CN113388891B - Preparation method of high-performance calcium sulfate whisker based on inorganic-organic hybridization modification - Google Patents
Preparation method of high-performance calcium sulfate whisker based on inorganic-organic hybridization modification Download PDFInfo
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- CN113388891B CN113388891B CN202110658783.2A CN202110658783A CN113388891B CN 113388891 B CN113388891 B CN 113388891B CN 202110658783 A CN202110658783 A CN 202110658783A CN 113388891 B CN113388891 B CN 113388891B
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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 172
- 238000009396 hybridization Methods 0.000 title claims abstract description 14
- 230000004048 modification Effects 0.000 title claims abstract description 14
- 238000012986 modification Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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
- 108010010803 Gelatin Proteins 0.000 claims abstract description 38
- 229920002494 Zein Polymers 0.000 claims abstract description 38
- 239000008273 gelatin Substances 0.000 claims abstract description 38
- 229920000159 gelatin Polymers 0.000 claims abstract description 38
- 235000019322 gelatine Nutrition 0.000 claims abstract description 38
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 38
- 239000005019 zein Substances 0.000 claims abstract description 38
- 229940093612 zein Drugs 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 229910052582 BN Inorganic materials 0.000 claims abstract description 16
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000002156 mixing 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
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 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 18
- 238000000034 method Methods 0.000 claims description 14
- 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
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000000499 gel Substances 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- -1 phosphogypsum dihydrate Chemical class 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 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
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 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
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 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
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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
- 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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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The application discloses a preparation method of high-performance calcium sulfate whisker based on inorganic-organic hybridization modification, which comprises the following steps: purifying phosphogypsum to obtain purified phosphogypsum; adding purified phosphogypsum into a hot sodium chloride solution, and reacting at constant temperature to obtain calcium sulfate whiskers; adding zein and gelatin into acetic acid solution for dissolution, then adding calcium sulfate whisker, stirring, filtering, and drying the solid to obtain zein/gelatin composite modified calcium sulfate whisker; uniformly mixing an acrylamide monomer, N, N-methylene bisacrylamide, potassium persulfate and deionized water, dropwise adding a 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 application has good stability and excellent performance.
Description
Technical Field
The application relates to the field of inorganic material preparation, in particular to a preparation method of high-performance calcium sulfate whisker based on inorganic-organic hybridization modification.
Background
At present, the phosphogypsum to be utilized is faced in China, a large amount of phosphogypsum byproducts are generated in the phosphoric acid industry in China, the generation amount of the phosphogypsum byproducts is 4 to 5 times of the phosphoric acid output, and a large amount of phosphogypsum is piled up to cause serious social problems and environmental problems. At present, a dihydrate method is commonly used for producing wet-process phosphoric acid, but impurities in phosphogypsum which is a byproduct obtained by producing phosphoric acid by the process are complex. In order to make the phosphogypsum dihydrate well utilized, researchers at home and abroad mainly focus on the phosphogypsum utilization. A large amount of phosphogypsum occupies land resources, the phosphogypsum is piled up with high operation cost, and the phosphogypsum impurities may be leached out along with rainwater to pollute the environment in the piling up process. The calcium sulfate whisker belongs to one kind of inorganic salt whisker, and is fibrous monocrystal of calcium sulfate, and has the advantages of high mechanical strength, no toxicity, high stability, low cost, etc. and may be used as reinforcing material in polyurethane, plastic, rubber, cement, ceramic, papermaking, adhesive, friction material, etc. The preparation of the calcium sulfate whisker by taking 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 whisker from phosphogypsum, which comprises the steps of preparing calcium sulfate dihydrate whisker by removing impurities; preparing whiskers; washing; drying to obtain calcium sulfate dihydrate whisker; through carrying out preheating treatment on hydrochloric acid and carrying out a certain amount of proportioning with phosphogypsum under the constant temperature condition, the reaction can be carried out, the raw materials are ensured not to be wasted, the 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 whisker is reduced, the content of calcium sulfate components is improved, the production rate of the calcium sulfate dihydrate whisker is improved, and the production cost of comprehensively utilizing and producing the calcium sulfate dihydrate whisker by phosphogypsum is reduced. The patent with the application number of CN200810058324.5 provides a method for preparing calcium sulfate whiskers by using phosphogypsum as a raw material, and preparing a calcium sulfate whisker product with the whisker diameter of 1-4 mu m, the length of 50-200 mu m and controllable diameter and length by using solid waste residue phosphogypsum as a raw material through synthesis reaction, filtration, heating and dissolution, hot filtration and cooling crystallization. The calcium sulfate whisker is prepared from the solid waste phosphogypsum, so that the exploitation amount of natural gypsum is reduced, resources are saved, waste is changed into benefit, and the production cost of the calcium sulfate whisker is reduced. From the prior art, the pretreated phosphogypsum is taken as a raw material, and the normal pressure acidification method and the hydrothermal method are adopted to prepare the calcium sulfate whisker, but no research is carried out on how to modify the prepared calcium sulfate whisker to improve the application performance of the calcium sulfate whisker.
