 865kg/m 3 ; the ultimate shear force of the phosphogypsum slurry is 80Pa, and the ratio of the half-life of the prefabricated foam to the final setting time of the slurry is 1: 1.3, the ratio of ultimate shear force to average Feret diameter is 145:1.
  • a kind of phosphogypsum-based ecological cement foam lightweight soil material the raw materials are weighed according to the following mass parts: 45 parts of the first phosphogypsum, 50 parts of slag powder, 5 parts of ordinary Portland cement, phosphogypsum fine aggregate (the second 200 parts of phosphogypsum), 3.52 parts of composite admixture (1 part of water-reducing agent, 2.5 parts of coagulant, 0.02 part of rheological additive, the mass ratio of rheological additive, water-reducing agent and coagulant is 1: 50:125), 10 parts of prefabricated foam, 100 parts of water, where the SiO 2 /Al 2 O 3 ratio is 2.8, and the CaO / SO 3 ratio is 2.0.
  • Example 1 The specific preparation steps are as described in Example 1; wherein during the preparation of the prefabricated foam , the components and dosage (the mass added per 1000ml of water) are: 5.0g sodium ⁇ -alkenesulfonate (AOS) foaming agent, 3.0g xanthan gum foam stabilizer; the half-life of the obtained prefabricated foam is 315min, and the average Feret The diameter is 0.245mm.
  • AOS sodium ⁇ -alkenesulfonate
  • xanthan gum foam stabilizer 3.0g xanthan gum foam stabilizer
  • the half-life of the obtained prefabricated foam is 315min
  • the average Feret The diameter is 0.245mm.
  • the main performance indicators of the phosphogypsum-based ecological cement foam lightweight soil test block obtained in this comparative example are: fluidity is 140mm, initial setting time is 8h45min, final setting time is 10h30min, 7d compressive strength is 0.45MPa, 14d The compressive strength is 1.02MPa, the 28d compressive strength is 1.86MPa, and the dry density is 915kg/m 3 .
  • the porosity is 30%, the roundness is 1.358, the average Feret diameter is 0.245mm, the ultimate shear force of the phosphogypsum slurry is 105Pa, the ratio of the half-life of the prefabricated foam to the final setting time of the slurry is 1:2.0, the ultimate shear force and The average Feret diameter ratio is 429:1.
  • the specific preparation steps are as described in Example 1.
  • the components and dosage (The mass added per 1000ml of water) is: 4.0g sodium ⁇ -alkenesulfonate (AOS) foaming agent, 1.5g xanthan gum foam stabilizer; the half-life of the obtained prefabricated foam is 285min, and the average Feret diameter is 0.227mm.
  • AOS sodium ⁇ -alkenesulfonate
  • the main performance indicators of the phosphogypsum-based ecological cement foam lightweight soil test block obtained in this comparative example are: fluidity is 150mm, initial setting time is 10h40min, final setting time is 13h15min, 7d compressive strength is 0.68MPa, 14d The compressive strength is 1.25MPa, the 28d compressive strength is 1.72MPa, and the dry density is 876kg/m 3 ; the ultimate shear force of the phosphogypsum slurry is 25Pa, and the ratio of the half-life of the prefabricated foam to the final setting time of the slurry is 1: 2.8, the ratio of ultimate shear force to average Feret diameter is 110:1.
  • a kind of phosphogypsum-based ecological cement foam lightweight earth material the raw materials are weighed according to the following mass parts: 50 parts of the first phosphogypsum, 50 parts of slag powder, 5 parts of ordinary Portland cement, phosphogypsum fine aggregate (the second 160 parts of phosphogypsum, 5.2 parts of composite admixture (3 parts of water-reducing agent, 2 parts of coagulant, 0.2 part of rheological additive, the mass ratio of rheological additive, water-reducing agent and coagulant is 1: 15:10), 8 parts of prefabricated foam, 85 parts of water, where the SiO 2 /Al 2 O 3 ratio is 2.4, and the CaO / SO 3 ratio is 1.7.
