CN116425497A - High-strength gypsum 3D printing material prepared from high-chlorine desulfurization gypsum and preparation method thereof - Google Patents
High-strength gypsum 3D printing material prepared from high-chlorine desulfurization gypsum and preparation method thereof Download PDFInfo
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- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 165
- 239000010440 gypsum Substances 0.000 title claims abstract description 165
- 238000010146 3D printing Methods 0.000 title claims abstract description 44
- 239000000460 chlorine Substances 0.000 title claims abstract description 40
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 32
- 230000023556 desulfurization Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000000227 grinding Methods 0.000 claims abstract description 27
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 27
- 239000011707 mineral Substances 0.000 claims abstract description 27
- 239000004088 foaming agent Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000009466 transformation Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 239000010881 fly ash Substances 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 8
- 235000010755 mineral Nutrition 0.000 claims description 25
- 239000011268 mixed slurry Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 238000005188 flotation Methods 0.000 claims description 9
- 238000010025 steaming Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- AFIVDKCWAVJVJN-UHFFFAOYSA-N Nc1nc(N)[n+]([S-])c(N)n1 Chemical compound Nc1nc(N)[n+]([S-])c(N)n1 AFIVDKCWAVJVJN-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 6
- 239000011654 magnesium acetate Substances 0.000 claims description 6
- 229940069446 magnesium acetate Drugs 0.000 claims description 6
- 235000011285 magnesium acetate Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 4
- 229960000411 camphor oil Drugs 0.000 claims description 4
- 239000010624 camphor oil Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000001739 pinus spp. Substances 0.000 claims description 4
- 229940036248 turpentine Drugs 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000004683 dihydrates Chemical class 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000010642 eucalyptus oil Substances 0.000 claims description 3
- 229940044949 eucalyptus oil Drugs 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000006253 efflorescence Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 206010037844 rash Diseases 0.000 abstract description 3
- 238000007665 sagging Methods 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 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
- C04B28/144—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 a flue gas desulfurization product
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
-
- 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
- C04B2201/50—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The high-strength gypsum 3D printing material prepared from the high-chlorine desulfurized gypsum comprises the following components in parts by weight: 65 to 85 parts of high-chlorine desulfurization gypsum, 14 to 34 parts of chloride ion curing mineral, 0.06 to 0.10 part of foaming agent and 0.32 to 1.52 parts of crystal transformation agent. The invention takes the solid waste desulfurized gypsum of the thermal power plant as a matrix material, and is assisted with fly ash, slag, bauxite and the like as the solidified mineral of harmful impurity free chloride ions in the desulfurized gypsum, and a proper amount of distilled water is added for wet mixed grinding in a ball mill, thereby being beneficial to improving the conversion rate of the desulfurized gypsum into high-strength gypsum, finally improving the strength of gypsum products, being beneficial to improving the effect of solidifying the free chloride ions and reducing the quantity of the free chloride ions in the gypsum products. As the free chloride ion content in the 3D printing high-strength gypsum product prepared by the invention is less than 100ppm, the high-strength gypsum product is not easy to generate the defects of moisture regain, alkali efflorescence, sagging, yellowing, poor mechanical property and the like in the use process, and the application of the high-strength gypsum in the field of building materials is facilitated to be enlarged.
Description
Technical Field
The invention belongs to the technical field of preparing high-strength gypsum 3D printing materials, and particularly relates to a high-strength gypsum 3D printing material prepared from high-chlorine desulfurized gypsum and a preparation method thereof.
Background
The desulfurized gypsum is solid waste of a thermal power plant, and is mainly used for preparing desulfurized gypsum whisker and high-strength gypsum powder in the prior art. The desulfurized gypsum whisker is mainly used in the fields of papermaking, friction materials, adhesives and the like, and plays a role in strengthening and toughening. The high-strength gypsum powder is mainly used for paper gypsum boards, gypsum blocks and part of decorative building materials for buildings. With the development of 3D printing technology, the decorative high-strength gypsum product can be formed by 3D printing. The desulfurization gypsum has the advantages of low cost, easy obtainment, small toxic and side effects and the like, and can be the first choice material of the 3D printing decorative building material.
