CN111995352B - Inorganic cement board and preparation method thereof - Google Patents

Inorganic cement board and preparation method thereof Download PDF

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Publication number
CN111995352B
CN111995352B CN202010829891.7A CN202010829891A CN111995352B CN 111995352 B CN111995352 B CN 111995352B CN 202010829891 A CN202010829891 A CN 202010829891A CN 111995352 B CN111995352 B CN 111995352B
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inorganic
calcium
cement board
parts
inorganic cement
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CN111995352A (en
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郑四荣
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Dongguan Lixin Environmental Protection Technology Co ltd
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Dongguan Chuangli Technology Development Co ltd
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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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • 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
    • C04B18/0436—Dredged harbour or river sludge
    • 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
    • C04B18/12—Waste materials; Refuse from quarries, mining or the like
    • 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
    • C04B18/18—Waste materials; Refuse organic
    • C04B18/24—Vegetable refuse, e.g. rice husks, maize-ear refuse; Cellulosic materials, e.g. paper, cork
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Mining & Mineral Resources (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to the technical field of inorganic cement boards, and particularly provides an inorganic cement board and a preparation method thereof. The invention provides an inorganic cement board, which at least comprises 20-40 parts of stone tailings, 15-30 parts of crop wastes, 10-20 parts of quicklime, 65-90 parts of sludge and 10-20 parts of water glass.

Description

Inorganic cement board and preparation method thereof
Technical Field
The invention relates to the technical field of inorganic cement boards, and particularly provides an inorganic cement board and a preparation method thereof.
Background
A lot of garbage is generated in the building construction process, the dismantling process, the agricultural production process and the lake bottom dredging process, the garbage is utilized singly at present, the building garbage is treated in a landfill mode, the crop garbage is treated in a field returning and burning mode, and the lake bottom sludge is accumulated to cause odor and pollute the environment, so that no good measures are taken for treatment.
At present, clay, mineral products, ceramics or concrete is mainly used as a raw material for making bricks, but the natural resources are non-renewable, and excessive mining can even cause damage to the ecological environment. Therefore, research and application of green and environmentally friendly materials must be considered and strengthened.
Disclosure of Invention
In order to solve the technical problems, the invention provides an inorganic cement board in a first aspect, which at least comprises 20-40 parts of stone tailings, 15-30 parts of crop wastes, 10-20 parts of quick lime, 65-90 parts of sludge and 10-20 parts of water glass.
As a preferable technical scheme of the invention, the preparation raw material also comprises an inorganic dispersant.
According to a preferable technical scheme of the invention, the mass ratio of the inorganic dispersant to the water glass is 1: (1.2-5).
In a preferred embodiment of the present invention, the raw materials for preparing the inorganic dispersant include a calcium-containing inorganic salt, a phosphorus-containing substance, and a modifier.
As a preferable technical scheme of the invention, the calcium-containing inorganic salt is one or a combination of more of tetrahydrate calcium nitrate, calcium chloride, calcium carbonate, calcium sulfate, calcium chlorate, calcium hydroxide and calcium oxide.
As a preferable technical scheme of the invention, the phosphorus-containing substance is selected from one or a combination of more of diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium metaphosphate, sodium hexametaphosphate, ammonium dihydrogen phosphate, sodium polyphosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate and phosphoric acid.
As a preferable technical scheme of the invention, the specific surface area of the calcium carbonate is 13000-14000 cm2/g。
As a preferable technical scheme of the invention, the phosphoric acid is a phosphoric acid aqueous solution with the concentration of 0.9-1.1 mol/L.
As a preferable technical scheme of the invention, the molecular formula of the water glass is Na2O·nSiO2The modulus n is 1.8 to 2.5.
The second aspect of the present invention provides a method for preparing the inorganic cement board, comprising at least the following steps:
(1) crushing and grinding the stone tailings to obtain stone particles;
(2) drying and crushing crop waste to obtain crop particles;
(3) putting the sludge into a stirrer, adding quicklime, adding stone particles and crop particles after reaction, stirring, then adding water glass and an inorganic dispersant, and uniformly stirring to obtain inorganic cement board slurry;
(4) and (3) introducing the inorganic cement board slurry into a mold, performing compression molding by using a compression molding machine, and performing autoclaved curing to obtain the inorganic cement board slurry.
