CN112941633B - Preparation process of calcium sulfate whisker - Google Patents
Preparation process of calcium sulfate whisker Download PDFInfo
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- CN112941633B CN112941633B CN202110113619.3A CN202110113619A CN112941633B CN 112941633 B CN112941633 B CN 112941633B CN 202110113619 A CN202110113619 A CN 202110113619A CN 112941633 B CN112941633 B CN 112941633B
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- calcium sulfate
- whisker
- calcium
- concentrated sulfuric
- sulfuric acid
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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 135
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 78
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 66
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 39
- 238000001914 filtration Methods 0.000 claims abstract description 31
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 4
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 151
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000001110 calcium chloride Substances 0.000 description 15
- 229910001628 calcium chloride Inorganic materials 0.000 description 15
- 239000002994 raw material Substances 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002351 wastewater 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
-
- 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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The application provides a preparation process of calcium sulfate whiskers, and relates to the technical field of material preparation. The preparation process of the calcium sulfate whisker comprises the following steps: mixing calcium carbonate and hydrochloric acid, performing primary filtration to obtain a calcium chloride solution, adding concentrated sulfuric acid, performing secondary filtration to obtain calcium sulfate dihydrate whisker, performing tertiary filtration after modification of the calcium sulfate dihydrate whisker, and then drying to obtain the calcium sulfate whisker; the preparation process of the calcium sulfate whisker can reduce energy consumption in the preparation process, so that the preparation process is more environment-friendly, the preparation process of the calcium sulfate whisker is simple and convenient, and the prepared calcium sulfate whisker is more complete and is not easy to generate short breakage and the like.
Description
Technical Field
The application relates to the technical field of material preparation, in particular to a preparation process of calcium sulfate whiskers.
Background
At present, the calcium sulfate whisker is mainly applied to industries such as friction materials, engineering plastics and the like. Because the existing calcium sulfate whisker products have high manufacturing cost and general quality, the problems of uneven dispersion, difficult fusion and the like occur in the industries of high polymer materials, plastics, treatment of printing and dyeing wastewater, papermaking and the like. Causing application difficulties and failing to promote cost reduction in the related application industries.
At present, the domestic calcium sulfate whisker is prepared by adopting a hydrothermal method, a microemulsion method, an ion exchange method and the like. The yield of the calcium sulfate whisker prepared by the hydrothermal method is higher than that of the calcium sulfate whisker prepared by other preparation processes, and the pollution is less. However, the process is complex, and in addition, whisker products are easy to generate short fragments, flaky shapes, incomplete shapes and the like.
The existing preparation process of the calcium sulfate whisker is old, so that the conditions of high energy consumption, complex process, poor whisker form quality and the like are caused, and the existing preparation process of the calcium sulfate whisker can not meet the requirements of people on environmental protection, simplicity and high quality at present of industrial high-speed development.
Disclosure of Invention
The application aims to provide a preparation process of calcium sulfate whisker, which can reduce energy consumption in the preparation process, so that the preparation process is more environment-friendly, the preparation process of the calcium sulfate whisker is simple and convenient, and the prepared calcium sulfate whisker is more complete and is not easy to generate short breakage and the like.
The application solves the technical problems by adopting the following technical scheme.
The embodiment of the application provides a preparation process of calcium sulfate whisker, which comprises the following steps: mixing calcium carbonate and hydrochloric acid, performing primary filtration to obtain a calcium chloride solution, adding concentrated sulfuric acid, performing secondary filtration to obtain calcium sulfate dihydrate whisker, performing tertiary filtration after modification of the calcium sulfate dihydrate whisker, and then drying to obtain the calcium sulfate whisker.
Compared with the prior art, the embodiment of the application has at least the following advantages or beneficial effects:
the embodiment of the application provides a preparation process of calcium sulfate whisker, which can be carried out at normal temperature and normal pressure without high-temperature and high-pressure reaction, thereby saving energy sources; and the common hydrochloric acid, calcium carbonate and concentrated sulfuric acid are adopted as main raw materials, and the preparation method can be obtained through multiple reactions, has simple and convenient operation steps, and reduces the operation difficulty of the technicians in the field; in addition, the calcium sulfate whisker prepared by the preparation process has simple operation steps, repeated operation is not needed, the situations of short breakage and the like are avoided, and the quality of the calcium sulfate whisker is ensured.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of the present application;
FIG. 2 is a schematic diagram I of a calcium sulfate whisker under a 400-fold microscope;
fig. 3 is a schematic diagram II of calcium sulfate whiskers under a 400-fold microscope.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to specific examples.
