CN116655342A - Titanium gypsum-based cementing material, product and preparation method thereof - Google Patents
Titanium gypsum-based cementing material, product and preparation method thereof Download PDFInfo
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- CN116655342A CN116655342A CN202310493555.3A CN202310493555A CN116655342A CN 116655342 A CN116655342 A CN 116655342A CN 202310493555 A CN202310493555 A CN 202310493555A CN 116655342 A CN116655342 A CN 116655342A
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- titanium gypsum
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 135
- 239000010440 gypsum Substances 0.000 title claims abstract description 135
- 239000010936 titanium Substances 0.000 title claims abstract description 135
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 135
- 239000000463 material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000002893 slag Substances 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 54
- 239000010959 steel Substances 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000012360 testing method Methods 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 4
- 239000004568 cement Substances 0.000 claims description 22
- 238000001723 curing Methods 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- 238000010276 construction Methods 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000004566 building material Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000008030 superplasticizer Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000011127 sodium aluminium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
-
- 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
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Press-Shaping Or Shaping Using Conveyers (AREA)
Abstract
The titanium gypsum-based cementing material, the product and the preparation method thereof comprise the following steps of S1: the preparation method comprises the following steps of: 40-70 parts of finely ground titanium gypsum, 15-40 parts of finely ground steel slag, 15-40 parts of aggregate, 0.5-3.0 parts of water glass, 0.1-2.0 parts of polycarboxylic acid water reducer and 10-20 parts of water; s2, adding the additive sodium silicate and the polycarboxylate water reducer into water in sequence, and stirring to obtain a mixed solution; s3, sequentially adding the fine-ground titanium gypsum, the fine-ground steel slag and the aggregate into stirring equipment, stirring to obtain a mixture, and then adding the mixed solution obtained in the step S2 into the stirring equipment to uniformly mix and stir the mixture and the mixed solution to obtain a mixed material; s4, pouring the mixed material obtained in the step S3 into a mold or extruding the mixed material to obtain a test block; s5, curing the test block obtained in the step S4 at normal pressure or autoclaved curing to obtain the titanium gypsum-based cementing material. The invention solves the problems of low utilization rate of titanium gypsum resource, serious environmental pollution and poor physical and mechanical properties at present, and provides a low-carbon environment-friendly building material for the building industry.
Description
Technical Field
The invention belongs to the technical field of building materials, and relates to a titanium gypsum-based cementing material, a product and a preparation method thereof.
Background
Titanium gypsum is industrial waste residue discharged when titanium pigment is produced by a sulfuric acid method. According to statistics, the production of 1 ton of titanium dioxide by a sulfuric acid method can produce 6-7 tons of titanium gypsum, the production of 2021 national titanium dioxide is 379 ten thousand tons, the same ratio is increased by 28 ten thousand tons, the amplification is 8.0 percent, the creation history is novel, the total production of 2274-2653 ten thousand tons of titanium gypsum is realized, and the main component of the titanium gypsum is CaSO 4 ·2H 2 O. Titanium gypsum is mainly used for roadbed materials, cement retarders, wall materials and the like, researchers also use titanium gypsum to prepare sintered bricks, but the overall recycling utilization rate is low, most of the titanium gypsum adopts a piling mode, occupies land, pollutes surface water and underground water, even pollutes the atmosphere, and becomes a main pollution source in a titanium gypsum discharge area. Along with the continuous promotion of national environmental protection policies, the environmental protection pressure of titanium dioxide emission enterprises is increased, and the high-quality resource utilization of titanium gypsum becomes an important constraint factor for the production and development of enterprises.
The invention is as follows: a method for repairing the abandoned mine by using titanium gypsum as impervious lining layer (publication No. 2022.01.18, publication No. CN113944150A, publication No. 2021112222671) discloses a technical scheme that the integral structure of repairing abandoned mine is composed of impervious lining layer, percolate drainage layer, filler layer and sealing soil layer from bottom to top, wherein the impervious lining layer is made of titanium gypsum. The construction method comprises the following steps: firstly, laying an impermeable layer, secondly, laying a percolate guide and discharge layer, and then filling a material layer to finally obtain the field-sealing soil-covering layer. The method has the following problems: the technology uses titanium gypsum as a mine restoration material, only serves as a common filling material, and the gelation property of the titanium gypsum is not fully exerted, so that the filling strength is low, the environmental pollution risk still exists, and the added value is low.