However, in view of cost, a wet desulfurization process is generally adopted in a thermal power plant, so that the moisture content of the desulfurized gypsum is very large and can reach more than 10% -15%, the desulfurized gypsum with excessive moisture content cannot be directly processed, drying is needed, and the production cost of gypsum products is increased. In addition, because chloride ions in the supplementing water, HCl in the flue gas and chloride ions removed in the production process can cause the content of free chloride ions in the desulfurized gypsum to be too high, the free chloride ions are a harmful impurity in the desulfurized gypsum, and the defects of moisture regain, alkali efflorescence, sagging, yellowing, poor mechanical properties and the like of the gypsum product in the use process can be caused, so that the application of the high-strength gypsum in the field of building materials is severely restricted.
Disclosure of Invention
The invention mainly solves the technical problems existing in the prior art, and provides a high-strength gypsum 3D printing material prepared from high-chlorine desulfurized gypsum and a preparation method thereof.
The technical problems of the invention are mainly solved by the following technical proposal: the high-strength gypsum 3D printing material prepared from the high-chlorine desulfurization gypsum comprises the following components in parts by weight: 65 to 85 parts of high-chlorine desulfurization gypsum, 14 to 34 parts of chloride ion curing mineral, 0.06 to 0.10 part of foaming agent and 0.32 to 1.52 parts of crystal transformation agent.
Preferably, the high-strength gypsum 3D printing material comprises the following components in parts by weight: 75 parts of high-chlorine desulfurized gypsum, 24 parts of chloride ion solidified mineral, 0.08 part of foaming agent and 0.92 part of crystal transformation agent.
Preferably, the chloride ion solidification mineral is one or more of fly ash, slag and bauxite.
Preferably, the foaming agent is one of turpentine, eucalyptus oil and camphor oil.
Preferably, the crystal transfer agent is one or two of magnesium acetate and melamine sulfide.
The method for preparing the high-strength gypsum 3D printing material from the high-chlorine desulfurization gypsum comprises the following steps: step (1), adding high-chlorine desulfurization gypsum and chloride ion solidified minerals into a ball mill according to a proportion, adding a proper amount of distilled water to ensure that the comprehensive water content is 20-30%, uniformly stirring, carrying out wet mixed grinding, and solidifying free chloride ions of harmful impurities to obtain primary-preparation mixed slurry; step (2), adding a foaming agent into the primary mixed slurry prepared in the step (1) according to a proportion, uniformly stirring, and then continuously carrying out wet mixed grinding to prepare flotation mixed slurry so as to carry out flotation; step (3), discharging the flotation mixed slurry prepared in the step (2) in a container, standing for 5-8 hours, removing organic impurities in the desulfurized gypsum by using the chemical adsorption action of a foaming agent, removing metal ion impurities by using the coating action of the foaming agent, and leaving the gypsum slurry below for later use; step (4), placing the gypsum slurry prepared in the step (3) into an autoclave, adding a crystal transformation agent into the autoclave according to a proportion, and steaming the mixture after the mixture is uniformly stirred to convert the desulfurized gypsum slurry mainly comprising dihydrate gypsum into high-strength gypsum slurry mainly comprising alpha-hemihydrate gypsum; step (5), drying the high-strength gypsum slurry prepared in the step (4) to prepare high-strength gypsum; and (6) grinding the dried high-strength gypsum to a granularity of less than 120 mu m to obtain high-strength gypsum powder meeting the requirement of 3D printing, and adding distilled water as required to prepare a high-strength gypsum 3D printing material when in use to perform 3D printing. Wherein the rotation speed of wet mixed grinding in the step (1) is 200-400 rpm, the ball milling time is 20-40 min, and the particle size of solid particles in the prepared primary mixed slurry is 0.5-5 mu m; the rotation speed of wet mixed grinding in the step (2) is 200-400 rpm, and the ball milling time is 3-15 min; the steaming time of the steaming kettle in the step (4) is 1-5 h, and the steaming temperature is 100-140 ℃; the drying temperature in the step (5) is 30-60 ℃ and the drying time is 2-6 hours.
The invention takes the solid waste desulfurized gypsum of the thermal power plant as a matrix material, and is supplemented with fly ash, slag, bauxite and the like as solidified minerals of free chloride ions of harmful impurities in the desulfurized gypsum, and a proper amount of distilled water is added to carry out wet mixed grinding in a ball mill. On the one hand, the wet mixed grinding can improve the grinding efficiency of the desulfurized gypsum, so that the particle size of the desulfurized gypsum is smaller after grinding, the conversion rate of the desulfurized gypsum into high-strength gypsum is improved, and finally the strength of gypsum products can be improved; on the other hand, the wet mixing grinding ensures that the chloride ion solidified mineral and the desulfurized gypsum are mixed more uniformly, thereby being beneficial to improving the effect of solidifying free chloride ions and reducing the quantity of free chloride ions in gypsum products. In addition, the invention can directly add the chloride ion solidified mineral for wet mixed grinding under the condition of high water content of the desulfurized gypsum, thereby avoiding the link of drying the desulfurized gypsum and being beneficial to reducing the production cost.