The embodiment of the application provides a preparation process of calcium sulfate whisker, which comprises the following steps: mixing calcium carbonate and hydrochloric acid, performing primary filtration to obtain a calcium chloride solution, adding concentrated sulfuric acid, performing secondary filtration to obtain calcium sulfate dihydrate whisker, performing tertiary filtration after modification of the calcium sulfate dihydrate whisker, and then drying to obtain the calcium sulfate whisker. Adopts more common raw materials: the method has the advantages that the calcium sulfate whisker is directly prepared by mixing reaction of calcium carbonate, hydrochloric acid, concentrated sulfuric acid and the like, the steps are simple, when the hydrochloric acid reacts with the calcium carbonate, part of the hydrochloric acid volatilizes into gas, the volatilized hydrochloric acid is sucked into an acid mist tower for centralized treatment through an anti-corrosion fan, after the treatment reaches the standard of environmental emission, the gas in the acid mist tower is discharged into the atmosphere, the hydrochloric acid treated in the acid mist tower can be continuously recycled after being filtered, the materials are saved, and the method contributes to environmental protection. Because the water absorption of the calcium sulfate whisker after water removal is stronger, the dried calcium sulfate whisker needs to be immediately and rapidly packaged after being cooled, so that the calcium sulfate whisker is prevented from being exposed in the air for a long time and is excessively long in contact with water molecules in the air, and the calcium sulfate whisker is combined with the water again to form the calcium sulfate dihydrate whisker. The whole process flow except drying can be carried out at normal temperature and normal pressure, the reaction can be carried out without high temperature and high pressure, the energy consumption is saved, the operation difficulty is reduced, the contribution is made to the environmental protection, and the policy of advocating environmental protection is met.
In some embodiments of the application, the modifying agent used in the modification is a silane coupling agent, and the mass ratio of the silane coupling agent to the calcium sulfate dihydrate whisker is (2.5-3.5): 100. The common silane coupling agents include vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane and the like, in the scheme, the silane coupling agent is vinyl triethoxysilane, and the vinyl triethoxysilane is easy to hydrolyze, so that the mechanical strength and the electric conductivity of the calcium sulfate whisker can be improved, the situation that the calcium sulfate whisker is crushed shortly and the like is avoided, the performance of the calcium sulfate whisker used as an electric conductor is enhanced, and the practicability of the calcium sulfate whisker is enhanced.
In some embodiments of the application, the modification time is 15-25 minutes. When the modification time is too short, part of the calcium sulfate whisker can not be completely modified, so that the overall quality of the calcium sulfate whisker is poor, and the physical properties such as strength, toughness, conductivity and the like of the calcium sulfate whisker can not meet the required standards. When the modification time is too long, the surface hardness of the calcium sulfate whisker is too high, and the toughness of the calcium sulfate whisker is poor, so that the calcium sulfate whisker becomes brittle, and the physical properties of the calcium sulfate whisker are affected.
In some embodiments of the present application, the above-mentioned silane coupling agent further includes the step of preparing the silane coupling agent into an aqueous solution of the silane coupling agent before use. The amount of water added is such that the calcium sulfate dihydrate whisker can be completely submerged in water after the modifier is mixed with the calcium sulfate dihydrate whisker. The silane coupling agent is completely hydrolyzed by adding water, so that the silane coupling agent dissolved in water is completely contacted with the calcium sulfate dihydrate whisker, thereby achieving the purpose of fully modifying the calcium sulfate dihydrate whisker and enhancing the physical properties of the calcium sulfate dihydrate whisker.