The invention is as follows: a baking-free and steaming-free titanium gypsum brick and a preparation method thereof (application publication date: 2015.04.01, application number: 2014108191651, publication number: CN 104478388A) are provided, wherein the titanium gypsum brick comprises the following components in percentage by mass: 24.1-32.3% of titanium gypsum, 52-63.8% of aggregate, 11.2-18.5% of cement/mineral powder and 0.8-1.0% of additive, wherein the additive is a mixture of anhydrous sodium sulfate, alum and curing agent, and the aggregate is one or more of industrial slag, broken stone and river sand. The preparation method of the titanium gypsum brick comprises the following steps: s1, extruding and stirring slurry type titanium gypsum to form hydraulic slurry; s2, mixing the crushed titanium gypsum with aggregate, and stirring for 2-4min; s3, mixing the materials prepared in the step S2 with additives, cement/mineral powder and stirring for 1-3min; s4, extrusion molding, namely, adopting spray watering to keep the water content of each part in the hopper consistent, wherein the ratio of the mass of water to the mass of the material prepared in S3 is as follows: 1:32-40. The method has the following problems: cement and mineral powder are used as main strength component sources, the hydration characteristics of the titanium gypsum are not fully exerted, the strength of the product is low, the using amount of the titanium gypsum is small, the additive is a conventional product, and the technical advancement is not strong; extrusion of a product is required, the size of the product is limited by a die, and the shape and variety of the product are small.
Problems and disadvantages of prior art preparation of titanium gypsum: the main problems of the prior art are that the titanium gypsum product has low physical and mechanical properties, the application range of the product is narrow, the utilization rate of resources is low, and the added value of the product is low. The composite material cannot be widely used as building materials for various buildings, and is not in accordance with the national energy-saving low-carbon environment-friendly policy requirements.
Solves the difficulty in the prior art: aiming at the characteristics of low grade of titanium gypsum, high impurity content and high adhering water content, the characteristics of the coupling synergistic effect of titanium gypsum and metallurgical slag are brought into play, and the problem of low strength of titanium gypsum products is solved.
The meaning of the prior art is solved: solves the difficult problem of high-efficiency resource utilization of titanium gypsum, solves the difficult problem of enterprise production, protects the environment, and has better social benefit and economic benefit.
Disclosure of Invention
Aiming at the problems of the prior art, the invention provides a preparation method of a titanium gypsum-based cementing material according to market demands and characteristics of titanium gypsum, solves the problems of low utilization rate of titanium gypsum resources, serious environmental pollution and poor physical and mechanical properties at present, and provides a low-carbon environment-friendly building material for the building industry.
The technical scheme of the invention is as follows:
the preparation method of the titanium gypsum-based cementing material comprises the following steps: s1: the preparation method comprises the following steps of: 40-70 parts of finely ground titanium gypsum, 15-40 parts of finely ground steel slag, 15-40 parts of aggregate, 0.5-3.0 parts of water glass, 0.1-2.0 parts of polycarboxylic acid water reducer and 10-20 parts of water; s2, adding the additive sodium silicate and the polycarboxylate water reducer into water in sequence, and stirring to obtain a mixed solution; s3, sequentially adding the fine-ground titanium gypsum, the fine-ground steel slag and the aggregate into stirring equipment, stirring to obtain a mixture, and then adding the mixed solution obtained in the step S2 into the stirring equipment to uniformly mix and stir the mixture and the mixed solution to obtain a mixed material; s4, pouring the mixed material obtained in the step S3 into a mold or extruding the mixed material to obtain a test block; s5, curing the test block obtained in the step S4 at normal pressure or autoclaved curing to obtain the titanium gypsum-based cementing material.
Optionally, in the preparation method of the titanium gypsum-based cementing material, in the step S1, finely grinding titanium gypsum is to mix titanium gypsum and steel slag according to the weight percentage of 60-90:10-40, and grind the mixture to the specific surface area of 450-500m 2 /kg; or grinding wet titanium gypsum and wet steel slag containing adhesive water with water content of 30-50% of dry solid content to specific surface area of 450-500m 2 /kg。
Optionally, in the preparation method of the titanium gypsum-based cementing material, in the step S1, finely grinding the steel slag is to mix the steel slag and the slag according to the weight percentage of 50-80:20-50, and grind the steel slag and the slag to the specific surface area of 550-700m 2 /kg。
Optionally, in the preparation method of the titanium gypsum-based cementing material, in the step S1, the aggregate is natural building middle sand with fineness modulus of 3.0-2.3; or crushing and screening the metallurgical slag to obtain building middle sand with fineness modulus of 3.0-2.3; or the tailings are crushed and screened to form building middle sand with fineness modulus of 3.0-2.3; or the construction waste is crushed and screened to form the construction middlings with fineness modulus of 3.0-2.3.