Has the advantages that: the invention provides an inorganic cement board and a preparation method thereof, wherein the specific inorganic dispersant and the water glass with specific modulus are selected to be added to interact with each component in the system, so that the compressive strength and the flexural strength of the inorganic cement board can be obviously improved, the service life is long, and the cost is low; the stone tailings and the crop waste are used as raw materials, so that the utilization rate of resources is improved, the environment is protected, and the sustainable development of the resources is realized.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
In order to solve the technical problems, the invention provides an inorganic cement board in a first aspect, which at least comprises 20-40 parts of stone tailings, 15-30 parts of crop wastes, 10-20 parts of quick lime, 65-90 parts of sludge and 10-20 parts of water glass.
In one embodiment, the raw materials for preparing the inorganic cement board further comprise 30 parts of stone tailings, 22 parts of crop wastes, 15 parts of quicklime, 70 parts of sludge and 15 parts of water glass in parts by weight.
In a more preferred embodiment, the preparation feedstock further comprises an inorganic dispersant.
<Stone tailings>
The stone tailings are granite tailings.
<Waste of crops>
The crop waste of the invention comprises fiber powder made of crop straws, branches of various trees and wood chips generated by wood processing.
In a preferred embodiment, the crop waste comprises wheat straw and rice straw.
In a more preferred embodiment, the mass ratio of the wheat straw to the rice straw is 1: (1.2-1.4); more preferably, the mass ratio of the wheat straws to the rice straws is 1: 1.3.
<sludge treatment>
The sludge of the invention is one or the mixture of municipal sludge and lake bottom sludge.
In a preferred embodiment, the sludge is lake bottom sludge, and the water content is 75-95%; preferably, the water content is 80%.
<Water glass>
The water glass is commonly called sodium silicate and is water-soluble silicate compounded by alkali metal oxide and silicon dioxide in different proportions. Silicon dioxide (SiO)2) With sodium oxide (Na)2O) is the ratio of the number of moles n, called the modulus of the water glass, n is more than or equal to 3 and called neutral water glass, n<3 is called alkaline water glass.
In a preferred embodiment, the water glass has the formula Na2O·nSiO2The modulus n is 1.8 to 2.5.
In a more preferred embodiment, the water glass has a modulus n of 1.9 to 2.1 and is purchased from SSP-20 of Jinan Yi vast chemical Co.
In a more preferred embodiment, the mass ratio of the inorganic dispersant to the water glass is 1: (1.2-5); more preferably, the mass ratio of the inorganic dispersant to the water glass is 1: (2-4); more preferably, the mass ratio of the inorganic dispersant to the water glass is 1: 3.1.
<inorganic dispersant>
The raw materials for preparing the inorganic dispersant comprise calcium-containing inorganic salt, a phosphorus-containing substance and a modifier.
Inorganic salt containing calcium
The calcium-containing inorganic salt is one or a combination of more of tetrahydrate calcium nitrate, calcium chloride, calcium carbonate, calcium sulfate, calcium chlorate, calcium hydroxide and calcium oxide.
In a preferred embodiment, the calcium-containing inorganic salt is calcium carbonate.
In a more preferred embodiment, the specific surface area of the calcium carbonate is 13000-14000 cm2(ii)/g; more preferably, the specific surface area of the calcium carbonate is 13500cm2/g。
In a more preferred embodiment, the calcium carbonate is purchased from Douduo e-commerce, Inc. of Beijing.
The specific surface area can be determined by a GSL-101BII type laser particle size analyzer.
Phosphorus-containing substance
The phosphorus-containing substance is selected from one or a combination of more of diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium metaphosphate, sodium hexametaphosphate, ammonium dihydrogen phosphate, sodium polyphosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate and phosphoric acid.
In a preferred embodiment, the phosphorus-containing material is phosphoric acid.
In a more preferred embodiment, the phosphoric acid is an aqueous phosphoric acid solution with a concentration of 0.9 to 1.1 mol/L; more preferably, the phosphoric acid is an aqueous phosphoric acid solution having a concentration of 1 mol/L.