In some embodiments of the present application, the calcium chloride solution is 20-40% by mass and the concentrated sulfuric acid is 70-90% by mass. Calcium chloride forms calcium sulfate by direct reaction with concentrated sulfuric acid. When the content of calcium chloride in the calcium chloride solution is too low, the yield of the formed calcium sulfate whisker is low, and the cost of raw materials is increased. When the content of calcium chloride in the calcium chloride solution is too high, moisture is easily absorbed, and the calcium chloride in the calcium chloride solution reacts with carbon dioxide in the air and calcium carbonate ions in water, so that calcium carbonate precipitation is generated, the utilization rate of the calcium chloride in the calcium chloride solution is reduced, and the purity of the calcium sulfate whisker is further reduced seriously. The sulfuric acid with the mass percent of more than or equal to 70 percent is concentrated sulfuric acid, commonly called bad water. The concentrated sulfuric acid has strong oxidizing property, can react with calcium chloride to generate calcium sulfate dihydrate whisker, and when the concentration of the concentrated sulfuric acid is too low, the oxidizing property of the concentrated sulfuric acid is insufficient, and the concentrated sulfuric acid cannot fully react with calcium chloride in a calcium chloride solution, so that the utilization rate of the calcium chloride is insufficient, and the yield of the generated calcium sulfate dihydrate whisker is low. When the concentration of the concentrated sulfuric acid is too high, the oxidizing property of the concentrated sulfuric acid is too high, and a part of calcium oxide is generated, and although the calcium oxide is continuously reacted into calcium sulfate, an intermediate reaction is generated, thereby reducing the reaction rate.
In some embodiments of the application, the ratio of the volume of the calcium chloride solution to the mass of the concentrated sulfuric acid is (1L): (300-700 g). Wherein the addition amount of the concentrated sulfuric acid is changed according to the concentration of the calcium chloride solution, and 300g of 70% concentrated sulfuric acid is added when the concentration of the calcium chloride solution is 20%. When the concentration of the calcium chloride solution is 40%, 700g of 70% concentrated sulfuric acid is added to ensure that calcium chloride in the calcium chloride solution can fully react with the concentrated sulfuric acid, so that the utilization rate of the calcium chloride is improved, the yield of the calcium sulfate whisker is improved, the raw materials are saved, and the cost is reduced.
In some embodiments of the present application, the above-mentioned adding of concentrated sulfuric acid and the second filtering further comprises stirring the mixed calcium chloride solution with concentrated sulfuric acid and standing for 3-8min, and standing for 20-30min. The concentrated sulfuric acid and the calcium chloride solution are fully contacted by stirring, so that the reaction area of the concentrated sulfuric acid and the calcium chloride solution is increased, the utilization rate of calcium chloride is improved, and the yield of the calcium sulfate dihydrate whisker is further improved. Through standing, the concentrated sulfuric acid and the calcium chloride fully react, so that the calcium chloride in the calcium chloride solution can be completely oxidized by the concentrated sulfuric acid to form calcium sulfate dihydrate whisker, and the yield of the calcium sulfate dihydrate whisker is increased.
In some embodiments of the present application, the calcium carbonate is heavy calcium carbonate, the purity of the heavy calcium carbonate is not less than 99%, and the mass percentage of the hydrochloric acid is 20-34%. The heavy calcium carbonate is called heavy calcium for short, is prepared by grinding and crushing raw materials such as white marble scraps, calcite and the like, and has the characteristics of high whiteness, soft texture, low hardness, wear resistance, good dispersibility and the like. Compared with light calcium carbonate, the heavy calcium carbonate has higher purity and is more convenient to prepare, and the heavy calcium carbonate has better fluidity during reaction and can be more easily and fully reacted with hydrochloric acid, thereby ensuring that the concentration of the calcium chloride solution meets the requirement.
In some embodiments of the present application, the temperature of the drying is 100-200deg.C, and the drying time is 20-30min. The moisture in the calcium sulfate dihydrate whisker is removed through drying, so that the calcium sulfate whisker is obtained, the moisture content in the obtained calcium sulfate whisker can be less than 1.5% in the time and temperature interval of drying, and the physical or chemical properties of the calcium sulfate whisker cannot be changed due to overhigh temperature, so that the quality of the calcium sulfate whisker is affected. If the moisture in the calcium sulfate whisker is higher than 1.5%, the mechanical properties of the calcium sulfate whisker are reduced, so that the hardness of the calcium sulfate whisker is reduced, and the quality of the calcium sulfate whisker is reduced.