Optionally, in the preparation method of the titanium gypsum-based cementing material, in the step S1, the water glass is sodium water glass with a modulus of 1.5-3.5, and the water reducing rate of the polycarboxylate water reducer is more than 20%.
Optionally, in the preparation method of the titanium gypsum-based cementing material, in the step S2, the additive water glass and the polycarboxylate water reducer are sequentially added into water, and stirred for 5-15 minutes at the temperature of 25-45 ℃ to prepare the mixed solution.
Optionally, in the preparation method of the titanium gypsum-based cementing material, in step S3, sequentially adding the finely ground titanium gypsum, the finely ground steel slag and the aggregate into a stirring device, stirring for 3-5 minutes to obtain a mixture, adding the mixed solution in step S2 into the stirring device, stirring at a low speed for 3 minutes, stirring at a high speed for 1 minute, uniformly mixing and stirring the mixture and the mixed solution, and standing for 30 minutes to obtain the mixed material.
Optionally, in the above preparation method of the titanium gypsum-based cement, in step S4, casting with a mold in the case where the high water-adding mixture has fluidity; under the condition that the low water adding mixture is dry and hard, the molding is carried out by using equipment; pouring and molding for 4-8 hours, demolding, extruding and molding for 5-30 minutes, and demolding to obtain the test block.
Optionally, in the preparation method of the titanium gypsum-based binding material, in step S5, the test block in step S4 is placed in a rapid curing box for steam curing after being left for 4 hours.
Optionally, in the preparation method of the titanium gypsum-based cementing material, in the step S5, the test block obtained in the step S4 is stored at normal temperature and maintained under the condition that the air humidity is more than 90%; or curing the test block obtained in the step S4 at 60-90 ℃ for 4-6 hours, and taking out to obtain the finished product.
A titanium gypsum-based cementing material is characterized in that: the titanium gypsum-based cementing material is prepared according to a preparation method of the titanium gypsum-based cementing material.
A titanium gypsum-based cement product, characterized in that: the titanium gypsum-based cementing material product is prepared according to the preparation method of the titanium gypsum-based cementing material.
Compared with the prior art, the invention has the following beneficial effects:
the invention fully utilizes the advantages of a gypsum-based cementing material system, combines the characteristics of titanium gypsum, utilizes an ultrafine grinding process to improve the cementing property of the titanium gypsum-steel slag-slag system by adding an exciting agent, bonds the aggregates together to generate better strength, and the prepared titanium gypsum-based cementing material has excellent physical and mechanical properties, and the prepared 40mm multiplied by 160mm test body has the flexural strength of 3-7MPa after moisture curing for 28 days, the compressive strength of 25-60MPa, the steam curing for 4-6 hours at 60-90 ℃, the flexural strength of 3.5-6.5MPa and the compressive strength of 30-55MPa.
The cementing material can be in a plastic flow state or a dry and hard state when in use; the casting can be directly performed, and the casting can also be extruded; the product can be cured at normal temperature or low temperature steam, and the preparation method is more environment-friendly.
Drawings
FIG. 1 is a flow chart of a method of preparing a titanium gypsum-based cement of the present invention;
FIG. 2 is a graph showing the variation of material strength of the titanium gypsum-based cement according to the amount of titanium gypsum blended;
FIG. 3 is a graph showing the variation of material strength with steel slag doping amount of the titanium gypsum-based cement of the present invention;
FIG. 4 is a graph showing the variation of material strength with aggregate loading for a titanium gypsum-based cement of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
A preparation method of a titanium gypsum-based cementing material comprises the following steps:
s1: the preparation method comprises the following steps of: 40-70 parts of finely ground titanium gypsum, 15-40 parts of finely ground steel slag, 15-40 parts of aggregate, 0.5-3.0 parts of water glass, 0.1-2.0 parts of polycarboxylic acid water reducer and 10-20 parts of water.