The 3D printed high-strength gypsum product prepared by the invention takes 40mm 160mm test pieces of standard building gypsum as an example, and the free chloride ion content is less than 100ppm, the flexural strength is 3-6 MPa, and the compressive strength is 35-45 MPa. As the free chloride ion content in the 3D printing high-strength gypsum product prepared by the invention is less than 100ppm, the high-strength gypsum product is not easy to generate the defects of moisture regain, alkali efflorescence, sagging, yellowing, poor mechanical property and the like in the use process, and the application of the high-strength gypsum in the field of building materials is facilitated to be enlarged.
Detailed Description
The technical scheme of the invention is further specifically described by the following examples.
Example 1: the high-strength gypsum 3D printing material prepared from the high-chlorine desulfurization gypsum comprises the following components in parts by weight: 75 parts of high-chlorine desulfurization gypsum, 24 parts of chloride ion curing mineral, 0.08 part of foaming agent and 0.92 part of crystal transition agent, wherein the chloride ion curing mineral comprises 8 parts of fly ash, 8 parts of slag and 8 parts of bauxite, the foaming agent comprises turpentine, and the crystal transition agent comprises 0.46 part of magnesium acetate and 0.46 part of melamine sulfide.
The method for preparing the high-strength gypsum 3D printing material from the high-chlorine desulfurization gypsum comprises the following steps: step (1), adding high-chlorine desulfurization gypsum and chloride ion solidified minerals into a ball mill according to a proportion, adding a proper amount of distilled water to ensure that the comprehensive water content is 20-30%, uniformly stirring, carrying out wet mixed grinding, and solidifying free chloride ions of harmful impurities to obtain primary-preparation mixed slurry; step (2), adding a foaming agent into the primary mixed slurry prepared in the step (1) according to a proportion, uniformly stirring, and then continuously carrying out wet mixed grinding to prepare flotation mixed slurry so as to carry out flotation; step (3), discharging the flotation mixed slurry prepared in the step (2) in a container, standing for 5-8 hours, removing organic impurities in the desulfurized gypsum by using the chemical adsorption action of a foaming agent, removing metal ion impurities by using the coating action of the foaming agent, and leaving the gypsum slurry below for later use; step (4), placing the gypsum slurry prepared in the step (3) into an autoclave, adding a crystal transformation agent into the autoclave according to a proportion, and steaming the mixture after the mixture is uniformly stirred to convert the desulfurized gypsum slurry mainly comprising dihydrate gypsum into high-strength gypsum slurry mainly comprising alpha-hemihydrate gypsum; step (5), drying the high-strength gypsum slurry prepared in the step (4) to prepare high-strength gypsum; and (6) grinding the dried high-strength gypsum to a granularity of less than 120 mu m to obtain high-strength gypsum powder meeting the requirement of 3D printing, and adding distilled water as required to prepare a high-strength gypsum 3D printing material when in use to perform 3D printing. Wherein the rotation speed of wet mixed grinding in the step (1) is 200-400 rpm, the ball milling time is 20-40 min, and the particle size of solid particles in the prepared primary mixed slurry is 0.5-5 mu m; the rotation speed of wet mixed grinding in the step (2) is 200-400 rpm, and the ball milling time is 3-15 min; the steaming time of the steaming kettle in the step (4) is 1-5 h, and the steaming temperature is 100-140 ℃; the drying temperature in the step (5) is 30-60 ℃ and the drying time is 2-6 hours.