In some embodiments of the application, the mixing of the calcium carbonate and the hydrochloric acid and the primary filtration may further comprise stirring for a period of 1-4 hours. The hydrochloric acid and the calcium carbonate are fully reacted through continuous stirring, so that the concentration of the calcium chloride in the calcium chloride solution is ensured, more hydrochloric acid in the calcium chloride solution is volatilized, the calcium chloride in the calcium chloride solution is prevented from reacting with carbonate ions to generate calcium carbonate precipitation, and the generation rate of the calcium chloride is reduced.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment of the application provides a calcium sulfate whisker, which is prepared by the following process: 1 ton of heavy calcium carbonate with the purity of 99 percent and 2.9 tons of hydrochloric acid with the mass percent of 20 percent are selected, the heavy calcium carbonate and the hydrochloric acid are put into a reaction tank for stirring reaction for 4 hours and then are filtered for the first time, a calcium chloride solution with the mass percent of 20 percent is prepared, 100 kg of the calcium chloride solution and 13 kg of concentrated sulfuric acid with the mass percent of 70 percent are put into a reaction kettle for stirring for 5 minutes, standing for 20 minutes and then are filtered for the second time, 124 kg of calcium sulfate dihydrate whisker is obtained, 3.1 kg of silane coupling agent is taken, water is added for hydrolysis, the calcium sulfate dihydrate whisker and the silane coupling agent after water addition are mixed, water is added until the calcium sulfate dihydrate whisker just gets out after the calcium sulfate dihydrate whisker is modified for 20 minutes, then the calcium sulfate dihydrate whisker is dried for 20 minutes by hot air for the third time and filtered, and 121 kg of calcium sulfate whisker is immediately poured into a material bin for cooling and then is packaged for standby.
Example 2
The embodiment of the application provides a calcium sulfate whisker, which is prepared by the following process: 1 ton of heavy calcium carbonate with the purity of 99 percent and 2.9 tons of hydrochloric acid with the mass percent of 25 percent are selected, the heavy calcium carbonate and the hydrochloric acid are put into a reaction tank for stirring reaction for 4 hours and then are subjected to primary filtration to prepare a calcium chloride solution with the mass percent of 40 percent, then 100 kg of the calcium chloride solution and 25 kg of concentrated sulfuric acid with the mass percent of 70 percent are put into a reaction kettle for stirring for 5 minutes, standing for 30 minutes and then secondary filtration are carried out to obtain 132 kg of calcium sulfate dihydrate whisker, 4.62 kg of silane coupling agent is taken, water is added for hydrolysis, the calcium sulfate dihydrate whisker and the silane coupling agent after water addition are mixed, water is added until the calcium sulfate dihydrate whisker just gets out after the calcium sulfate dihydrate whisker is modified for 20 minutes, then the calcium sulfate dihydrate whisker is dried for 30 minutes by hot air for secondary filtration at 200 ℃, and 128 kg of calcium sulfate whisker is immediately poured into a material bin for cooling and then immediately packaged for standby.
Example 3
The embodiment of the application provides a calcium sulfate whisker, which is prepared by the following process: 1 ton of heavy calcium carbonate with the purity of 99.4 percent and 2.9 tons of hydrochloric acid with the mass percent of 34 percent are selected, the heavy calcium carbonate and the hydrochloric acid are put into a reaction tank to be stirred and reacted for 1 hour and then are subjected to primary filtration to prepare a calcium chloride solution with the mass percent of 30 percent, then 100 kg of the calcium chloride solution and 25 kg of concentrated sulfuric acid with the mass percent of 90 percent are put into a reaction kettle to be stirred for 3 minutes, the mixture is kept stand for 25 minutes and then subjected to secondary filtration to obtain 134 kg of calcium sulfate dihydrate whisker, 4.02 kg of silane coupling agent is taken, water is added for hydrolysis, the calcium sulfate dihydrate whisker and the silane coupling agent after water addition are mixed, water is added until just after the calcium sulfate dihydrate whisker is soaked, the calcium sulfate dihydrate whisker is taken out after 15 minutes of modification, then the calcium sulfate dihydrate whisker is dried for 25 minutes by hot air and is subjected to secondary filtration to obtain 129 kg of calcium sulfate whisker, and the obtained calcium sulfate whisker is immediately poured into a material bin for packaging for standby after cooling.