In a more preferred embodiment, the molar ratio of the phosphorus in the calcium and phosphorus-containing substances in the calcium-containing inorganic salt is 1.6 to 1.8; more preferably, the molar ratio of calcium in the calcium-containing inorganic salt to phosphorus in the phosphorus-containing substance is 1.7.
<Modifying agent>
In one embodiment, the modifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyacrylamide, stearic acid, citric acid, polyethylene glycol, sodium alginate, sodium carboxymethyl cellulose and alkylphenol polyoxyethylene ether.
In a preferred embodiment, the modifier comprises sodium carboxymethylcellulose, citric acid and alkylphenol ethoxylates.
In a more preferred embodiment, the viscosity of the sodium carboxymethylcellulose is from 100 to 200 mPa-s; more preferably, the viscosity of the sodium carboxymethyl cellulose is 150 to 200 mPas.
In a more preferred embodiment, the sodium carboxymethylcellulose is purchased from FZ-1 of Shandong hundred million chemical industries, Inc.
In a more preferred embodiment, the alkylphenol ethoxylates have a hydroxyl value of 60 to 73mgKOH/g and an HLB value of 14.5 to 15; more preferably, the alkylphenol polyoxyethylene ether has a hydroxyl value of 60 to 68mgKOH/g and an HLB value of 15.
In a more preferred embodiment, the alkylphenol ethoxylate is purchased from OP-15 of southeast Union chemical Co.
In a more preferred embodiment, the mass ratio of the sodium carboxymethyl cellulose to the citric acid to the alkylphenol ethoxylate is 1: (0.4-0.6): (0.1 to 0.3); more preferably, the mass ratio of the sodium carboxymethylcellulose to the citric acid to the alkylphenol ethoxylates is 1: 0.5: 0.2.
the viscosity is measured at 25 ℃ in a 2 wt% aqueous solution, and the measurement method is not particularly limited in the present invention.
The preparation method of the inorganic dispersant comprises the following steps:
(1) adding calcium-containing inorganic salt into a three-neck flask filled with distilled water, heating to 55-60 ℃, stirring and dropwise adding a phosphorus-containing substance, then adding a modifier aqueous solution, stirring, and aging at 48-55 ℃ for 2-5 hours; the concentration of the modifier aqueous solution is 0.01-0.03 g/L; the volume ratio of the modifier aqueous solution to the distilled water is 1: (200-300);
(2) and cooling and centrifuging the aged product, washing, performing suction filtration, performing vacuum drying at 80 ℃ for 12-24 hours, and calcining at 900-1000 ℃ for 2-3 hours to obtain the catalyst.
In a preferred embodiment, the mass ratio of the calcium-containing inorganic salt to the distilled water is 1: (10-15); more preferably, the mass ratio of the calcium-containing inorganic salt to the distilled water is 1: 13.
the applicant finds that by adding a self-made inorganic dispersant and water glass with a modulus of 1.8-2.5, the mass ratio of the inorganic dispersant to the water glass is limited to 1: (1.2-5), can better interact with each component in the system, can show the compressive strength and the rupture strength that improve inorganic cement board, long service life, can be better applied to the constitution of roofing, wall, floor.
The second aspect of the present invention provides a method for preparing an inorganic cement board, comprising the steps of:
(1) crushing and grinding the stone tailings to obtain stone particles;
(2) drying and crushing crop waste to obtain crop particles;
(3) putting the sludge into a stirrer, adding quicklime, adding stone particles and crop particles after reaction, stirring, then adding water glass and an inorganic dispersant, and uniformly stirring to obtain inorganic cement board slurry;
(4) and (3) introducing the inorganic cement board slurry into a mold, performing compression molding by using a compression molding machine, and performing autoclaved curing to obtain the inorganic cement board slurry.