Wherein, the raw materials such as titanium gypsum, mineral powder, cement and the like are ground to a certain fineness by a ball mill, specifically, the finely ground titanium gypsum is prepared by superfine grinding titanium gypsum and steel slag, the titanium gypsum and the steel slag are mixed according to the weight percentage of 60-90:10-40, and the mixture is ground to the specific surface area of 450-500m 2 /kg. The grinding can be that titanium gypsum and steel slag are dried and then ground; or grinding wet titanium gypsum and wet steel slag containing adhesive water with water content of 30-50% of dry solid content to specific surface area of 450-500m 2 /kg。
The chemical components of the titanium gypsum are (dry basis) SiO 2 2.0 to 8.0 weight percent of Al 2 O 3 1.5 to 3.5 weight percent of Fe 2 O 3 7.0 to 12.0 weight percent, 25 to 30 weight percent of CaO, 2.0 to 11.0 weight percent of MgO and SO 3 30.0 to 41.0 weight percent, and 8.0 to 22.0 weight percent of loss. 30-50% of titanium gypsum adhesive water.
The finely ground steel slag is prepared by mixing the steel slag and the slag according to the weight percentage of 50-80:20-50, and grinding the mixture to the specific surface area of 550-700 square meters per kg.
The chemical components of the steel slag are (dry basis) SiO 2 16.5 to 21.7 weight percent of Al 2 O 3 2.5 to 7.0 weight percent of Fe 2 O 3 16.5 to 19.0 weight percent, 38.5 to 47.5 weight percent of CaO, 7.5 to 12.5 weight percent of MgO and SO 3 0.1 to 0.3wt percent,
the chemical composition of the slag is (dry basis) SiO 2 32.0 to 41.0 weight percent of Al 2 O 3 6.5 to 17.0 weight percent of Fe 2 O 3 0.2 to 4.0 weight percent, 32.5 to 49.0 weight percent of CaO, 2.0 to 13.0 weight percent of MgO and SO 3 0.5 to 5.0 weight percent, 0.1 to 4.0 weight percent of MnO and TiO 2 1.0 to 6.0wt percent.
The aggregate is natural building middle sand with fineness modulus of 3.0-2.3; or crushing and screening the metallurgical slag to obtain building middle sand with fineness modulus of 3.0-2.3; or the tailings are crushed and screened to form building middle sand with fineness modulus of 3.0-2.3; or the construction waste is crushed and screened to form the construction middlings with fineness modulus of 3.0-2.3.
The water glass is sodium water glass with the modulus of 1.5-3.5.
The water reducing rate of the polycarboxylate water reducer is more than 20%.
As shown in fig. 2, the strength of the titanium gypsum-based cement material of the present invention increases with the increase of the titanium gypsum doping amount, and when the titanium gypsum doping amount exceeds about 40%, the strength is correspondingly reduced; as shown in fig. 3, the material strength tends to increase and then decrease with the increase of the steel slag doping amount; as shown in fig. 4, a certain amount of aggregate was added, and the strength of the material tended to increase first due to a decrease in the amount of added water, but after increasing to a certain amount, the strength was significantly decreased. The invention therefore selects and adds the appropriate amount of raw materials to ensure the strength of the material produced.
S2, adding the additive sodium silicate and the polycarboxylate water reducer into water in sequence, and stirring for 5-15 minutes at the temperature of 25-45 ℃ to prepare a mixed solution;
s3, sequentially adding the fine-ground titanium gypsum, the fine-ground steel slag and the aggregate into stirring equipment, stirring for 3-5 minutes to obtain a mixture, adding the mixed solution prepared in the step S2 into the stirring equipment, stirring at a low speed for 3 minutes, stirring at a high speed for 1 minute, uniformly mixing and stirring the mixture and the mixed solution, and standing for 30 minutes to obtain a mixed material;
s4, pouring the mixed material obtained in the step S3 into a mold or extruding the mixed material into a mold to obtain a test block. Specifically, under the condition that the high water adding mixture has fluidity, pouring and forming are carried out by using a mould; under the condition that the low water adding mixture is dry and hard, the molding is carried out by using equipment; pouring and molding for 4-8 hours, demolding, extruding and molding for 5-30 minutes, and demolding to obtain a test block, wherein the size of the test block is preferably 40mm multiplied by 160mm.
