CN113388891A - Preparation method of inorganic-organic hybrid modification-based high-performance calcium sulfate whisker - Google Patents
Preparation method of inorganic-organic hybrid modification-based high-performance calcium sulfate whisker Download PDFInfo
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- CN113388891A CN113388891A CN202110658783.2A CN202110658783A CN113388891A CN 113388891 A CN113388891 A CN 113388891A CN 202110658783 A CN202110658783 A CN 202110658783A CN 113388891 A CN113388891 A CN 113388891A
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- calcium sulfate
- phosphogypsum
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- sulfate whisker
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 164
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000012986 modification Methods 0.000 title claims abstract description 17
- 230000004048 modification Effects 0.000 title claims abstract description 17
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 108010010803 Gelatin Proteins 0.000 claims abstract description 36
- 229920002494 Zein Polymers 0.000 claims abstract description 36
- 239000008273 gelatin Substances 0.000 claims abstract description 36
- 229920000159 gelatin Polymers 0.000 claims abstract description 36
- 235000019322 gelatine Nutrition 0.000 claims abstract description 36
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 36
- 239000005019 zein Substances 0.000 claims abstract description 36
- 229940093612 zein Drugs 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 229910052582 BN Inorganic materials 0.000 claims abstract description 15
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000004683 dihydrates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of high-performance calcium sulfate whiskers based on inorganic-organic hybrid modification, which comprises the following steps: purifying the phosphogypsum to obtain purified phosphogypsum; adding the purified phosphogypsum into a hot sodium chloride solution, and reacting at constant temperature to prepare calcium sulfate whiskers; adding zein and gelatin into an acetic acid solution for dissolving, then adding calcium sulfate whiskers, stirring, filtering, and drying the solid to obtain zein/gelatin composite modified calcium sulfate whiskers; uniformly mixing acrylamide monomer, N, N-methylene bisacrylamide, potassium persulfate and deionized water, dropwise adding boron nitride nanosheet dispersion liquid, heating for reaction, cooling the reaction liquid to room temperature after the reaction is finished, adding zein/gelatin composite modified calcium sulfate whisker, stirring, filtering, and drying the solid to obtain the high-performance calcium sulfate whisker. The calcium sulfate whisker prepared by the method has good stability and excellent performance.
Description
Technical Field
The invention relates to the field of inorganic material preparation, in particular to a preparation method of high-performance calcium sulfate whiskers based on inorganic-organic hybrid modification.
Background
At present, China faces the problem of phosphogypsum to be utilized, the phosphoric acid industry of China can generate a large amount of phosphogypsum byproducts, the yield of the phosphogypsum byproducts can reach 4 to 5 times of the yield of phosphoric acid, and the stacking of a large amount of phosphogypsum causes serious social problems and environmental problems. At present, the production of wet-process phosphoric acid is commonly carried out by a dihydrate method, but the impurities in the byproduct phosphogypsum obtained by producing the phosphoric acid by the process are complex. In order to make the dihydrate phosphogypsum well utilized, researchers at home and abroad mainly concentrate on the dihydrate gypsum for the utilization of the phosphogypsum. A large amount of phosphogypsum occupies land resources, high operation cost is required for stacking the phosphogypsum, and impurities of the phosphogypsum may leach out along with rainwater to pollute the environment in the stacking process. The calcium sulfate whisker belongs to one of inorganic salt whiskers, and is fibrous single crystal of calcium sulfate, which has the advantages of good mechanical strength, no toxicity, stability, low cost and the like. The preparation of the calcium sulfate crystal whisker by taking the phosphogypsum as the raw material has important significance.