  • Example 1 The specific preparation steps are as described in Example 1, where in the prefabricated foam preparation process , the components and dosage (the mass added per 1000ml of water) are: 5.0g sodium ⁇ -alkenesulfonate (AOS) foaming agent, 0.5g xanthan gum foam stabilizer; the half-life of the obtained prefabricated foam is 350min, and the average Feret The diameter is 0.550mm.
  • AOS sodium ⁇ -alkenesulfonate
  • the main performance indicators of the phosphogypsum-based ecological cement foam lightweight soil test block obtained in this comparative example are: fluidity is 155mm, initial setting time is 6h35min, final setting time is 8h40min, 7d compressive strength is 0.42MPa, 14d The compressive strength is 0.95MPa, the 28d compressive strength is 1.47MPa, and the dry density is 924kg/m 3 .
  • the average Feret diameter of the prefabricated foam is 0.620mm
  • the ultimate shear force of the phosphogypsum slurry is 23Pa
  • the ratio of the half-life of the prefabricated foam to the final setting time of the slurry is 1:3.6
  • the ratio of the ultimate shear force to the average Feret diameter is 37 :1.

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Abstract

本发明公开了一种磷石膏基生态水泥泡沫轻质土，磷石膏基生态水泥泡沫轻质土由第一磷石膏、第二磷石膏、矿渣粉、硅酸盐水泥、减水剂、促凝剂、流变助剂、预制泡沫和水为主要原料制备而成。本发明在实现大掺量磷石膏基工业废弃物资源化利用的基础上，可有效兼顾所得水泥泡沫轻质土良好的力学性能、工作性能和稳定性能；同时可有效简化制备工艺，降低能耗，具有重要的经济和环境效益，适合推广应用。

Description

一种磷石膏基生态水泥泡沫轻质土及其制备方法 技术领域
本发明属于建筑材料技术领域，具体涉及一种磷石膏基生态水泥泡沫轻质土及其制备方法。
背景技术
磷石膏是湿法制磷过程中产生的一种副产物，生产工艺不同使其主要成分为含磷二水石膏或半水石膏，还含有无机残留杂质，使其呈酸性。由于它会对环境资源直接或间接造成侵占和污染，通常只能当作一种废渣处理。目前，我国大量的磷石膏只能露天堆放，磷石膏的随意排放堆积不仅占用大量土地，而且对我们生活的大气环境、土壤、水资源等都造成污染，磷石膏的处理利用问题已经迫在眉睫。为了制磷工业的绿色发展，处置大量堆积的磷石膏的问题已经刻不容缓；需进一步拓宽磷石膏利用途径，探索磷石膏在路基材料等领域的高附加值应用。