S5, curing the test block obtained in the step S4 at normal pressure or autoclaved curing to obtain the titanium gypsum-based cementing material. And (3) standing the test block in the step (S4) for 4 hours, and then placing the test block into a rapid curing box for steam curing. Specifically, the test block obtained in the step S4 is stored at normal temperature and maintained under the condition that the air humidity is more than 90%; or curing the test block obtained in the step S4 at 60-90 ℃ for 4-6 hours, and taking out to obtain the finished product. Preferably, the water is heated to 90 ℃ at a constant speed, and the test block is cured in the steam for 6 hours and then taken out, thus obtaining the product.
The main technical principle of the invention is as follows: 1. adopts physical activation technology to grind titanium gypsum superfine powder, and steel slag is added in grinding to improve grindability of titanium gypsum. The surface energy of titanium gypsum and steel slag is improved through superfine grinding, and the hydration activity of the titanium gypsum and the steel slag is stimulated. 2. The superfine grinding is carried out on the steel slag and the slag, and the hydration activity of the glass body and mineral substances is stimulated. 3. By utilizing the alkali excitation effect of the water glass, the water glass is coupled with sulfate in the titanium gypsum to synergistically excite the glass body and mineral substances in the mixture, so that a hydration product mainly comprising hydrated calcium sulfoaluminate is generated. 4. The addition of the aggregate can obviously reduce the mixing water quantity, improve the compactness of the hardened body, improve the dimensional stability of the hardened body, increase the strength and improve the water resistance. 5. In the ingredients of the titanium gypsum-based cementing material, titanium gypsum, steel slag, slag and various aggregates are all solid wastes, and are all solid waste materials. The material can be applied in a dry and hard state or in a plastic state, and has a wide application range.
Example 1:
a titanium gypsum-based low-carbon environment-friendly product and a preparation method thereof comprise the following steps:
s1, preparing raw materials according to the following parts by weight: 45 parts of finely ground titanium gypsum, 25 parts of finely ground steel slag, 25 parts of tailing aggregate, 2.0 parts of water glass, 2.0 parts of polycarboxylate superplasticizer and 20 parts of water.
Specifically, 35 parts of titanium gypsum and 10 parts of steel slag are respectively mixed and ground into powder with a specific surface area of 450-500m by a ball mill 2 The fine grinding steel slag is prepared by mixing 15 parts of steel slag and 10 parts of slag, grinding to a specific surface area of 450-500m 2 /kg; crushing and screening the tailing aggregate until the fineness modulus is 3.0-2.3;
s2, sequentially adding water glass and a polycarboxylate water reducer into water, and stirring for 10 minutes at 30 ℃ to prepare a mixed solution;
s3, sequentially adding the finely ground titanium gypsum, the finely ground steel slag and the tailing aggregate into stirring equipment, stirring for 3-5 minutes, adding the mixed solution prepared in the step S2 into a stirrer, stirring at a low speed for 3 minutes, stirring at a high speed for 1 minute, and standing for 30 minutes to obtain a mixed material;
s4, pouring and molding the mixed material obtained in the step S3 by using a mold, and demolding after 4-8 hours to obtain a test block;
s5, curing the test block obtained in the step S4 at 60-90 ℃ for 4-6 hours, and taking out to obtain the titanium gypsum-based cementing material, wherein the flexural strength is 3.7MPa and the compressive strength is 32MPa.
Example 2:
a titanium gypsum-based low-carbon environment-friendly product and a preparation method thereof comprise the following steps:
s1, preparing raw materials according to the following parts by weight: 48 parts of finely ground titanium gypsum, 30 parts of finely ground steel slag, 25 parts of metallurgical slag aggregate, 2.5 parts of water glass, 1.0 part of polycarboxylate superplasticizer and 10 parts of water.
Specifically, the fine grinding titanium gypsum is to respectively mix and grind 40 parts of titanium gypsum and 8 parts of steel slag to a specific surface area of 450-500m by a ball mill 2 The fine grinding of the steel slag is to mix and grind 15 parts of the steel slag and 15 parts of the slag to a specific surface area of 450-500m 2 /kg; the metallurgical slag is crushed and screened until the fineness modulus is 3.0-2.3.