The patent with the application number of CN201410135538.3 provides a method for preparing calcium sulfate dihydrate crystal whisker by phosphogypsum, which is prepared by removing impurities from calcium sulfate dihydrate; preparing whiskers; washing; drying to obtain calcium sulfate dihydrate crystal whisker; after the hydrochloric acid is preheated, the reaction can be carried out with the phosphogypsum in a certain proportion under the condition of constant temperature, the reaction can be carried out, the raw materials are ensured not to be wasted, impurities contained in the phosphogypsum can be properly removed to the maximum extent, the generation influence rate of the impurities on the calcium sulfate dihydrate crystal whisker is reduced, the content of calcium sulfate components is improved, the productivity of the calcium sulfate dihydrate crystal whisker is improved, and the production cost of producing the calcium sulfate dihydrate crystal whisker by comprehensively utilizing the phosphogypsum is reduced. The patent with the application number of CN200810058324.5 provides a method for preparing calcium sulfate whiskers from phosphogypsum, which is characterized in that solid waste phosphogypsum is used as a raw material, and calcium sulfate whisker products with the diameter of 1-4 microns, the length of 50-200 microns and controllable diameter and length are prepared through synthesis reaction, filtration, heating dissolution, hot filtration and cooling crystallization. The solid waste phosphogypsum is used for preparing the calcium sulfate whisker, so that the exploitation amount of natural gypsum is reduced, the resource is saved, the waste is changed into the benefit, and the production cost of the calcium sulfate whisker is reduced. It can be known from the prior art that the calcium sulfate whisker can be prepared by taking the pretreated phosphogypsum as a raw material and adopting a normal pressure acidification method and a hydrothermal method, but no research is made on how to modify the prepared calcium sulfate whisker to improve the application performance of the calcium sulfate whisker.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the invention provides a preparation method of a high-performance calcium sulfate whisker based on inorganic-organic hybrid modification.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of high-performance calcium sulfate whiskers based on inorganic-organic hybrid modification comprises the following steps:
(1) purifying the phosphogypsum, and then drying the purified phosphogypsum to obtain the purified phosphogypsum; adding the purified phosphogypsum into a hot sodium chloride solution, dropwise adding a hydrochloric acid solution to adjust the pH value of the solution, reacting at a constant temperature, filtering while the solution is hot after the reaction is finished, washing the filtered solid to be neutral, and drying in vacuum to obtain calcium sulfate whiskers;
(2) adding zein and gelatin into an acetic acid solution, stirring until solid is dissolved, then adding calcium sulfate whiskers, stirring, filtering, and drying the solid to obtain zein/gelatin composite modified calcium sulfate whiskers;
(3) dispersing boron nitride nanosheets in absolute ethyl alcohol to prepare dispersion liquid, uniformly mixing acrylamide monomers, N, N-methylene bisacrylamide, potassium persulfate and deionized water, dropwise adding the dispersion liquid, heating for reaction, cooling the reaction liquid to room temperature after the reaction is finished, adding zein/gelatin composite modified calcium sulfate whiskers, stirring, filtering, and drying the solid to prepare the high-performance calcium sulfate whiskers.
Preferably, in the step (1), the phosphogypsum is ground and then added into water, the ratio of materials to liquid is controlled to be 1:4, the mixture is stirred and washed, then the mixture is kept standing and precipitated, the upper-layer impurity solution is removed, and the precipitation is continuously added with water for washing, and the steps are repeated for 3 to 5 times.
Preferably, in the step (1), the concentration of the hot sodium chloride solution is 15-20 wt%, and the mass ratio of the hot sodium chloride solution to the purified phosphogypsum is 5: 1-2.
Preferably, in the step (1), the isothermal reaction is carried out at 90-95 ℃ for 2-4 h.
Preferably, in the step (1), the concentration of the hydrochloric acid solution is 1mol/L, and the pH of the solution is adjusted to 2-3.
Preferably, in the step (1), the temperature of the vacuum drying is 80-85 ℃ and the time is 10-12 h.
Preferably, in the step (2), the concentration of the acetic acid solution is 75-80 wt%, and the dosage ratio of the zein, the gelatin, the acetic acid solution and the calcium sulfate whiskers is 2-3 g: 0.65-0.85 g: 10-15 ml: 4-5 g.