In a preferred embodiment, the method for preparing the inorganic cement board at least comprises the following steps:
(1) crushing the stone tailings, and sieving the crushed stone tailings with a 20-50-mesh sieve to obtain stone particles;
(2) drying crop waste, and crushing to obtain crop particles with particle size less than 1 mm;
(3) putting the sludge into a stirrer, adding quicklime, reacting for 2-3 h, adding stone particles and crop particles, stirring for 1-2 h, adding water glass and an inorganic dispersant, and uniformly stirring to obtain inorganic cement board slurry;
(4) introducing the inorganic cement board slurry into a mold, and performing compression molding by using a compression molding machine to obtain an inorganic cement board blank;
(5) and (3) placing the inorganic cement slab at the temperature of 180-190 ℃ and under the pressure of 0.9-1.0 MPa for autoclaving for 8-9 h to obtain the inorganic cement slab.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
The embodiment 1 of the invention provides an inorganic cement board, which is prepared from the following raw materials, by weight, 30 parts of stone tailings, 22 parts of crop wastes, 15 parts of quicklime, 70 parts of sludge and 15 parts of water glass.
The preparation raw materials also comprise an inorganic dispersant.
The stone tailings are granite tailings; the crop waste comprises wheat straw and rice straw; the mass ratio of the wheat straws to the rice straws is 1: 1.3; the sludge is lake bottom sludge and has a water content of 80%.
The molecular formula of the water glass is Na2O·nSiO2The modulus n is 1.9-2.1, and is purchased from SSP-20 of Jinan Yi vast chemical industry Co.
The mass ratio of the inorganic dispersant to the water glass is 1: 3.1.
the preparation raw materials of the inorganic dispersant comprise calcium-containing inorganic salt, phosphorus-containing substances and a modifier.
The calcium-containing inorganic salt is calcium carbonate; the specific surface area of the calcium carbonate is 13500cm2(ii)/g, purchased from Douduo electronic commerce, Inc., of Beijing.
The phosphorus-containing substance is a phosphoric acid aqueous solution with the concentration of 1 mol/L.
The molar ratio of the calcium in the calcium-containing inorganic salt to the phosphorus in the phosphorus-containing substance is 1.7.
The modifier comprises sodium carboxymethylcellulose, citric acid and alkylphenol polyoxyethylene; the mass ratio of the sodium carboxymethylcellulose to the citric acid to the alkylphenol polyoxyethylene is 1: 0.5: 0.2.
the sodium carboxymethylcellulose is purchased from FZ-1 of Shandong Yi Hongkong chemical industry Co., Ltd; the alkylphenol ethoxylates was purchased from OP-15 of the Union-sparrow chemical Co., Ltd.
The preparation method of the inorganic dispersant comprises the following steps:
(1) adding calcium-containing inorganic salt into a three-neck flask filled with distilled water, heating to 58 ℃, stirring and dropwise adding a phosphorus-containing substance, then adding a modifier aqueous solution, stirring, and aging at 50 ℃ for 3 hours; the concentration of the modifier aqueous solution is 0.02 g/L; the volume ratio of the modifier aqueous solution to the distilled water is 1: 250 of (a);
(2) cooling and centrifuging the aged product, washing, performing suction filtration, performing vacuum drying at 80 ℃ for 20h, and then calcining at 950 ℃ for 2h to obtain the catalyst.
The mass ratio of the calcium-containing inorganic salt to the distilled water is 1: 13.
the preparation method of the inorganic cement board comprises the following steps:
(1) crushing the stone tailings, and sieving with a 500-mesh sieve after grinding to obtain stone particles;
(2) drying crop waste, and crushing to obtain crop particles with particle size less than 1 mm;
(3) putting the sludge into a stirrer, adding quicklime, reacting for 2h, adding stone particles and crop particles, stirring for 2h, then adding water glass and an inorganic dispersant, and uniformly stirring to obtain inorganic cement board slurry;
(4) introducing the inorganic cement board slurry into a mold, and performing compression molding by using a compression molding machine to obtain an inorganic cement board blank;
(5) and (3) placing the inorganic cement slab at the temperature of 190 ℃ and under the pressure of 1.0MPa for autoclaving for 8 hours to obtain the cement.
Example 2
The embodiment 2 of the invention provides an inorganic cement board, which is prepared from the following raw materials, by weight, 30 parts of stone tailings, 22 parts of crop wastes, 15 parts of quicklime, 70 parts of sludge and 15 parts of water glass.