泡沫轻质土是一种较常见的路基材料，将磷石膏制备泡沫轻质土不仅可以拓宽磷石膏利用途径，还可以实现磷石膏大掺量、规模化、高值化利用。目前这方面的研究尚处于起步阶段，如：专利CN112062529A公开了一种大掺量磷石膏的石膏基泡沫混凝土，以磷石膏、水泥、纤维、缓凝剂、发泡剂、稳泡剂、催化剂和水为原料制备而成；该方案中采用的磷石膏需在恒温130℃烘箱中烘干60min，通过高温预处理使磷石膏具有气硬性胶凝特性，并采用化学发泡的方式制备泡沫混凝土；采用的高温预处理手段会额外增加能耗，不经济也不环保，同时磷石膏的掺量有限；专利CN112811858A公开了一种全固废泡沫混凝土，以湿磨超细矿渣、磷石膏、钢渣、铁尾矿等固废物为主要原料，在复配激发剂(磷石膏、钢渣、碳酸钠的混合物)和复配稳泡剂的作用下制备轻质高强的全固废泡沫混凝土；该方案中复配激发剂占原料组成的4～10％，其中磷石膏掺量占50％左右，磷石膏掺量整体上并不高。此外，有相关学者提出采用化学激发方式制备碱激发胶凝材料，利用碱激发胶凝材料固化磷石膏，但化学激发剂往往价格高昂，并且制备的固化磷石膏材料存在易返碱、易开裂与强度倒缩等问题，明显限制了其推广应用。
发明内容
本发明的主要目的在于针对现有技术存在的问题和不足，提供一种磷石膏基生态水泥泡沫轻质土，在实现大掺量磷石膏基工业废弃物资源化利用的基础上， 可有效兼顾良好的力学性能、工作性能和稳定性能；同时可有效简化制备工艺，降低能耗，具有重要的经济和环境效益，适合推广应用。
为实现上述目的，本发明采用的技术方案为：
一种磷石膏基生态水泥泡沫轻质土材料，它以磷石膏基生态水泥、磷石膏细集料、预制复合泡沫、复合外加剂和水为主要原料，其中磷石膏基生态水泥作为胶凝材料，由第一磷石膏、矿渣粉、硅酸盐水泥组成；磷石膏细集料采用第二磷石膏；复合外加剂由促凝剂、减水剂和流变助剂组成；各组分及所占重量份数包括：第一磷石膏40～70份，第二磷石膏60～180份，矿渣粉40～70份，硅酸盐水泥2～5份，复合外加剂1.5～7.5份，预制复合泡沫2～20份，水40～95份。
上述方案中，所述复合外加剂中各组分及其所占质量份数为：流变助剂0～0.5份，减水剂0.5～2份，促凝剂1～5份。
优选的，所述流变助剂、减水剂与促凝剂的质量比为1:(5～20):(20～80)。
更优选的，所述流变助剂、减水剂与促凝剂的质量比为1:(8～15):(30～50)。
上述方案中，所述磷石膏基生态水泥泡沫轻质土原料的SiO2/Al2O3摩尔比控制为2.3～2.6，CaO/SO3摩尔比控制为1.5～1.8。
上述方案中，所述第一磷石膏采用原状磷石膏经低温烘干破碎后制得，粒径不大于0.08mm，其比表面积为250～450m2/kg；第二磷石膏采用原状磷石膏进行低温烘干后过筛得到，其粒径不大于2.36mm；其中，原状磷石膏的含水量不大于25％，CaSO4·2H2O质量分数不小于75％，水溶性P2O5质量分数不大于0.8％，水溶性F-质量分数不大于0.5％。
上述方案中，所述低温烘干采用的烘干温度为45～55℃，时间为18～36h。
上述方案中，所述矿渣粉为不低于S95级的粒化高炉矿渣粉，主要成分为CaO、Al2O3和SiO2，比表面积不小于400m2/kg。
上述方案中，所述水泥为硅酸盐水泥或普通硅酸盐水泥，强度等级不低于P.O 42.5。
上述方案中，所述促凝剂为氢氧化钠、生石灰和快硬型硫铝酸盐水泥等中的一种或几种。
上述方案中，所述减水剂为聚羧酸高性能减水剂，含固量10～25％，减水率为20～30％。
上述方案中，所述流变助剂为羟丙基甲基纤维素(HPMC)、羧甲基纤维素 钠(CMC)等中的一种或几种；HPMC与CMC的纯度不低于98％。