Preferably, in step (3), the usage ratio of the boron nitride nanosheet, the acrylamide monomer, the N, N-methylene bisacrylamide, the potassium persulfate, the deionized water, and the zein/gelatin composite modified calcium sulfate whisker is 1-2 g: 80-100g, 0.1-0.2 g:0.1-0.2 g: 200 ml: 50-80 g.
Preferably, in the step (3), the temperature of the temperature-raising reaction is 50-60 ℃ and the time is 2-4 h.
Preferably, in the steps (2) and (3), the rotation speed of the stirring treatment is 2000-5000rpm, and the time is 30-60 min.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the method comprises the steps of preparing the calcium sulfate whisker from phosphogypsum serving as a raw material by a normal-pressure hydrothermal method, effectively controlling reaction conditions to prepare the calcium sulfate whisker with large length-diameter ratio and stable size, wherein the length-diameter ratio of the prepared calcium sulfate whisker is 100, and in order to improve the surface hydrophobicity of the calcium sulfate whisker and improve the application performance of the calcium sulfate whisker, firstly, dip-coating a zein/gelatin composite layer on the surface of the calcium sulfate whisker, wherein the zein/gelatin composite layer is uniformly adhered on the surface of the calcium sulfate whisker, and then spraying the prepared boron nitride nanosheet/polyacrylamide composite gel solution.
The invention adopts the zein and the gelatin to be compounded as the adhesion layer to adhere the zein and the gelatin on the surface of the calcium sulfate whisker, on one hand, the dispersibility of the calcium sulfate whisker is improved, in order to further improve the mechanical property and the dispersibility of the calcium sulfate whisker, the invention adopts an in-situ polymerization method to prepare the polyacrylamide gel modified by the boron nitride nanosheets, the boron nitride nanosheets are distributed around the pores of the gel or are filled in the meshes of the gel, crosslinking with polyacrylic acid to improve the strength of the gel, coating the gel on the surface of the zein/gelatin composite modified calcium sulfate whisker, adhering and interpenetrating the polyacrylamide gel modified by the boron nitride nanosheet and the zein/gelatin layer, the stable modified layer is formed on the surface of the calcium sulfate whisker, and the calcium sulfate whisker prepared by the method has good dispersibility and obviously improved mechanical property.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
Grinding the phosphogypsum, mixing the ground phosphogypsum with water, controlling the ratio of material to liquid to be 1:4, stirring and washing for 10min, standing and precipitating, removing an upper-layer impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain the purified phosphogypsum; adding 100g of purified phosphogypsum into 500g of hot sodium chloride solution with the temperature of 95 ℃ and the concentration of 15 wt%, dropwise adding 1mol/L hydrochloric acid solution to adjust the pH value of the solution to 2.2, reacting for 2 hours at constant temperature, filtering while hot after the reaction is finished, washing the filtered solid to be neutral, and drying in vacuum to obtain calcium sulfate whiskers;
adding 2g of zein and 0.65g of gelatin into 10ml of 75 wt% acetic acid solution, stirring until the solids are dissolved, then adding 4g of calcium sulfate whisker, stirring at 2000rpm for 30min, filtering, and drying the solids to obtain zein/gelatin composite modified calcium sulfate whisker;
dispersing 1g of boron nitride nanosheet in 50ml of absolute ethyl alcohol to prepare a dispersion liquid, uniformly mixing 80g of acrylamide monomer, 0.1g N, N-methylene bisacrylamide, 0.1g of potassium persulfate and 200ml of deionized water, dropwise adding the dispersion liquid, heating to 50 ℃ for reaction for 2 hours, cooling the reaction liquid to room temperature after the reaction is finished, adding 50g of zein/gelatin composite modified calcium sulfate whisker, stirring at 2000rpm for 30 minutes, filtering, and drying the solid to prepare the high-performance calcium sulfate whisker.