Disclosure of Invention
The technical problems to be solved by the application are as follows: aiming at the defects existing in the prior art, the application provides a preparation method of high-performance calcium sulfate whisker based on inorganic-organic hybridization modification, which takes phosphogypsum as a raw material to prepare the calcium sulfate whisker, then coats a zein/gelatin composite layer on the surface of the calcium sulfate whisker, and deposits a boron nitride nano-sheet modified polyacrylamide layer under the adhesion effect of the zein/gelatin composite layer, thereby preparing an inorganic = organic hybridization layer on the surface of the calcium sulfate whisker, improving the dispersibility of the calcium sulfate whisker and improving the performance of the calcium sulfate whisker.
In order to solve the technical problems, the technical scheme of the application is as follows:
the preparation method of the high-performance calcium sulfate whisker based on inorganic-organic hybridization modification comprises the following steps:
(1) Purifying phosphogypsum, and then drying the purified phosphogypsum to obtain purified phosphogypsum; adding purified phosphogypsum into a hot sodium chloride solution, dropwise adding a hydrochloric acid solution to regulate the pH 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 acetic acid solution, stirring until the solids are dissolved, then adding calcium sulfate whiskers, stirring, filtering, and drying the solids to obtain zein/gelatin composite modified calcium sulfate whiskers;
(3) Dispersing the boron nitride nano-sheet in absolute ethyl alcohol to prepare dispersion liquid, uniformly mixing acrylamide monomer, 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 whisker, stirring, filtering, and drying the solid to prepare the high-performance calcium sulfate whisker.
In the step (1), phosphogypsum is ground and then added into water, the ratio of the phosphogypsum to the water is controlled to be 1:4, stirring and washing are performed, then standing and precipitating are performed, the upper impurity solution is removed, and water is continuously added into the precipitate for washing for 3-5 times.
As the preferable choice of the technical scheme, in the step (1), the concentration of the hot sodium chloride solution is 15-20wt%, and the mass ratio of the hot sodium chloride solution to the purified phosphogypsum is 5:1-2.
As the preferable choice of the technical scheme, in the step (1), the temperature of the constant temperature reaction is 90-95 ℃ and the time is 2-4h.
As a preferable mode of the technical scheme, in the step (1), the concentration of the hydrochloric acid solution is 1mol/L, and the pH of the solution is regulated to be 2-3.
As a preferable mode of the technical scheme, in the step (1), the temperature of the vacuum drying is 80-85 ℃ and the time is 10-12h.
As the preferable choice of the technical scheme, in the step (2), the concentration of the acetic acid solution is 75-80wt%, and the dosage ratio of zein, gelatin, acetic acid solution and calcium sulfate whisker is 2-3g:0.65-0.85g:10-15ml:4-5g.
As a preferable mode of the above technical scheme, in the step (3), the usage ratio of the boron nitride nanosheets, acrylamide monomers, N-methylene bisacrylamide, potassium persulfate, deionized water and zein/gelatin composite modified calcium sulfate whisker is 1-2g:80-100g, 0.1-0.2g:0.1-0.2g:200ml:50-80g.
As a preferable mode of the technical scheme, in the step (3), the temperature of the heating reaction is 50-60 ℃ and the time is 2-4h.