上述方案中，所述预制泡沫由发泡剂、稳泡剂溶于水经物理发泡方式制得，其中发泡剂为α-烯基磺酸钠(AOS)，其纯度不低于96％；稳泡剂为黄原胶，其纯度不低于96％；按重量计，所述预制泡沫组分及用量为：发泡剂2.0～5.0g，稳泡剂0.5～2.5g，水1000ml。
上述方案中，所述所得预制泡沫的半衰期不小于200min，平均Feret直径为0.10～0.60mm。
上述方案中，所得预制泡沫的半衰期(单位为min)与磷石膏料浆的凝结时间(单位为min)之比控制在1:(1～1.5)；磷石膏料浆的极限剪切力(单位为Pa)与预制泡沫平均Feret直径(单位为mm)之比控制在(100～300):1，磷石膏料浆的极限剪切应力为35～85Pa；其中磷石膏料浆由磷石膏基生态水泥、磷石膏细集料、复合外加剂和水进行均匀拌制得到(步骤S2所得)。
上述方案中，所述泡沫轻质土的干密度为800～1400kg/m3，流动度为160～210mm，7d抗压强度为0.5～3.0MPa，28d抗压强度为1.5～8.0MPa。
上述一种磷石膏基生态水泥泡沫轻质土及其制备方法，包括如下步骤：
S1、制备预制泡沫：将发泡剂、稳泡剂和水混合，通过空气压缩机发泡，得到预制泡沫；
S2、制备磷石膏基生态水泥料浆：将称取的磷石膏基生态水泥和复合外加剂混合均匀，然后放于搅拌锅中加水和磷石膏细集料搅拌均匀，制得磷石膏料浆；
S3、制备泡沫轻质土：将步骤S1制备的预制泡沫加入步骤S2制备的料浆中，搅拌至预制泡沫与料浆混合均匀，得泡沫轻质土混合料；
S4、浇筑、养护：将所得泡沫轻质土混合料进行浇筑、养护，即得泡沫轻质土试件。
上述方案中，所述养护步骤采用的温度为18～22℃，湿度为95％以上，养护不低于7天。
上述方案中，所述步骤S1具体包括：
S1.1、称取一定量的发泡剂、稳泡剂和水，将发泡剂和稳泡剂加入水中搅拌得到混合溶液；
S1.2、将步骤S1.1中的混合溶液置于泡沫装置中，泡沫装置通过软管与空气压缩机相连；利用空气压缩机进行发泡即得到预制泡沫。
与现有技术相比，本发明的有益效果为：
1)本发明以磷石膏基生态水泥替代普硅水泥作为胶凝材料，极大减少了水泥的使用；并以磷石膏作为细集料制备；同时达到大掺量(磷石膏含量可高达80％以上)、规模化、高值化消纳磷石膏的目的；磷石膏兼具有胶凝材料原料、细集料骨架填充双重功能；为使组成体系兼顾良好的力学性能、工作性能、耐久性能及环保性能，进一步通过优化组成设计，精准调控水化产物，有效固化磷石膏中可溶性磷、氟等污染物，实现性能优良与环保达标的双重目的，同时达到大掺量、规模化、高值化消纳磷石膏的目的；适用于工程填料等领域；
2)通过调控磷石膏基生态水泥内部原材料SiO2/Al2O3与CaO/SO3摩尔比，以确保磷石膏基生态水泥浆体具备良好的力学性能与耐久性能；同时，通过对复合外加剂进行优选，并进一步调控促凝剂、流变助剂、减水剂之间的配比，宏观方面调控料浆凝结时间与预制泡沫半衰期之间的比例关系，在微观方面调控磷石膏料浆的极限剪切力与预制泡沫平均Feret直径之间的比例关系，实现对磷石膏基生态水泥泡沫轻质土工作性能、保水性能、早期强度、料浆结构均匀、致密性等多重效果的同步提升；
3)本发明所得磷石膏基生态水泥泡沫轻质土具有显著的节能环保优势，相比通用水泥CO2减排90％以上；无须借助常规的高温煅烧、蒸压养护等手段，可有效兼顾良好的力学性能、工作性能和稳定性能，可为磷石膏等工业废弃物的高附加值应用提供一条新思路。
附图说明
图1为磷石膏基生态水泥泡沫轻质土的制作流程示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
为使本发明的目的、技术方案和优点更加清楚，下面对本发明实施方式作进一步地描述。