Example 2
Grinding the phosphogypsum, mixing the ground phosphogypsum with water, controlling the ratio of material to liquid to be 1:4, stirring and washing for 20min, standing and precipitating, removing an upper-layer impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain the purified phosphogypsum; adding 200g of purified phosphogypsum into 500g of hot sodium chloride solution with the temperature of 95 ℃ and the concentration of 20 wt%, dropwise adding 1mol/L hydrochloric acid solution to adjust the pH value of the solution to 2.2, reacting at a constant temperature for 4 hours, filtering while the solution is hot after the reaction is finished, washing the filtered solid to be neutral, and drying in vacuum to obtain calcium sulfate whiskers;
adding 3g of zein and 0.85g of gelatin into 15ml of 80 wt% acetic acid solution, stirring until the solids are dissolved, then adding 4-5g of calcium sulfate whiskers, stirring at 5000rpm for 60min, filtering, and drying the solids to obtain zein/gelatin composite modified calcium sulfate whiskers;
dispersing 2g of boron nitride nanosheets in 100ml of absolute ethyl alcohol to prepare a dispersion liquid, uniformly mixing 100g of acrylamide monomers, 0.2g N, N-methylene bisacrylamide, 0.2g of potassium persulfate and 200ml of deionized water, dropwise adding the dispersion liquid, heating to 60 ℃ for reaction for 4 hours, cooling the reaction liquid to room temperature after the reaction is finished, adding 80g of zein/gelatin composite modified calcium sulfate whiskers, stirring at 5000rpm for 60 minutes, filtering, and drying the solid to prepare the high-performance calcium sulfate whiskers.
Example 3
Grinding the phosphogypsum, mixing the ground phosphogypsum with water, controlling the ratio of material to liquid to be 1:4, stirring and washing for 20min, standing and precipitating, removing an upper-layer impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain the purified phosphogypsum; adding 180g of purified phosphogypsum into 500g of hot sodium chloride solution with the temperature of 95 ℃ and the concentration of 15 wt%, dropwise adding 1mol/L hydrochloric acid solution to adjust the pH value of the solution to 2.2, reacting for 3 hours at constant temperature, filtering while the solution is hot after the reaction is finished, washing the filtered solid to be neutral, and drying in vacuum to obtain calcium sulfate whiskers;
adding 2.5g of zein and 0.7g of gelatin into 15ml of 75 wt% acetic acid solution, stirring until the solids are dissolved, then adding 4.5g of calcium sulfate whisker, stirring at 3000rpm for 3 hours, then filtering, and drying the solids to obtain zein/gelatin composite modified calcium sulfate whisker;
dispersing 1.5g of boron nitride nanosheets in 80ml of absolute ethyl alcohol to prepare a dispersion liquid, uniformly mixing 85g of acrylamide monomers, 0.15N, N-methylene bisacrylamide, 0.1g of potassium persulfate and 200ml of deionized water, dropwise adding the dispersion liquid, heating to 50 ℃ for reaction for 3 hours, cooling the reaction liquid to room temperature after the reaction is finished, adding 60g of zein/gelatin composite modified calcium sulfate whisker, stirring at 3000rpm for 40min, filtering, and drying the solid to prepare the high-performance calcium sulfate whisker.