As a preferable mode of the technical scheme, in the steps (2) and (3), the rotating speed of the stirring treatment is 2000-5000rpm, and the time is 30-60min.
Due to the adoption of the technical scheme, the application has the beneficial effects that:
according to the application, phosphogypsum is used as a raw material, a normal-pressure hydrothermal method is adopted to prepare the calcium sulfate whisker, the reaction condition is effectively controlled, the prepared calcium sulfate whisker has a large length-diameter ratio and stable size, the length-diameter ratio of the prepared calcium sulfate whisker is 100, in order to improve the hydrophobicity of the surface of the calcium sulfate whisker and improve the application performance of the calcium sulfate whisker, a layer of zein/gelatin composite layer is firstly coated on the surface of the calcium sulfate whisker in a dip-coating manner, and uniformly adhered to the surface of the calcium sulfate whisker, and then the boron nitride nano-sheet/polyacrylamide composite gel liquid is sprayed and prepared, and is stably and uniformly coated on the surface of the calcium sulfate whisker under the action of the zein/gelatin composite layer, so that the dispersibility of the calcium sulfate whisker is effectively improved, and the mechanical performance of the calcium sulfate whisker is also improved.
According to the application, zein and gelatin are compounded to be used as an adhesive layer, the zein and gelatin are adhered to 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 boron nitride nano-sheet modified polyacrylamide gel is prepared by adopting an in-situ polymerization method, the boron nitride nano-sheet is distributed around gel pores or filled in gel meshes and crosslinked with polyacrylamide, the strength of the gel is improved, the zein/gelatin compounded modified calcium sulfate whisker is coated on the surface of the zein/gelatin, the boron nitride nano-sheet modified polyacrylamide gel is mutually adhered and inserted with the zein/gelatin layer, and a stable modified layer is formed on the surface of the calcium sulfate whisker, so that the calcium sulfate whisker prepared by the application has good dispersibility and obviously improved mechanical property.
Detailed Description
The application is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
Example 1
Grinding phosphogypsum, mixing the ground phosphogypsum with water, controlling the feed-liquid ratio to be 1:4, stirring and washing for 10min, standing and precipitating, removing upper impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain purified phosphogypsum; adding 100g of purified phosphogypsum into 500g of hot sodium chloride solution with the temperature of 95 ℃ and the concentration of 15wt%, dripping 1mol/L hydrochloric acid solution to adjust the pH value of the solution to 2.2, reacting at constant temperature for 2 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 whisker;
adding 2g of zein and 0.65g of gelatin into 10ml of 75wt% acetic acid solution, stirring until the solid is dissolved, then adding 4g of calcium sulfate whisker, stirring at 2000rpm for 30min, filtering, and drying the solid to obtain zein/gelatin composite modified calcium sulfate whisker;
dispersing 1g of boron nitride nano-sheet in 50ml of absolute ethyl alcohol to prepare dispersion liquid, uniformly mixing 80g of acrylamide monomer, 0.1g of 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 for 30 minutes at 2000rpm, filtering, and drying the solid to prepare the high-performance calcium sulfate whisker.
Example 2
Grinding phosphogypsum, mixing the ground phosphogypsum with water, controlling the feed-liquid ratio to be 1:4, stirring and washing for 20min, standing and precipitating, removing upper impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain purified phosphogypsum; 200g of purified phosphogypsum is added into 500g of hot sodium chloride solution with the temperature of 95 ℃ and the concentration of 20wt%, 1mol/L hydrochloric acid solution is added dropwise to adjust the pH value of the solution to 2.2, the reaction is carried out for 4 hours at constant temperature, the hot filtration is carried out after the reaction is finished, the filtered solid is washed to be neutral, and the calcium sulfate whisker is prepared by vacuum drying;
adding 3g of zein and 0.85g of gelatin into 15ml of 80wt% acetic acid solution, stirring until the solids are dissolved, then adding 4-5g of calcium sulfate whisker, stirring at 5000rpm for 60min, filtering, and drying the solids to obtain zein/gelatin composite modified calcium sulfate whisker;
dispersing 2g of boron nitride nano-sheets in 100ml of absolute ethyl alcohol to prepare dispersion liquid, uniformly mixing 100g of acrylamide monomer, 0.2g of 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 whisker, stirring at 5000rpm for 60 minutes, filtering, and drying the solid to prepare the high-performance calcium sulfate whisker.