Example 4
The embodiment of the application provides a calcium sulfate whisker, which is prepared by the following process: 1 ton of heavy calcium carbonate with the purity of 99.2 percent and 2.9 tons of hydrochloric acid with the mass percent of 21 percent are selected, the heavy calcium carbonate and the hydrochloric acid are put into a reaction tank to be stirred and reacted for 1.5 hours and then are subjected to primary filtration to prepare a calcium chloride solution with the mass percent of 22 percent, then 100 kg of the calcium chloride solution and 25 kg of concentrated sulfuric acid with the mass percent of 71 percent are put into a reaction kettle to be stirred for 8 minutes, the mixture is kept stand for 22 minutes and then subjected to secondary filtration to obtain 141 kg of calcium sulfate dihydrate whisker, 5.08 kg of silane coupling agent is taken, water is added for hydrolysis, the calcium sulfate dihydrate whisker and the silane coupling agent after water addition are mixed, water is added until just over the calcium sulfate dihydrate whisker is removed after 16 minutes of modification, then the calcium sulfate dihydrate whisker is dried for 21 minutes by hot air and then is subjected to secondary filtration to obtain 137 kg of calcium sulfate whisker, and the obtained calcium sulfate whisker is immediately poured into a material bin for packaging for standby after being cooled.
Example 5
The embodiment of the application provides a calcium sulfate whisker, which is prepared by the following process: 1 ton of heavy calcium carbonate with the purity of 99.1 percent and 2.9 tons of hydrochloric acid with the mass percent of 22 percent are selected, the heavy calcium carbonate and the hydrochloric acid are put into a reaction tank to be stirred and reacted for 2.5 hours and then are subjected to primary filtration to prepare a calcium chloride solution with the mass percent of 24 percent, then 100 kg of the calcium chloride solution and 25 kg of concentrated sulfuric acid with the mass percent of 80 percent are put into a reaction kettle to be stirred for 6 minutes, after standing for 26 minutes, secondary filtration is carried out to obtain 136 kg of calcium sulfate dihydrate whisker, 4.08 kg of silane coupling agent is taken, water is added for hydrolysis, the calcium sulfate dihydrate whisker and the silane coupling agent after water addition are mixed, water is added until the calcium sulfate dihydrate whisker just gets out, the calcium sulfate dihydrate whisker is taken out after 17 minutes of modification, then the calcium sulfate dihydrate whisker is dried for 23 minutes by hot air and is subjected to tertiary filtration, and 128 kg of calcium sulfate whisker is immediately poured into a material bin for packaging for standby after cooling.
Example 6
The embodiment of the application provides a calcium sulfate whisker, which is prepared by the following process: 1 ton of heavy calcium carbonate with the purity of 99.5 percent and 2.9 tons of hydrochloric acid with the mass percent of 27 percent are selected, the heavy calcium carbonate and the hydrochloric acid are put into a reaction tank to be stirred and reacted for 3 hours and then are filtered for the first time, a calcium chloride solution with the mass percent of 26 percent is prepared, 100 kg of calcium chloride solution and 25 kg of concentrated sulfuric acid with the mass percent of 74 percent are put into a reaction kettle to be stirred for 7 minutes, standing is carried out for 28 minutes and then is filtered for the second time, 133 kg of calcium sulfate dihydrate whisker is obtained, 3.99 kg of silane coupling agent is taken, water is added for hydrolysis, the calcium sulfate dihydrate whisker and the silane coupling agent after water addition are mixed, water is added until just after the calcium sulfate dihydrate whisker is soaked, the calcium sulfate dihydrate whisker is taken out after being modified for 24 minutes, then the calcium sulfate dihydrate whisker is dried for 27 minutes by hot air and filtered for the third time, and 129 kg of calcium sulfate whisker is immediately poured into a material bin for packaging for standby after being cooled.