Example 4
Grinding the phosphogypsum, mixing the ground phosphogypsum with water, controlling the ratio of material to liquid to be 1:4, stirring and washing for 15min, standing and precipitating, removing an upper-layer impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain the purified phosphogypsum; adding 180g of purified phosphogypsum into 500g of hot sodium chloride solution with the temperature of 90 ℃ and the concentration of 18 wt%, dropwise adding 1mol/L hydrochloric acid solution to adjust the pH value of the solution to 2.2, reacting at a constant temperature for 3.5h, filtering while the solution is hot after the reaction is finished, washing the filtered solid to be neutral, and drying in vacuum to obtain calcium sulfate whiskers;
adding 2g of zein and 0.85g of gelatin into 10ml of 75 wt% acetic acid solution, stirring until the solid is dissolved, then adding 4g of calcium sulfate whisker, stirring at 4000rpm for 3 hours, filtering, and drying the solid to obtain zein/gelatin composite modified calcium sulfate whisker;
dispersing 1g of boron nitride nanosheet in 70ml of absolute ethyl alcohol to prepare a dispersion liquid, uniformly mixing 90g of acrylamide monomer, 0.12g N, N-methylene bisacrylamide, 0.15g of potassium persulfate and 200ml of deionized water, dropwise adding the dispersion liquid, heating to 50 ℃ for reaction for 4 hours, cooling the reaction liquid to room temperature after the reaction is finished, adding 70g of zein/gelatin composite modified calcium sulfate whisker, stirring at 4000rpm for 50 minutes, filtering, and drying the solid to prepare the high-performance calcium sulfate whisker.
Example 5
Grinding the phosphogypsum, mixing the ground phosphogypsum with water, controlling the ratio of material to liquid to be 1:4, stirring and washing for 15min, standing and precipitating, removing an upper-layer impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain the purified phosphogypsum; adding 150g of purified phosphogypsum into 500g of hot sodium chloride solution with the temperature of 95 ℃ and the concentration of 18 wt%, dropwise adding 1mol/L hydrochloric acid solution to adjust the pH value of the solution to 2.2, reacting at a constant temperature for 3.5h, filtering while the solution is hot after the reaction is finished, washing the filtered solid to be neutral, and drying in vacuum to obtain calcium sulfate whiskers;
adding 2g of zein and 0.7g of gelatin into 15ml of 80 wt% acetic acid solution, stirring until the solids are dissolved, then adding 5g of calcium sulfate whisker, stirring at 4500rpm for 3 hours, filtering, and drying the solids to obtain zein/gelatin composite modified calcium sulfate whisker;
dispersing 2g of boron nitride nanosheets in 80ml of absolute ethyl alcohol to prepare a dispersion liquid, uniformly mixing 95g of acrylamide monomer, 0.2g N, N-methylene bisacrylamide, 0.1g of potassium persulfate and 200ml of deionized water, dropwise adding the dispersion liquid, heating to 50 ℃ for reaction for 3 hours, cooling the reaction liquid to room temperature after the reaction is finished, adding 75g of zein/gelatin composite modified calcium sulfate whisker, stirring at 3000rpm for 50 minutes, filtering, and drying the solid to prepare the high-performance calcium sulfate whisker.
Comparative example 1
The zein/gelatin composite layer was not coated and other preparation conditions were the same as in example 5.
Comparative example 2
The boron nitride nanosheet is directly coated on the surface of the zein/gelatin composite modified calcium sulfate whisker. The conditions were otherwise the same as in example 5, except that no polyacrylamide was added.
Taking 100g of absolutely dry bleached hardwood pulp board pulp, pulping by a disc grinder, adjusting the pulp concentration to 10 percent, pulping the pulp to 42 DEG SR, adjusting the pulp concentration to (25 +/-5.0)%, and balancing the water for later use. Then, 10g of the calcium sulfate whiskers obtained in the above examples and comparative examples were added, and uniformly mixed to make (80. + -.2) g/m2 basis weight paper, and the properties of the paper were measured, and the results are shown in Table 1.