以下实施例中，采用的原状磷石膏的主要化学组成为CaO和SO3，主要成分为CaSO4·2H2O，附着水质量分数不大于25％，CaSO4·2H2O质量分数为81％， 水溶性P2O5质量分数为0.04％，水溶性F-质量分数为0.1％。其中第一磷石膏通过将原状磷石膏经低温烘干(45℃，36h)、粉磨破碎后制得，粒径不大于0.08mm，其比表面积为415m2/kg；第二磷石膏为原状磷石膏低温烘干(45℃，36h)处理后过筛得到，粒径不大于2.36mm，其比表面积为86m2/kg。
采用的矿渣粉为S95级粒化高炉矿渣粉，主要成分为CaO、Al2O3和SiO2，测得矿渣粉比表面积424m2/kg。
采用的水泥为普通硅酸盐水泥，强度等级为P.O 42.5。
采用的促凝剂为快硬型硫铝酸盐水泥。
采用的减水剂为聚羧酸高性能减水剂，含固量20％，减水率为28％。
采用的流变助剂为羟丙基甲基纤维素(HPMC)。
以下实施例中，所得磷石膏基生态水泥泡沫轻质土相关宏观性能与预制泡沫孔结构参数的测试方法如下：
(1)流动度：将新拌的磷石膏基生态水泥泡沫轻质土浆料(泡沫轻质土混合料)缓慢倒入圆筒模中，所述圆筒模的尺寸为：直径为80mm，高度为80mm；
(2)凝结时间：将新拌的磷石膏基生态水泥泡沫轻质土浆料倒入试模中，所述试模的尺寸为：试模为深40mm±0.2mm、顶内径Φ65mm±0.5mm、底内径Φ75mm±0.5mm的截顶圆锥体；每只试模应配备一个大于试模、厚度≥2.5mm的平板玻璃底板进行凝结时间的测定；
(3)抗压强度：制备边长为100mm的磷石膏基生态水泥泡沫轻质土试块，参考实施例所述养护方法脱模后，测量不同龄期的抗压强度；
(4)干密度：制备边长为100mm的立方体泡沫混凝土试块，置于温度为20±2℃，相对湿度为95％以上的环境中养护，并测量其干密度；
(5)极限剪切力：首先将刚搅拌好的磷石膏基生态水泥泡沫轻质土浆料装入一个内径为170mm，高为100mm的圆柱体容器内，随后将一块厚度小于1mm，宽为50mm，高为75mm，表面粗糙度为25的电工绝缘塑料薄片埋在料浆内，埋入深度为65mm，最后用拉力计(精度为0.0001N)勾住埋在料浆中的塑料片，将其匀速缓慢拉出料浆，则料浆的极限剪切应力可由下式求得：
式中：F为拉力计的测量值(N)；b为薄板的宽度(m)；h为薄板埋入料 浆的深度(m)；τm为地质聚合物净浆的极限剪切应力(Pa)；
(6)用载玻片取少量制备的预制泡沫，使之缓慢分层后置于光学显微镜下观察并采集图像；对采集的图像进行灰度和二值化处理，设置标尺后对图像进行孔结构参数的测定。
实施例1
一种磷石膏基生态水泥泡沫轻质土材料，按照下列质量份数称取原材料：第一磷石膏45份，矿渣粉50份，普通硅酸盐水泥5份，磷石膏细集料(第二磷石膏)60份，复合外加剂2.55份(减水剂0.5份，促凝剂2份，流变助剂0.05份，流变助剂、减水剂、促凝剂三者质量比为1:10:40)，预制泡沫10份，水50份，其中SiO2/Al2O3比为2.3，CaO/SO3比为1.8；
其制备流程示意图见图1，具体包括如下步骤：
S1、制备预制泡沫：将发泡剂、稳泡剂和水混合，通过空气压缩机发泡，得到预制泡沫；各组分及用量(每1000ml水中加入的质量)为：4.0gα-烯基磺酸钠(AOS)发泡剂，1.5g黄原胶稳泡剂；所得预制泡沫的半衰期为260min，平均Feret直径为0.227mm；
S2、制备磷石膏基生态水泥料浆：将称取的磷石膏基生态水泥和复合外加剂混合均匀，然后放于搅拌锅中加水和磷石膏细集料搅拌均匀，制得磷石膏料浆；所得料浆的极限剪切力为60Pa；
S3、制备泡沫轻质土：将步骤S1制备的预制泡沫加入步骤S2制备的磷石膏料浆中，搅拌至预制泡沫与料浆混合均匀，得泡沫轻质土混合料；
S4、浇筑、养护：将所得泡沫轻质土混合料进行浇筑、养护(养护步骤采用的温度为18～22℃，湿度为95％以上)，即得泡沫轻质土试件。