Example 7
The embodiment of the application provides a calcium sulfate whisker, which is prepared by the following process: 1 ton of heavy calcium carbonate with the purity of 99.3 percent and 2.9 tons of hydrochloric acid with the mass percent of 30 percent are selected, the heavy calcium carbonate and the hydrochloric acid are put into a reaction tank to be stirred and reacted for 3.5 hours and then are subjected to primary filtration to prepare a calcium chloride solution with the mass percent of 32 percent, then 100 kg of the calcium chloride solution and 25 kg of concentrated sulfuric acid with the mass percent of 82 percent are put into a reaction kettle to be stirred for 4 minutes, the mixture is kept stand for 29 minutes and then subjected to secondary filtration to obtain 139 kg of calcium sulfate dihydrate whisker, 4.17 kg of silane coupling agent is taken, water is added for hydrolysis, the calcium sulfate dihydrate whisker and the silane coupling agent after water addition are mixed, water is added until just over the calcium sulfate dihydrate whisker is taken out after the calcium sulfate dihydrate whisker is modified for 22 minutes, then the calcium sulfate dihydrate whisker is dried for 29 minutes by hot air and is subjected to secondary filtration to obtain 132 kg of calcium sulfate whisker, and the obtained calcium sulfate whisker is immediately poured into a material bin for packaging for standby after being cooled.
Effect example 1
The calcium sulfate whiskers obtained in examples 1 to 7 were taken, and then prepared according to the conventional hydrothermal method and used as a control group, and the lengths, widths and average length-diameter ratios of the calcium sulfate whiskers in examples 1 to 7 and the control group were detected and calculated, and the obtained results are shown in table 1.
TABLE 1 calcium sulfate whisker size Table
From the results shown in Table 1, the calcium sulfate whiskers produced in examples 1 to 7 were not significantly different in length and width from those produced in the control group, and the difference in average aspect ratio was also hardly large, so it can be concluded that: the quality of the calcium sulfate whisker prepared by the preparation process of the calcium sulfate whisker provided by the application is not obviously different from that of the calcium sulfate whisker prepared by the traditional process.
Effect example 2
The yield of the calcium sulfate whisker was calculated from the yield of the calcium sulfate whisker produced in examples 1 to 7 and the amount of the raw material, and the yield of the calcium sulfate whisker produced in the control group and the amount of the raw material, according to the formula M/M, where M is the mass of the produced calcium sulfate whisker, and M is the mass of the raw material, and in examples 1 to 7, M is the sum of the mass of the calcium chloride solution and the mass of the concentrated sulfuric acid, and M is the mass of the gypsum dihydrate. In the control group, the mass of the obtained calcium sulfate whisker was 162 kg, the mass of the adopted dihydrate gypsum was 160 kg, and the obtained yield results are shown in Table 2.
TABLE 2 calcium sulfate whisker yield tables
| Numbering device | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Control group |
| Yield rate of | 107.08％ | 102.4％ | 103.2％ | 109.6％ | 102.4％ | 103.2％ | 105.6％ | 101.25％ |
From the results in Table 2, the yield of the calcium sulfate whiskers produced in examples 1 to 7 was slightly higher than that produced in the control group, and it can be concluded that: the yield of the calcium sulfate whisker prepared by the preparation process of the calcium sulfate whisker provided by the application is slightly higher than that of the calcium sulfate whisker prepared by the prior art.
Effect example 3
The calcium sulfate whiskers obtained in examples 1 to 7 and the calcium sulfate whiskers obtained in the control group were taken and subjected to tests of whiteness, tensile strength and electric conductivity, respectively, wherein 0 to 5 points indicate good or bad tensile strength and electric conductivity, 5 points indicate very good electric conductivity and tensile strength, and 0 points indicate very poor electric conductivity and tensile strength, and the obtained results are shown in table 3.
TABLE 3 results of physical Properties of calcium sulfate whisker
As shown by the results in Table 3, the whiteness of the calcium sulfate whiskers produced in examples 1 to 7 was slightly higher than that of the control group, and the tensile strength and the conductivity of the calcium sulfate whiskers produced in examples 1 to 7 were substantially the same as those of the calcium sulfate whiskers produced in the control group. It can thus be concluded that: the whiteness of the calcium sulfate whisker prepared by the preparation process of the calcium sulfate whisker provided by the application is slightly higher than that of the calcium sulfate whisker prepared by the prior process, and the tensile strength and the conductivity are almost the same.