Example 3
Grinding phosphogypsum, mixing the ground phosphogypsum with water, controlling the feed-liquid ratio to be 1:4, stirring and washing for 20min, standing and precipitating, removing upper impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain purified phosphogypsum; 180g of purified phosphogypsum is added into 500g of hot sodium chloride solution with the temperature of 95 ℃ and the concentration of 15wt%, 1mol/L hydrochloric acid solution is added dropwise to adjust the pH value of the solution to 2.2, the reaction is carried out for 3 hours at constant temperature, the hot solution is filtered after the reaction is finished, the filtered solid is washed to be neutral, and the calcium sulfate whisker is prepared by vacuum drying;
adding 2.5g of zein and 0.7g of gelatin into 15ml of 75wt% acetic acid solution, stirring until the solid is dissolved, then adding 4.5g of calcium sulfate whisker, stirring at 3000rpm for 3 hours, filtering, and drying the solid to prepare the zein/gelatin composite modified calcium sulfate whisker;
1.5g of boron nitride nanosheets are dispersed in 80ml of absolute ethyl alcohol to prepare dispersion liquid, 85g of acrylamide monomer, 0.15g of N, N-methylene bisacrylamide, 0.1g of potassium persulfate and 200ml of deionized water are uniformly mixed, the dispersion liquid is dropwise added, then the temperature is raised to 50 ℃ for reaction for 3 hours, the reaction liquid is cooled to room temperature after the reaction is finished, then 60g of zein/gelatin composite modified calcium sulfate whisker is added, stirring treatment is carried out for 40 minutes at 3000rpm, and then the solid is filtered and dried to prepare the high-performance calcium sulfate whisker.
Example 4
Grinding phosphogypsum, mixing the ground phosphogypsum with water, controlling the feed-liquid ratio to be 1:4, stirring and washing for 15min, standing and precipitating, removing upper impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain purified phosphogypsum; 180g of purified phosphogypsum is added into 500g of hot sodium chloride solution with the temperature of 90 ℃ and the concentration of 18wt%, 1mol/L hydrochloric acid solution is added dropwise to adjust the pH value of the solution to 2.2, the constant temperature reaction is carried out for 3.5h, the solution is filtered while the solution is hot after the reaction is finished, the filtered solid is washed to be neutral, and the calcium sulfate whisker is prepared by vacuum drying;
adding 2g of zein and 0.85g of gelatin into 10ml of 75wt% acetic acid solution, stirring until the solids are dissolved, then adding 4g of calcium sulfate whisker, stirring at 4000rpm for 3 hours, filtering, and drying the solids to obtain zein/gelatin composite modified calcium sulfate whisker;
dispersing 1g of boron nitride nano-sheet in 70ml of absolute ethyl alcohol to prepare dispersion liquid, uniformly mixing 90g of acrylamide monomer, 0.12g of 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 for 50 minutes at 4000rpm, filtering, and drying the solid to prepare the high-performance calcium sulfate whisker.
Example 5
Grinding phosphogypsum, mixing the ground phosphogypsum with water, controlling the feed-liquid ratio to be 1:4, stirring and washing for 15min, standing and precipitating, removing upper impurity solution, continuously adding water into the precipitate for washing, and repeating the steps for 3-5 times to obtain purified phosphogypsum; 150g of purified phosphogypsum is added into 500g of hot sodium chloride solution with the temperature of 95 ℃ and the concentration of 18wt%, 1mol/L hydrochloric acid solution is added dropwise to adjust the pH value of the solution to 2.2, the constant temperature reaction is carried out for 3.5h, the solution is filtered while the solution is hot after the reaction is finished, the filtered solid is washed to be neutral, and the calcium sulfate whisker is prepared by vacuum drying;
adding 2g of zein and 0.7g of gelatin into 15ml of 80wt% 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 nano-sheets in 80ml of absolute ethyl alcohol to prepare dispersion liquid, uniformly mixing 95g of acrylamide monomer, 0.2g of 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 solids to prepare the high-performance calcium sulfate whisker.