S2, sequentially adding water glass and a polycarboxylate water reducer into water, and stirring for 10 minutes at 30 ℃ to prepare a mixed solution;
s3, sequentially adding the fine-ground titanium gypsum, the fine-ground steel slag and the metallurgical slag aggregate into stirring equipment, stirring for 3-5 minutes, adding the mixed solution prepared in the step S2 into a stirrer, stirring for 3 minutes at a low speed, stirring for 1 minute at a high speed, and standing for 30 minutes to obtain a mixed material;
s4, extruding and molding the mixed material obtained in the step S3, and demolding after 30 minutes to obtain a test block;
s5, curing the test block obtained in the step S4 for 28 days at normal temperature under the condition of moisture, and taking out to obtain the titanium gypsum-based cementing material, wherein the flexural strength is 6.5MPa and the compressive strength is 50MPa.
Example 3:
a titanium gypsum-based low-carbon environment-friendly product and a preparation method thereof comprise the following steps:
s1, preparing raw materials according to the following parts by weight: 35 parts of finely ground titanium gypsum, 40 parts of finely ground steel slag, 25 parts of building rubbish aggregate, 3.0 parts of water glass, 1.0 part of polycarboxylate superplasticizer and 8 parts of water.
Specifically, 30 parts of titanium gypsum and 5 parts of steel slag are mixed and ground into powder with a specific surface area of 450-500m by a ball mill respectively 2 The fine grinding steel slag is prepared by mixing 30 parts of steel slag and 10 parts of slag, grinding to a specific surface area of 450-500m 2 /kg; the construction waste is crushed and screened until the fineness modulus is 3.0-2.3.
S2, sequentially adding water glass and a polycarboxylate water reducer into water, and stirring for 10 minutes at 30 ℃ to prepare a mixed solution;
s3, sequentially adding the fine-ground titanium gypsum, the fine-ground steel slag and the building rubbish aggregate prepared in the step S1 into stirring equipment, stirring for 3-5 minutes, adding the mixed solution prepared in the step S2 into a stirrer, stirring for 3 minutes at a low speed, stirring for 1 minute at a high speed, and standing for 30 minutes to obtain a mixed material;
s4, extruding and molding the mixed material obtained in the step S3, and demolding after 30 minutes to obtain a test block;
s5, curing the test block obtained in the step S4 for 28 days at normal temperature under the condition of moisture, and taking out to obtain the titanium gypsum-based cementing material, wherein the flexural strength is 3.0MPa and the compressive strength is 25MPa.
Example 4:
a titanium gypsum-based low-carbon environment-friendly product and a preparation method thereof comprise the following steps:
s1, preparing raw materials according to the following parts by weight: 53 parts of finely ground titanium gypsum, 25 parts of finely ground steel slag, 25 parts of metallurgical slag aggregate, 2.5 parts of water glass, 2.0 parts of polycarboxylate superplasticizer and 20 parts of water.
Specifically, the fine grinding titanium gypsum is to respectively mix and grind 40 parts of titanium gypsum and 13 parts of steel slag to a specific surface area of 450-500m by a ball mill 2 The fine-grinding steel slag is 20 parts of steel slag and 5 parts of slag, and the mixture is ground to the specific surface area of 450-500m 2 /kg; the metallurgical slag is crushed and screened until the fineness modulus is 3.0-2.3.
S2, sequentially adding water glass and a polycarboxylate water reducer into water, and stirring for 10 minutes at 30 ℃ to prepare a mixed solution;
s3, sequentially adding the finely ground titanium gypsum, the finely ground steel slag and the building rubbish aggregate into stirring equipment, stirring for 3-5 minutes, adding the mixed solution prepared in the step S3 into a stirrer, stirring for 3 minutes at a low speed, stirring for 1 minute at a high speed, and standing for 30 minutes;
s4, pouring and molding the mixed material obtained in the step S3, and demolding after 4-6 hours to obtain a test block;
s5, curing the test block obtained in the step S4 for 28 days at normal temperature under the condition of moisture, and taking out to obtain the titanium gypsum-based cementing material, wherein the flexural strength is 5.5MPa and the compressive strength is 43.5MPa.
As can be seen from the above examples, the titanium gypsum-based cementing material prepared by the invention has higher strength, the size is 40mm multiplied by 160mm test block, the flexural strength is 3-7MPa after moisture curing for 28 days, the compressive strength is 25-60MPa, the flexural strength is 3.5-6.5MPa after steam curing for 4-6 hours at 60-90 ℃, the compressive strength is 30-55MPa, and the titanium gypsum-based cementing material has excellent physical and mechanical properties; the preparation method of the invention has high utilization rate of titanium gypsum resource and is environment-friendly.