The preparation raw materials also comprise an inorganic dispersant.
The stone tailings are granite tailings; the crop waste comprises wheat straw and rice straw; the mass ratio of the wheat straws to the rice straws is 1: 1.3; the sludge is lake bottom sludge and has a water content of 80%.
The molecular formula of the water glass is Na2O·nSiO2The modulus n is 1.9-2.1, and is purchased from SSP-20 of Jinan Yi vast chemical industry Co.
The mass ratio of the inorganic dispersant to the water glass is 1: 2.
the preparation raw materials of the inorganic dispersant comprise calcium-containing inorganic salt, phosphorus-containing substances and a modifier.
The calcium-containing inorganic salt is calcium carbonate; the specific surface area of the calcium carbonate is 13500cm2(ii)/g, purchased from Douduo electronic commerce, Inc., of Beijing.
The phosphorus-containing substance is a phosphoric acid aqueous solution with the concentration of 1 mol/L.
The molar ratio of the calcium in the calcium-containing inorganic salt to the phosphorus in the phosphorus-containing substance is 1.7.
The modifier comprises sodium carboxymethylcellulose, citric acid and alkylphenol polyoxyethylene; the mass ratio of the sodium carboxymethylcellulose to the citric acid to the alkylphenol polyoxyethylene is 1: 0.4: 0.1.
the sodium carboxymethylcellulose is purchased from FZ-1 of Shandong Yi Hongkong chemical industry Co., Ltd; the alkylphenol ethoxylates was purchased from OP-15 of the Union-sparrow chemical Co., Ltd.
The preparation method of the inorganic dispersant comprises the following steps:
(1) adding calcium-containing inorganic salt into a three-neck flask filled with distilled water, heating to 58 ℃, stirring and dropwise adding a phosphorus-containing substance, then adding a modifier aqueous solution, stirring, and aging at 50 ℃ for 3 hours; the concentration of the modifier aqueous solution is 0.02 g/L; the volume ratio of the modifier aqueous solution to the distilled water is 1: 250 of (a);
(2) cooling and centrifuging the aged product, washing, performing suction filtration, performing vacuum drying at 80 ℃ for 20h, and then calcining at 950 ℃ for 2h to obtain the catalyst.
The mass ratio of the calcium-containing inorganic salt to the distilled water is 1: 13.
the preparation method of the inorganic cement board comprises the following steps:
(1) crushing the stone tailings, and sieving with a 500-mesh sieve after grinding to obtain stone particles;
(2) drying crop waste, and crushing to obtain crop particles with particle size less than 1 mm;
(3) putting the sludge into a stirrer, adding quicklime, reacting for 2h, adding stone particles and crop particles, stirring for 2h, then adding water glass and an inorganic dispersant, and uniformly stirring to obtain inorganic cement board slurry;
(4) introducing the inorganic cement board slurry into a mold, and performing compression molding by using a compression molding machine to obtain an inorganic cement board blank;
(5) and (3) placing the inorganic cement slab at the temperature of 190 ℃ and under the pressure of 1.0MPa for autoclaving for 8 hours to obtain the cement.
Example 3
The embodiment 3 of the invention provides an inorganic cement board, which is prepared from the following raw materials, by weight, 30 parts of stone tailings, 22 parts of crop wastes, 15 parts of quicklime, 70 parts of sludge and 15 parts of water glass.
The preparation raw materials also comprise an inorganic dispersant.
The stone tailings are granite tailings; the crop waste comprises wheat straw and rice straw; the mass ratio of the wheat straws to the rice straws is 1: 1.3; the sludge is lake bottom sludge and has a water content of 80%.
The molecular formula of the water glass is Na2O·nSiO2The modulus n is 1.9-2.1, and is purchased from SSP-20 of Jinan Yi vast chemical industry Co.
The mass ratio of the inorganic dispersant to the water glass is 1: 4.
the preparation raw materials of the inorganic dispersant comprise calcium-containing inorganic salt, phosphorus-containing substances and a modifier.