In summary, the embodiment of the application provides a preparation process of calcium sulfate whisker, which can be performed at normal temperature and normal pressure without high-temperature and high-pressure reaction, thereby saving energy and contributing to environmental protection; and the common hydrochloric acid, calcium carbonate and concentrated sulfuric acid are adopted as main raw materials, and the preparation method can be obtained through multiple reactions, has simple and convenient operation steps, and reduces the operation difficulty of the technicians in the field; and the calcium sulfate whisker prepared by the preparation process has simple operation steps, does not need repeated operation, avoids the conditions of short breakage and the like, and ensures the quality of the calcium sulfate whisker. In addition, by adopting vinyl triethoxysilane as a modifier, the physical and chemical properties of the calcium sulfate whisker, such as strength, flexibility, conductivity and the like, can be increased, and the quality of the calcium sulfate whisker can be improved. The prepared calcium sulfate whisker has better size and length-diameter ratio, and meets the requirements in specification. The yield and whiteness of the finally obtained calcium sulfate whisker are slightly improved, the utilization rate of raw materials is increased, and the quality of the calcium sulfate whisker is improved.
The embodiments described above are some, but not all embodiments of the application. The detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Claims (8)
1. The preparation process of the calcium sulfate whisker is characterized by comprising the following steps of: mixing calcium carbonate and hydrochloric acid, and then primarily filtering to obtain a calcium chloride solution, wherein the mass percent of the calcium chloride solution is 20-40%, adding concentrated sulfuric acid, and then secondarily filtering to obtain calcium sulfate dihydrate whisker, the mass percent of the concentrated sulfuric acid is 70-90%, and the ratio of the volume of the calcium chloride solution to the mass of the concentrated sulfuric acid is (1L) (300-700 g);
and (3) carrying out third filtering and drying after modifying the calcium sulfate dihydrate whisker to obtain the calcium sulfate whisker, wherein the modifier used in the modification is a silane coupling agent.
2. The process for preparing calcium sulfate whisker according to claim 1, wherein the mass ratio of the silane coupling agent to the calcium sulfate dihydrate whisker is (2.5-3.5): 100.
3. The process for preparing calcium sulfate whisker according to claim 2, wherein the modification time is 15 to 25min.
4. A process for preparing calcium sulfate whiskers according to claim 3, wherein the silane coupling agent further comprises the step of preparing the silane coupling agent into an aqueous solution of the silane coupling agent before use.
5. The process according to any one of claims 1 to 4, further comprising stirring the mixed calcium chloride solution with concentrated sulfuric acid for 3 to 8 minutes and standing for 20 to 30 minutes after adding the concentrated sulfuric acid and before the second filtering.
6. The process for preparing calcium sulfate whiskers according to claim 5, wherein the calcium carbonate is heavy calcium carbonate, the purity of the heavy calcium carbonate is not less than 99%, and the mass percentage of the hydrochloric acid is 20-34%.
7. The process for preparing calcium sulfate whisker according to claim 6, wherein the temperature of the drying is 100-200 ℃, and the time of the drying is 20-30min.
8. The process for preparing calcium sulfate whiskers according to claim 7, wherein the mixing of calcium carbonate with hydrochloric acid and before primary filtration further comprises stirring the mixed calcium carbonate with hydrochloric acid for a period of time of 1-4h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286783A (en) * | 2011-09-30 | 2011-12-21 | 瓮福（集团）有限责任公司 | New method for preparing calcium sulfate whiskers |
| CN102534773A (en) * | 2012-02-02 | 2012-07-04 | 四川万润非金属矿物材料有限公司 | Production method of high-reinforcement modified anhydrous calcium sulfate crystal whiskers |
| CN107098372A (en) * | 2017-04-19 | 2017-08-29 | 湖北三宁化工股份有限公司 | A kind of method that hydrochloric acid decomposes phosphorus mine tailing extracting sulfuric acid calcium pyroborate and magnesium hydroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286783A (en) * | 2011-09-30 | 2011-12-21 | 瓮福（集团）有限责任公司 | New method for preparing calcium sulfate whiskers |
| CN102534773A (en) * | 2012-02-02 | 2012-07-04 | 四川万润非金属矿物材料有限公司 | Production method of high-reinforcement modified anhydrous calcium sulfate crystal whiskers |
| CN107098372A (en) * | 2017-04-19 | 2017-08-29 | 湖北三宁化工股份有限公司 | A kind of method that hydrochloric acid decomposes phosphorus mine tailing extracting sulfuric acid calcium pyroborate and magnesium hydroxide |
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