TABLE 1
From the test results, the inorganic-organic hybrid material is adopted to improve the calcium sulfate whisker, so that the bonding performance of the calcium sulfate whisker and a papermaking matrix can be effectively improved, and the performance of paper can be better improved.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (10)
1. A preparation method of high-performance calcium sulfate whiskers based on inorganic-organic hybrid modification is characterized by comprising the following steps:
(1) purifying the phosphogypsum, and then drying the purified phosphogypsum to obtain the purified phosphogypsum; adding the purified phosphogypsum into a hot sodium chloride solution, dropwise adding a hydrochloric acid solution to adjust the pH value of the solution, reacting at a constant temperature, filtering while the solution is hot after the reaction is finished, washing the filtered solid to be neutral, and drying in vacuum to obtain calcium sulfate whiskers;
(2) adding zein and gelatin into an acetic acid solution, stirring until solid is dissolved, then adding calcium sulfate whiskers, stirring, filtering, and drying the solid to obtain zein/gelatin composite modified calcium sulfate whiskers;
(3) dispersing boron nitride nanosheets in absolute ethyl alcohol to prepare dispersion liquid, uniformly mixing acrylamide monomers, N, N-methylene bisacrylamide, potassium persulfate and deionized water, dropwise adding the dispersion liquid, heating for reaction, cooling the reaction liquid to room temperature after the reaction is finished, adding zein/gelatin composite modified calcium sulfate whiskers, stirring, filtering, and drying the solid to prepare the high-performance calcium sulfate whiskers.
2. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the step (1), the purification treatment is to grind the phosphogypsum and add the ground phosphogypsum into water, control the material-liquid ratio to be 1:4, stir and wash, then stand and precipitate, remove the upper layer impurity solution, continue to add water into the precipitate for washing, and repeat the process for 3-5 times.
3. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the step (1), the concentration of the hot sodium chloride solution is 15-20 wt%, and the mass ratio of the hot sodium chloride solution to the purified phosphogypsum is 5: 1-2.
4. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the step (1), the constant temperature reaction is carried out at 90-95 ℃ for 2-4 h.
5. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the step (1), the concentration of the hydrochloric acid solution is 1mol/L, and the pH value of the solution is adjusted to 2-3.
6. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the step (1), the temperature of the vacuum drying is 80-85 ℃, and the time is 10-12 h.
7. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the step (2), the concentration of the acetic acid solution is 75-80 wt%, and the dosage ratio of the zein, the gelatin, the acetic acid solution and the calcium sulfate whiskers is 2-3 g: 0.65-0.85 g: 10-15 ml: 4-5 g.
8. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the step (3), the dosage ratio of the boron nitride nanosheet, the acrylamide monomer, the N, N-methylene bisacrylamide, the potassium persulfate, the deionized water and the zein/gelatin composite modified calcium sulfate whisker is 1-2 g: 80-100g, 0.1-0.2 g:0.1-0.2 g: 200 ml: 50-80 g.
9. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the step (3), the temperature of the heating reaction is 50-60 ℃ and the time is 2-4 h.
10. The preparation method of the inorganic-organic hybrid modification-based high-performance calcium sulfate whisker according to claim 1, characterized by comprising the following steps: in the steps (2) and (3), the rotation speed of the stirring treatment is 2000-.
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| GB515735A (en) * | 1937-03-23 | 1939-12-13 | Du Pont | Improvements in or relating to the fireproofing of combustible organic materials |
| GB1235259A (en) * | 1969-01-21 | 1971-06-09 | Columbia Ribbon & Carbon | Planographic plates |
| CN106634890A (en) * | 2016-12-18 | 2017-05-10 | 西南石油大学 | Boron-nitride-nanosheet-modified water-base drilling fluid |
| CN109912846A (en) * | 2019-03-30 | 2019-06-21 | 厦门大学 | A kind of high performance calcium sulfate crystal whisker material and preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB515735A (en) * | 1937-03-23 | 1939-12-13 | Du Pont | Improvements in or relating to the fireproofing of combustible organic materials |
| GB1235259A (en) * | 1969-01-21 | 1971-06-09 | Columbia Ribbon & Carbon | Planographic plates |
| CN106634890A (en) * | 2016-12-18 | 2017-05-10 | 西南石油大学 | Boron-nitride-nanosheet-modified water-base drilling fluid |
| CN109912846A (en) * | 2019-03-30 | 2019-06-21 | 厦门大学 | A kind of high performance calcium sulfate crystal whisker material and preparation process |
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