经测试，本实施例所得磷石膏基生态水泥泡沫轻质土试块的主要性能指标为：流动度为180mm，初凝时间为3h40min，终凝时间为5h15min，7d抗压强度为2.42MPa，14d抗压强度为3.36MPa，28d抗压强度为4.18MPa，干密度为850kg/m3，预制泡沫的半衰期与料浆终凝时间的比例为1:1.2，极限剪切力与平均Feret直径的比例为264:1。
实施例2
一种磷石膏基生态水泥泡沫轻质土材料，按照下列质量份数称取原材料：第一磷石膏45份，矿渣粉50份，普通硅酸盐水泥5份，磷石膏细集料(第二磷石膏)100份，复合外加剂2.7份(减水剂0.65份，促凝剂2份，流变助剂0.05份，流变助剂、减水剂、促凝剂三者质量比为1:13:40)预制泡沫5份，水65份，其中SiO2/Al2O3比为2.4，CaO/SO3比为1.7；其制备流程图参考图1，具体制备步骤如实施例1所述；其中预制泡沫制备过程中采用的各组分及用量(每1000ml水中加入的质量)为：3.0gα-烯基磺酸钠(AOS)发泡剂，1.0g黄原胶稳泡剂，所得预制泡沫的半衰期为290min，平均Feret直径为0.245mm。
经测试，所得磷石膏基生态水泥泡沫轻质土试块的主要性能指标为：流动度为190mm，初凝时间为4h15min，终凝时间为5h20min，7d抗压强度为1.65MPa，14d抗压强度为2.58MPa，28d抗压强度为4.86MPa，干密度为1230kg/m3，磷石膏料浆的极限剪切力为52Pa，预制泡沫的半衰期与料浆终凝时间的比例为1:1.1，极限剪切力与平均Feret直径的比例为212:1。
实施例3
一种磷石膏基生态水泥泡沫轻质土材料，按照下列质量份数称取原材料：第一磷石膏45份，矿渣粉50份，普通硅酸盐水泥5份，磷石膏细集料(第二磷石膏)140份，复合外加剂3.05份(减水剂1份，促凝剂2份，流变助剂0.05份，流变助剂、减水剂、促凝剂三者质量比为1:20:40)，预制泡沫15份，水75份，其中SiO2/Al2O3比为2.5，CaO/SO3比为1.6，其制备流程图参考图1，具体制备步骤如实施例1所述；其中预制泡沫制备过程中，各组分及用量(每1000ml水中加入的质量)为：3.5gα-烯基磺酸钠(AOS)发泡剂，1.5g黄原胶稳泡剂，所得预制泡沫的半衰期为340min，平均Feret直径为0.227mm。
经测试，所得磷石膏基生态水泥泡沫轻质土试块的主要性能指标为：流动度为160mm，初凝时间为5h30min，终凝时间为6h45min，7d抗压强度为1.35MPa，14d抗压强度为2.26MPa，28d抗压强度为3.60MPa，磷石膏料浆的极限剪切力为45Pa，预制泡沫的半衰期与料浆终凝时间的比例为1:1.2，极限剪切力与平均Feret直径的比例为198:1。
实施例4
一种磷石膏基生态水泥泡沫轻质土材料，按照下列质量份数称取原材料：第一磷石膏45份，矿渣粉50份，普通硅酸盐水泥5份，磷石膏细集料(第二磷石膏)180份，复合外加剂3.05份(减水剂1份，促凝剂2份，流变助剂0.05份，流变助剂、减水剂、促凝剂三者质量比为1:20:40)，预制泡沫10份，水85份，其中SiO2/Al2O3比为2.6，CaO/SO3比为1.5，其制备流程图参考图1，其制备流程图参考图1，具体制备步骤如实施例1所述；其中预制泡沫的制备过程中，各组分及用量(每1000ml水中加入的质量)为：5.0gα-烯基磺酸钠(AOS)发泡剂，2.0g黄原胶稳泡剂，所得预制泡沫的半衰期为315min，平均Feret直径为0.550mm。
经测试：本实施例所得磷石膏基生态水泥泡沫轻质土试块的主要性能指标为：流动度为190mm，初凝时间为5h25min，终凝时间为6h50min，7d抗压强度为0.85MPa，14d抗压强度为1.63MPa，28d抗压强度为2.74MPa，干密度为865kg/m3；磷石膏料浆的极限剪切力为80Pa，预制泡沫的半衰期与料浆终凝时间的比例为1:1.3，极限剪切力与平均Feret直径的比例为145:1。