The calcium-containing inorganic salt is calcium carbonate; the specific surface area of the calcium carbonate is 13500cm2(ii)/g, purchased from Douduo electronic commerce, Inc., of Beijing.
The phosphorus-containing substance is a phosphoric acid aqueous solution with the concentration of 1 mol/L.
The molar ratio of the calcium in the calcium-containing inorganic salt to the phosphorus in the phosphorus-containing substance is 1.7.
The modifier comprises sodium carboxymethylcellulose, citric acid and alkylphenol polyoxyethylene; the mass ratio of the sodium carboxymethylcellulose to the citric acid to the alkylphenol polyoxyethylene is 1: 0.6: 0.3.
the sodium carboxymethylcellulose is purchased from FZ-1 of Shandong Yi Hongkong chemical industry Co., Ltd; the alkylphenol ethoxylates was purchased from OP-15 of the Union-sparrow chemical Co., Ltd.
The preparation method of the inorganic dispersant comprises the following steps:
(1) adding calcium-containing inorganic salt into a three-neck flask filled with distilled water, heating to 58 ℃, stirring and dropwise adding a phosphorus-containing substance, then adding a modifier aqueous solution, stirring, and aging at 50 ℃ for 3 hours; the concentration of the modifier aqueous solution is 0.02 g/L; the volume ratio of the modifier aqueous solution to the distilled water is 1: 250 of (a);
(2) cooling and centrifuging the aged product, washing, performing suction filtration, performing vacuum drying at 80 ℃ for 20h, and then calcining at 950 ℃ for 2h to obtain the catalyst.
The mass ratio of the calcium-containing inorganic salt to the distilled water is 1: 13.
the preparation method of the inorganic cement board comprises the following steps:
(1) crushing the stone tailings, and sieving with a 500-mesh sieve after grinding to obtain stone particles;
(2) drying crop waste, and crushing to obtain crop particles with particle size less than 1 mm;
(3) putting the sludge into a stirrer, adding quicklime, reacting for 2h, adding stone particles and crop particles, stirring for 2h, then adding water glass and an inorganic dispersant, and uniformly stirring to obtain inorganic cement board slurry;
(4) introducing the inorganic cement board slurry into a mold, and performing compression molding by using a compression molding machine to obtain an inorganic cement board blank;
(5) and (3) placing the inorganic cement slab at the temperature of 190 ℃ and under the pressure of 1.0MPa for autoclaving for 8 hours to obtain the cement.
Comparative example 1
Comparative example 1 of the present invention provides an inorganic cement board, which is similar to example 1 in the embodiment, except that the water glass has a modulus n of 2.75 to 2.95 and is purchased from SSP-28 of Jinan Yi vast chemical Co.
Comparative example 2
Comparative example 2 of the present invention provides an inorganic cement sheet, which is similar to example 1 in the embodiment except that the mass ratio of the inorganic dispersant to the water glass is 1: 8.
comparative example 3
Comparative example 3 of the present invention provides an inorganic cement sheet, which is similar to example 1, except that the inorganic dispersant is sodium hexametaphosphate.
Comparative example 4
Comparative example 4 of the present invention provides an inorganic cement sheet, which is similar to example 1, except that no dispersant is present.
Comparative example 5
Comparative example 5 of the present invention provides an inorganic cement sheet, which is similar to example 1, except that the viscosity of the sodium carboxymethyl cellulose is 500mPa · s, which is purchased from NJ-1 of shandong yi hong chemical industries, ltd.
Comparative example 6
Comparative example 6 of the present invention provides an inorganic cement sheet, which is similar to example 1, except that the alkylphenol ethoxylate has a hydroxyl value of 72mgKOH/g and an HLB value of 14, and is purchased from OP-13 of southern Tong, Union-sparked chemical Co., Ltd.
Comparative example 7
Comparative example 7 of the present invention provides an inorganic cement sheet, which is similar to example 1, except that the alkylphenol ethoxylate has a hydroxyl value of 52mgKOH/g and an HLB value of 16, which is purchased from OP-16 of southeast songby chemical company, ltd.