The invention takes the solid waste desulfurized gypsum of the thermal power plant as a matrix material, and is supplemented with fly ash, slag, bauxite and the like as solidified minerals of free chloride ions of harmful impurities in the desulfurized gypsum, and a proper amount of distilled water is added to carry out wet mixed grinding in a ball mill. On the one hand, the wet mixed grinding can improve the grinding efficiency of the desulfurized gypsum, so that the particle size of the desulfurized gypsum is smaller after grinding, the conversion rate of the desulfurized gypsum into high-strength gypsum is improved, and finally the strength of gypsum products can be improved; on the other hand, the wet mixing grinding ensures that the chloride ion solidified mineral and the desulfurized gypsum are mixed more uniformly, thereby being beneficial to improving the effect of solidifying free chloride ions and reducing the quantity of free chloride ions in gypsum products. In addition, the invention can directly add the chloride ion solidified mineral for wet mixed grinding under the condition of high water content of the desulfurized gypsum, thereby avoiding the link of drying the desulfurized gypsum and being beneficial to reducing the production cost.
The 3D printed high-strength gypsum product prepared in example 1 of the present invention is exemplified by 40mm x 160mm test pieces of standard building gypsum, and the free chloride ion content is 90ppm, the flexural strength is 5MPa, and the compressive strength is 40MPa.
Example 2: the high-strength gypsum 3D printing material prepared from the high-chlorine desulfurization gypsum comprises the following components in parts by weight: 70 parts of high-chlorine desulfurization gypsum, 29 parts of chloride ion curing mineral, 0.10 part of foaming agent and 0.90 part of crystal transformation agent, wherein the chloride ion curing mineral is 15 parts of fly ash and 14 parts of slag, the foaming agent is eucalyptus oil, and the crystal transformation agent is magnesium acetate. The above method for preparing high-strength gypsum 3D printing material from high-chlorine desulfurized gypsum is referred to in example 1.
The 3D printed high-strength gypsum product prepared in example 2 of the present invention is tested by taking 40mm x 160mm test piece of standard building gypsum as an example, and the free chloride ion content is 80ppm, the flexural strength is 5.5MPa, and the compressive strength is 43MPa.
Example 3: the high-strength gypsum 3D printing material prepared from the high-chlorine desulfurization gypsum comprises the following components in parts by weight: 65 parts of high-chlorine desulfurization gypsum, 34 parts of chloride ion curing mineral, 0.10 part of foaming agent and 0.90 part of crystal transformation agent, wherein the chloride ion curing mineral is selected from 20 parts of fly ash and 14 parts of bauxite, the foaming agent is selected from camphor oil, and the crystal transformation agent is selected from melamine sulfide. The above method for preparing high-strength gypsum 3D printing material from high-chlorine desulfurized gypsum is referred to in example 1.
The 3D printed high-strength gypsum product prepared in example 3 of the present invention is tested by taking 40mm x 160mm test piece of standard building gypsum as an example, and the free chloride ion content is 70ppm, the flexural strength is 6MPa, and the compressive strength is 45MPa.
Example 4: the high-strength gypsum 3D printing material prepared from the high-chlorine desulfurization gypsum comprises the following components in parts by weight: 85 parts of high-chlorine desulfurization gypsum, 14 parts of chloride ion curing mineral, 0.06 part of foaming agent and 0.94 part of crystal transformation agent, wherein the chloride ion curing mineral comprises 7 parts of slag and 7 parts of bauxite, the foaming agent comprises camphor oil, and the crystal transformation agent comprises 0.47 part of magnesium acetate and 0.47 part of melamine sulfide. The above method for preparing high-strength gypsum 3D printing material from high-chlorine desulfurized gypsum is referred to in example 1.
The 3D printed high-strength gypsum product prepared in example 4 of the present invention is tested by taking 40mm x 160mm test pieces of standard building gypsum as an example, and has a free chloride ion content of 99.98ppm, a flexural strength of 4MPa and a compressive strength of 43MPa.
Example 5: the high-strength gypsum 3D printing material prepared from the high-chlorine desulfurization gypsum comprises the following components in parts by weight: 74.20 parts of high-chlorine desulfurization gypsum, 24.18 parts of chloride ion curing mineral, 0.10 part of foaming agent and 1.52 parts of crystal transition agent, wherein the chloride ion curing mineral is selected from 12.09 parts of fly ash and 12.09 parts of bauxite, the foaming agent is selected from turpentine, and the crystal transition agent is selected from 0.76 part of magnesium acetate and 0.76 part of melamine sulfide. The above method for preparing high-strength gypsum 3D printing material from high-chlorine desulfurized gypsum is referred to in example 1.
The 3D printed high-strength gypsum product prepared in example 5 of the present invention is exemplified by 40mm x 160mm test pieces of standard building gypsum, and the free chloride ion content is determined by test to be 85ppm, the flexural strength is 5.8MPa, and the compressive strength is 45MPa.