对比例1
一种磷石膏基生态水泥泡沫轻质土材料，按照下列质量份数称取原材料：第一磷石膏45份，矿渣粉50份，普通硅酸盐水泥5份，磷石膏细集料(第二磷石膏)200份，复合外加剂3.52份(减水剂1份，促凝剂2.5份，流变助剂0.02份，流变助剂、减水剂、促凝剂三者质量比为1:50:125)，预制泡沫10份，水100份，其中SiO2/Al2O3比为2.8，CaO/SO3比为2.0，具体制备步骤如实施例1所述；其中预制泡沫制备过程中，各组分及用量(每1000ml水中加入的质量)为：5.0gα-烯基磺酸钠(AOS)发泡剂，3.0g黄原胶稳泡剂；所得预制泡沫的半衰期为315min，平均Feret直径为0.245mm。
经测试，本对比例所得磷石膏基生态水泥泡沫轻质土试块的主要性能指标为：流动度为140mm，初凝时间为8h45min，终凝时间为10h30min，7d抗压强度为0.45MPa，14d抗压强度为1.02MPa，28d抗压强度为1.86MPa，干密度为915kg/m3。孔隙率30％，圆度1.358，平均Feret直径为0.245mm，磷石膏料浆的极限剪切力为105Pa，预制泡沫的半衰期与料浆终凝时间的比例为1:2.0，极限剪切力与平均Feret直径的比例为429:1。
对比例2
一种磷石膏基生态水泥泡沫轻质土材料，按照下列质量份数称取原材料：第一磷石膏60份，矿渣粉50份，普通硅酸盐水泥4份，第二磷石膏(第二磷石膏)150份，复合外加剂5.04(减水剂1份，促凝剂4份，流变助剂0.04份，流变助剂：减水剂：促凝剂＝1:25:100)，预制泡沫10份，水100份，其中SiO2/Al2O3比为2.0，CaO/SO3比为1.2，具体制备步骤如实施例1所述，其中预制泡沫制备过程中，各组分及用量(每1000ml水中加入的质量)为：4.0gα-烯基磺酸钠(AOS)发泡剂，1.5g黄原胶稳泡剂；所得预制泡沫的半衰期为285min，平均Feret直径为0.227mm。
经测试，本对比例所得磷石膏基生态水泥泡沫轻质土试块的主要性能指标为：流动度为150mm，初凝时间为10h40min，终凝时间为13h15min，7d抗压强度为0.68MPa，14d抗压强度为1.25MPa，28d抗压强度为1.72MPa，干密度为876kg/m3；磷石膏料浆的极限剪切力为25Pa，预制泡沫的半衰期与料浆终凝时间的比例为1:2.8，极限剪切力与平均Feret直径的比例为110:1。
对比例3
一种磷石膏基生态水泥泡沫轻质土材料，按照下列质量份数称取原材料：第一磷石膏50份，矿渣粉50份，普通硅酸盐水泥5份，磷石膏细集料(第二磷石膏)160份，复合外加剂5.2份(减水剂3份，促凝剂2份，流变助剂0.2份，流变助剂、减水剂、促凝剂三者质量比为1:15:10)，预制泡沫8份，水85份，其中SiO2/Al2O3比为2.4，CaO/SO3比为1.7，具体制备步骤如实施例1所述，其中预制泡沫制备过程中，各组分及用量(每1000ml水中加入的质量)为：5.0gα-烯基磺酸钠(AOS)发泡剂，0.5g黄原胶稳泡剂；所得预制泡沫的半衰期为350min，平均Feret直径为0.550mm。
经测试，本对比例所得磷石膏基生态水泥泡沫轻质土试块的主要性能指标为：流动度为155mm，初凝时间为6h35min，终凝时间为8h40min，7d抗压强度为0.42MPa，14d抗压强度为0.95MPa，28d抗压强度为1.47MPa，干密度为924kg/m3。预制泡沫平均Feret直径为0.620mm，磷石膏料浆的极限剪切力为23Pa，预制泡沫的半衰期与料浆终凝时间的比例为1:3.6，极限剪切力与平均Feret直径的比例为37:1。