Comparative example 1
The zein/gelatin composite layer was not coated and the other preparation conditions were the same as in example 5.
Comparative example 2
The boron nitride nano-sheet is directly coated on the surface of the zein/gelatin composite modified calcium sulfate whisker. The other conditions were the same as in example 5 except that polyacrylamide was not added.
Taking 100g of absolute dry bleached hardwood pulp, pulping by a disc mill to adjust the pulp concentration to 10%, pulping the pulp to 42 DEG SR, adjusting the pulp concentration to (25+/-5.0)%, and balancing the water content for standby. Then 10g of the calcium sulfate whisker prepared in the above examples and comparative examples was added, and the mixture was stirred and mixed to make (80.+ -.2) g/m2 quantitative paper, and the performance of the paper was tested, and the test 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 combination property of the calcium sulfate whisker and the papermaking matrix can be effectively improved, and the paper performance can be better improved.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (7)
1. The preparation method of the high-performance calcium sulfate whisker based on inorganic-organic hybridization modification is characterized by comprising the following steps of:
(1) Purifying phosphogypsum, and then drying the purified phosphogypsum to obtain purified phosphogypsum; adding purified phosphogypsum into a hot sodium chloride solution, dropwise adding a hydrochloric acid solution to regulate the pH 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 2-3g of zein and 0.65-0.85g of gelatin into 10-15ml of acetic acid solution with the concentration of 75-80wt% to be stirred until solid is dissolved, then adding 4-5g of calcium sulfate whisker, stirring, filtering, and drying the solid to prepare the zein/gelatin composite modified calcium sulfate whisker;
(3) Dispersing boron nitride nano-sheets in absolute ethyl alcohol to prepare dispersion liquid, uniformly mixing acrylamide monomer, N, N-methylene bisacrylamide, potassium persulfate and deionized water, dropwise adding the dispersion liquid, heating to 50-60 ℃ for reaction for 2-4 hours, cooling the reaction liquid to room temperature after the reaction is finished, adding zein/gelatin composite modified calcium sulfate whisker, stirring, filtering, and drying solids to prepare high-performance calcium sulfate whisker; the dosage ratio of the boron nitride nanosheets to the acrylamide monomers to the N, N-methylene bisacrylamide to the potassium persulfate to the deionized water to the zein/gelatin composite modified calcium sulfate whisker is 1-2g:80-100g, 0.1-0.2g:0.1-0.2g:200ml:50-80g.
2. The method for preparing the high-performance calcium sulfate whisker based on inorganic-organic hybridization modification, which is characterized in that: in the step (1), phosphogypsum is ground and then added into water, the ratio of feed to liquid is controlled to be 1:4, stirring and washing are carried out, then standing and precipitating are carried out, the upper impurity solution is removed, water is continuously added into the precipitate for washing, and the steps are repeated for 3-5 times.
3. The method for preparing the high-performance calcium sulfate whisker based on inorganic-organic hybridization modification, which is characterized in that: in the step (1), the concentration of the hot sodium chloride solution is 15-20wt%, and the mass ratio of the hot sodium chloride solution to the purified phosphogypsum is 5:1-2.
4. The method for preparing the high-performance calcium sulfate whisker based on inorganic-organic hybridization modification, which is characterized in that: in the step (1), the temperature of the constant temperature reaction is 90-95 ℃ and the time is 2-4h.
5. The method for preparing the high-performance calcium sulfate whisker based on inorganic-organic hybridization modification, which is characterized in that: in the step (1), the concentration of the hydrochloric acid solution is 1mol/L, and the pH value of the solution is regulated to be 2-3.
6. The method for preparing the high-performance calcium sulfate whisker based on inorganic-organic hybridization modification, which is characterized in that: in the step (1), the temperature of the vacuum drying is 80-85 ℃ and the time is 10-12h.
7. The method for preparing the high-performance calcium sulfate whisker based on inorganic-organic hybridization modification, which is characterized in that: in the steps (2) and (3), the rotation speed of the stirring treatment is 2000-5000rpm, and the time is 30-60min.
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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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