The above description is merely illustrative of the embodiments of the present invention, and the present invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principle of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (10)
1. The preparation method of the titanium gypsum-based cementing material is characterized by comprising the following steps of:
s1: the preparation method comprises the following steps of: 40-70 parts of finely ground titanium gypsum, 15-40 parts of finely ground steel slag, 15-40 parts of aggregate, 0.5-3.0 parts of water glass, 0.1-2.0 parts of polycarboxylic acid water reducer and 10-20 parts of water;
s2, adding the additive sodium silicate and the polycarboxylate water reducer into water in sequence, and stirring to obtain a mixed solution;
s3, sequentially adding the fine-ground titanium gypsum, the fine-ground steel slag and the aggregate into stirring equipment, stirring to obtain a mixture, and then adding the mixed solution obtained in the step S2 into the stirring equipment to uniformly mix and stir the mixture and the mixed solution to obtain a mixed material;
s4, pouring the mixed material obtained in the step S3 into a mold or extruding the mixed material to obtain a test block;
s5, curing the test block obtained in the step S4 at normal pressure or autoclaved curing to obtain the titanium gypsum-based cementing material.
2. The method for preparing a titanium gypsum-based cement according to claim 1, wherein in step S1, the finely ground titanium gypsum is obtained by mixing titanium gypsum with steel slag in a weight ratio of 60-90:10-40, and grinding the mixture to a specific surface area of 450-500m 2 /kg; or grinding wet titanium gypsum and wet steel slag containing adhesive water with water content of 30-50% of dry solid content to specific surface area of 450-500m 2 /kg。
3. The method for preparing titanium gypsum-based cement according to claim 1, wherein in step S1, the finely ground steel slag is obtained by mixing steel slag and slag in a weight ratio of 50-80:20-50, and grinding the mixture to a specific surface area of 550-700m 2 /kg。
4. The method for preparing a titanium gypsum-based cement according to claim 1, wherein in step S1, the aggregate is natural building middle sand having a fineness modulus of 3.0 to 2.3; or crushing and screening the metallurgical slag to obtain building middle sand with fineness modulus of 3.0-2.3; or the tailings are crushed and screened to form building middle sand with fineness modulus of 3.0-2.3; or the construction waste is crushed and screened to form the construction middlings with fineness modulus of 3.0-2.3.
5. The method for preparing a titanium gypsum-based cement according to claim 1, wherein in step S1, the water glass is sodium water glass having a modulus of 1.5 to 3.5, and the polycarboxylate water reducer has a water reduction rate of more than 20%.
6. The method for preparing a titanium gypsum-based cement according to claim 1, wherein in step S2, the admixture water glass and the polycarboxylate water reducer are sequentially added to water and stirred at a temperature of 25 to 45 ℃ for 5 to 15 minutes to prepare a mixed solution.
7. The method for preparing the titanium gypsum-based cementing material according to claim 1, wherein in the step S3, the fine-ground titanium gypsum, the fine-ground steel slag and the aggregate are sequentially added into a stirring device and stirred for 3-5 minutes to obtain the mixture, the mixed solution in the step S2 is added into the stirring device and stirred for 3 minutes at a low speed and then for 1 minute at a high speed, the mixture and the mixed solution are uniformly mixed and stirred, and the mixture is left stand for 30 minutes to obtain the mixed material.
8. The method for preparing a titanium gypsum-based cement according to claim 1, wherein in step S4, the cement is cast with a mold in the case where the high water-added mixture has fluidity; under the condition that the low water adding mixture is dry and hard, the molding is carried out by using equipment; pouring and molding for 4-8 hours, demolding, extruding and molding for 5-30 minutes, and demolding to obtain the test block.
9. The method for preparing a titanium gypsum-based cement according to claim 1, wherein in step S5, the test block in step S4 is left to stand for 4 hours and then put into a rapid curing box for steam curing. The method for preparing titanium gypsum-based cement according to claim 1, wherein in step S5, the test block obtained in step S4 is stored at room temperature and maintained with an air humidity of more than 90%; or curing the test block obtained in the step S4 at 60-90 ℃ for 4-6 hours, and taking out to obtain a finished product.
10. A titanium gypsum-based cement product, characterized in that: the product is prepared according to the preparation method of the titanium gypsum-based cementing material of any one of claims 1 to 9.
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