上述实施例仅是为了清楚地说明所做的实例，而并非对实施方式的限制。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或者变动，这里无需也无法对所有的实施方式予以穷举，因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围。

Claims (10)

  1. 一种磷石膏基生态水泥泡沫轻质土材料，其特征在于，它以磷石膏基生态水泥、磷石膏细集料、预制复合泡沫、复合外加剂和水为主要原料，其中磷石膏基生态水泥作为胶凝材料，由第一磷石膏、矿渣粉、硅酸盐水泥组成；磷石膏细集料采用第二磷石膏；复合外加剂由促凝剂、减水剂和流变助剂组成；各组分及其所占重量份数包括：第一磷石膏40～70份，第二磷石膏60～180份，矿渣粉40～70份，硅酸盐水泥2～5份，复合外加剂1.5～7.5份，预制复合泡沫2～20份，水40～95份。
  2. 根据权利要求1所述的磷石膏基生态水泥泡沫轻质土材料，其特征在于，所述复合外加剂中各组分及其所占质量份数为：流变助剂0～0.5份，减水剂0.5～2份，促凝剂1～5份。
  3. 根据权利要求1所述的磷石膏基生态水泥泡沫轻质土材料，其特征在于，所述磷石膏基生态水泥泡沫轻质土原料的SiO2/Al2O3摩尔比控制为2.3～2.6，CaO/SO3摩尔比控制为1.5～1.8。
  4. 根据权利要求1所述的磷石膏基生态水泥泡沫轻质土材料，其特征在于，所述第一磷石膏采用原状磷石膏经低温烘干破碎后制得，粒径不大于0.08mm，其比表面积为250～450m2/kg；第二磷石膏采用原状磷石膏进行低温烘干后过筛得到，其粒径不大于2.36mm。
  5. 根据权利要求4所述的磷石膏基生态水泥泡沫轻质土材料，其特征在于，所述低温烘干采用的烘干温度为45～55℃，时间为18～36h。
  6. 根据权利要求1所述的磷石膏基生态水泥泡沫轻质土材料，其特征在于，所述促凝剂为氢氧化钠、生石灰、快硬型硫铝酸盐水泥中的一种或几种；所述流变助剂为羟丙基甲基纤维素、羧甲基纤维素钠中的一种或几种。
  7. 根据权利要求1所述的磷石膏基生态水泥泡沫轻质土材料，其特征在于，所述预制泡沫由发泡剂、稳泡剂溶于水经物理发泡方式制得，其中发泡剂为α-烯基磺酸钠；稳泡剂为黄原胶；所述预制泡沫制备过程中各组分及用量为：发泡剂2.0～5.0g，稳泡剂0.5～2.5g，水1000ml。
  8. 根据权利要求7所述的磷石膏基生态水泥泡沫轻质土材料，其特征在于，所得预制泡沫的半衰期不小于200min，平均Feret直径为0.10～0.60mm。
  9. 根据权利要求1所述的磷石膏基生态水泥泡沫轻质土材料，其特征在于，所得预制泡沫的半衰期与磷石膏料浆的终凝时间之比控制在1:(1～1.5)；磷石膏料 浆的极限剪切力与预制泡沫平均Feret直径之比控制在(100～300):1；其中磷石膏料浆由磷石膏基生态水泥、磷石膏细集料、复合外加剂和水进行均匀拌制得到。
  10. 一种权利要求1～9任一项所述磷石膏基生态水泥泡沫轻质土材料的制备方法，其特征在于，包括如下步骤：
    S1、制备预制泡沫：将发泡剂、稳泡剂和水混合，通过空气压缩机发泡，得到预制泡沫；
    S2、制备磷石膏基生态水泥料浆：称取一定量的第一磷石膏、矿渣粉、水泥以及外加剂，混合均匀，然后放于搅拌锅中加水和第二磷石膏填料搅拌均匀，制得料浆；
    S3、制备泡沫轻质土：将步骤S1制备的预制泡沫加入步骤S2制备的料浆中，搅拌至预制泡沫与料浆混合均匀，得泡沫轻质土混合料；
    S4、浇筑、养护：将所得泡沫轻质土混合料进行浇注、养护，即得泡沫轻质土试件。
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