Comparative example 8
Comparative example 8 of the present invention provides an inorganic cement board, which is the same as example 1 in the specific embodiment, except that the mass ratio of sodium carboxymethylcellulose, citric acid, and alkylphenol ethoxylates is 1: 0.5: 1.
comparative example 9
Comparative example 9 of the present invention provides an inorganic cement sheet, which is similar to example 1, except that sodium carboxymethylcellulose is not included.
Comparative example 10
Comparative example 10 of the present invention provides an inorganic cement sheet, which is embodied in the same manner as in example 1, except that citric acid is not included.
Comparative example 11
Comparative example 11 of the present invention provides an inorganic cement sheet, which is similar to example 1, except that alkylphenol ethoxylates are not present.
Performance testing
Compression and rupture test
The test was carried out with reference to GB11945-1999 in MPa and the data were recorded.
TABLE 1
Figure BDA0002637548790000111
Figure BDA0002637548790000121
The data in the table 1 show that the inorganic cement board prepared by the invention has excellent compressive strength and flexural strength, and the stone tailings and the crop waste are used as raw materials, so that the inorganic cement board is green and environment-friendly, can be better applied to construction of roofs, wall surfaces and floors, and is a green and environment-friendly building material with better green and environment-friendly effects in building performance.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (4)

1. The inorganic cement board is characterized in that the preparation raw materials at least comprise, by weight, 20-40 parts of stone tailings, 15-30 parts of crop wastes, 10-20 parts of quicklime, 65-90 parts of sludge and 10-20 parts of water glass;
the molecular formula of the water glass is Na2O·nSiO2The modulus n is 1.8-2.5;
the preparation raw materials also comprise an inorganic dispersant;
the mass ratio of the inorganic dispersant to the water glass is 1: (1.2-5);
the preparation raw materials of the inorganic dispersant comprise calcium-containing inorganic salt, phosphorus-containing substances and a modifier;
the calcium-containing inorganic salt is selected from one or more of calcium nitrate tetrahydrate, calcium chloride, calcium carbonate, calcium sulfate, calcium chlorate, calcium hydroxide and calcium oxide;
the phosphorus-containing substance is selected from one or more of diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium metaphosphate, sodium hexametaphosphate, ammonium dihydrogen phosphate, sodium polyphosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate and phosphoric acid;
the modifier comprises sodium carboxymethylcellulose, citric acid and alkylphenol polyoxyethylene ether, wherein the mass ratio of the sodium carboxymethylcellulose to the citric acid to the alkylphenol polyoxyethylene ether is 1: (0.4-0.6): (0.1 to 0.3);
the preparation method of the inorganic dispersant comprises the following steps:
(1) adding calcium-containing inorganic salt into a three-neck flask filled with distilled water, heating to 55-60 ℃, stirring and dropwise adding a phosphorus-containing substance, then adding a modifier aqueous solution, stirring, and aging at 48-55 ℃ for 2-5 hours; the concentration of the modifier aqueous solution is 0.01-0.03 g/L; the volume ratio of the modifier aqueous solution to the distilled water is 1: (200-300);
(2) and cooling and centrifuging the aged product, washing, performing suction filtration, performing vacuum drying at 80 ℃ for 12-24 hours, and calcining at 900-1000 ℃ for 2-3 hours to obtain the catalyst.
2. The inorganic cement board as claimed in claim 1, wherein the specific surface area of the calcium carbonate is 13000-14000 cm2/g。
3. The inorganic cement board as claimed in claim 1, wherein the phosphoric acid is an aqueous phosphoric acid solution having a concentration of 0.9 to 1.1 mol/L.
4. The method for preparing an inorganic cement board as claimed in any one of claims 1 to 3, comprising at least the following steps:
(1) crushing and grinding the stone tailings to obtain stone particles;
(2) drying and crushing crop waste to obtain crop particles;
(3) putting the sludge into a stirrer, adding quicklime, adding stone particles and crop particles after reaction, stirring, then adding water glass and an inorganic dispersant, and uniformly stirring to obtain inorganic cement board slurry;
(4) and (3) introducing the inorganic cement board slurry into a mold, performing compression molding by using a compression molding machine, and performing autoclaved curing to obtain the inorganic cement board slurry.
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