Finally, it should be noted that the above embodiments are merely representative examples of the present invention. Obviously, the technical solution of the invention is not limited to the above-described embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (10)
1. The high-strength gypsum 3D printing material prepared from the high-chlorine desulfurization gypsum is characterized by comprising the following components in parts by weight: 65 to 85 parts of high-chlorine desulfurization gypsum, 14 to 34 parts of chloride ion curing mineral, 0.06 to 0.10 part of foaming agent and 0.32 to 1.52 parts of crystal transformation agent.
2. The high-strength gypsum 3D printing material prepared from high-chlorine desulfurization gypsum according to claim 1, wherein the high-strength gypsum 3D printing material is prepared from the following components in parts by weight: 75 parts of high-chlorine desulfurized gypsum, 24 parts of chloride ion solidified mineral, 0.08 part of foaming agent and 0.92 part of crystal transformation agent.
3. The high-strength gypsum 3D printing material prepared from high-chlorine desulfurization gypsum according to claim 1 or 2, wherein the chloride ion curing mineral is one or more of fly ash, slag and bauxite.
4. The high-strength gypsum 3D printing material prepared from high-chlorine desulfurization gypsum according to claim 1 or 2, wherein the foaming agent is one of turpentine, eucalyptus oil and camphor oil.
5. The high-strength gypsum 3D printing material prepared from high-chlorine desulfurization gypsum according to claim 1 or 2, wherein the crystal transformation agent is one or two of magnesium acetate and melamine sulfide.
6. A method for preparing a high-strength gypsum 3D printing material from high-chlorine desulfurized gypsum, which is characterized by comprising the following steps:
step (1), adding high-chlorine desulfurization gypsum and chloride ion solidified minerals into a ball mill according to a proportion, adding a proper amount of distilled water to ensure that the comprehensive water content is 20-30%, uniformly stirring, carrying out wet mixed grinding, and solidifying free chloride ions of harmful impurities to obtain primary-preparation mixed slurry;
step (2), adding a foaming agent into the primary mixed slurry prepared in the step (1) according to a proportion, uniformly stirring, and then continuously carrying out wet mixed grinding to prepare flotation mixed slurry so as to carry out flotation;
step (3), discharging the flotation mixed slurry prepared in the step (2) in a container, standing for 5-8 hours, removing organic impurities in the desulfurized gypsum by using the chemical adsorption action of a foaming agent, removing metal ion impurities by using the coating action of the foaming agent, and leaving the gypsum slurry below for later use;
step (4), placing the gypsum slurry prepared in the step (3) into an autoclave, adding a crystal transformation agent into the autoclave according to a proportion, and steaming the mixture after the mixture is uniformly stirred to convert the desulfurized gypsum slurry mainly comprising dihydrate gypsum into high-strength gypsum slurry mainly comprising alpha-hemihydrate gypsum;
step (5), drying the high-strength gypsum slurry prepared in the step (4) to prepare high-strength gypsum;
and (6) grinding the dried high-strength gypsum to a granularity of less than 120 mu m to obtain high-strength gypsum powder meeting the requirement of 3D printing, and adding distilled water as required to prepare a high-strength gypsum 3D printing material when in use to perform 3D printing.
7. The method for preparing the high-strength gypsum 3D printing material from the high-chlorine desulfurization gypsum according to claim 6, wherein the rotational speed of the wet mixing mill in the step (1) is 200-400 rpm, the ball milling time is 20-40 min, and the particle size of solid particles in the prepared primary mixed slurry is 0.5-5 μm.
8. The method for preparing the high-strength gypsum 3D printing material from the high-chlorine desulfurization gypsum according to claim 6, wherein the rotation speed of the wet mixing grinding in the step (2) is 200-400 rpm, and the ball milling time is 3-15 min.
9. The method for preparing high-strength gypsum 3D printing materials from high-chlorine desulfurization gypsum according to claim 6, wherein the autoclave time in the step (4) is 1-5 h, and the autoclave temperature is 100-140 ℃.
10. The method for preparing high-strength gypsum 3D printing materials from high-chlorine desulfurization gypsum according to claim 6, wherein the drying temperature in the step (5) is 30-60 ℃ and the drying time is 2-6 hours.
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| CN202310394451.7A CN116425497B (en) | 2023-04-13 | High-strength gypsum 3D printing material prepared from high-chlorine desulfurization gypsum and preparation method thereof |
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