CN116623272B - Preparation method of calcium sulfate whisker - Google Patents
Preparation method of calcium sulfate whisker Download PDFInfo
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- CN116623272B CN116623272B CN202310896962.9A CN202310896962A CN116623272B CN 116623272 B CN116623272 B CN 116623272B CN 202310896962 A CN202310896962 A CN 202310896962A CN 116623272 B CN116623272 B CN 116623272B
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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 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 150000007524 organic acids Chemical class 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 239000011575 calcium Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 72
- 229940095672 calcium sulfate Drugs 0.000 description 58
- 239000000047 product Substances 0.000 description 27
- 238000005303 weighing Methods 0.000 description 17
- 239000013078 crystal Substances 0.000 description 8
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion 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
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel 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
- 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
-
- 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
- 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
Abstract
The invention belongs to the technical field of inorganic material preparation, and relates to a preparation method of calcium sulfate whiskers. The invention takes solid waste calcium sulfate dihydrate as raw material and adopts an ordinary pressure acidification method to prepare the calcium sulfate whisker. And adding the solid waste calcium sulfate dihydrate into acetic acid, propionic acid or butyric acid, adding a certain amount of sulfuric acid, stirring at a certain rotating speed, controlling the temperature to be 115-125 ℃, and heating for 1.5-3.5 h. And after the reaction is finished, washing with boiled water, filtering, and drying at 80-110 ℃ for 1-4 hours to obtain the calcium sulfate whisker. The method directly utilizes the calcium-containing raw materials, is operated under normal pressure, has simple process, reasonably utilizes solid waste, reduces resource waste, and produces the product with large length-diameter ratio of 35-100 in the organic acid, high quality and repeatedly recycling the organic acid.
Description
Technical Field
The invention belongs to the technical field of inorganic material crystal preparation, and relates to a preparation method of calcium sulfate whiskers.
Background
The industrial byproduct gypsum refers to a byproduct rich in calcium sulfate dihydrate produced in the industrial production process. The comprehensive utilization rate of the industrial by-product gypsum is low, so that the industrial by-product gypsum is accumulated in China at present. By the year 2020, the accumulated gypsum piling amount in China exceeds 1100 ten thousand tons, and the total emission amount of industrial byproduct gypsum in China is about 200 ten thousand tons in 2020. The large amount of the waste water is accumulated, so that a plurality of problems are caused to the environment, not only are valuable land resources occupied, but also waste of the resources is caused. The utilization rate of the industrial byproduct gypsum is improved, which is a problem to be solved in the prior art.
Calcium sulfate whisker, also known as gypsum whisker, is an inorganic nonmetallic material with a relatively complete crystal structure. Calcium sulfate whiskers are classified into anhydrous, semi-hydrated and dihydrate according to the crystalline phase of the crystal. The high-strength high-temperature-resistant steel has the characteristics of complete structure, good toughness, high strength, high temperature resistance and the like, and is widely applied to various industries. The calcium sulfate whisker is high-quality, low-cost and environment-friendly, and has a wide market.
The calcium sulfate whisker has wide application in various industries due to its excellent performance. The product can be used as modifier of materials, such as calcium sulfate whisker can be used for modifying high impact polystyrene, fluororubber, nylon 6 and the like, and the service life of the modified product is prolonged and the use cost is reduced. The product can be used as an environmental protection purifying agent for adsorbing phosphorus and mercury in water and can also be used for decoloring printing and dyeing wastewater due to the special adsorption performance. In the paper industry, because the calcium sulfate whisker has strong adsorptivity, the use of materials can be reduced, and the ash content and strength of paper can be increased by adding the calcium sulfate whisker. The calcium sulfate whisker is also used in cement, and is made of superfine fiber material, so that the effects of load transmission, crack bridging, crack deflection and pulling out are generated after the calcium sulfate whisker is added, and the compressive strength and the bending strength of the product are improved. In the tile industry, calcium sulfate whiskers act as reinforcing agents to improve mechanical strength. In addition, the modified polypropylene resin has wide application in other aspects such as drinks, paints and the like.
The method for preparing the calcium sulfate whisker comprises an atmospheric acidification method, a hydrothermal synthesis method, an ion exchange method and a microemulsion method, wherein the atmospheric acidification method and the hydrothermal synthesis method are commonly used. The normal pressure acidification method is to make the raw material reach saturation state in acid environment at a certain temperature, according to the influence of temperature on the solubility of calcium sulfate, to realize the dissolution and precipitation crystallization of calcium sulfate, and then to obtain the product through the processes of filtering, washing, drying, etc. The method can be operated simply under normal pressure, but the used strong acid can corrode equipment, thereby increasing the cost and making the waste liquid difficult to treat. Aiming at the characteristic of indissolvable calcium sulfate, the hydrothermal synthesis method takes aqueous solution as a reaction system, adjusts the temperature and the pressure, and promotes the dissolution and crystallization of calcium sulfate to separate out crystals. The reaction precursor is crushed and ground, mixed with water to form slurry with certain concentration, pH value regulated, preheated reactant and reacted in a reaction kettle for certain period, and the reacted product is filtered, washed, dried, depolymerized and refined to obtain the final product. The product prepared by the method has higher purity and good dispersibility, but needs high equipment tightness.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of calcium sulfate whisker, which takes solid waste calcium sulfate dihydrate as a raw material and prepares the calcium sulfate whisker by adopting an ordinary pressure acidification method, wherein the calcium sulfate whisker is prepared in a pure organic acid system, and the obtained calcium sulfate whisker has high quality and can be recycled.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a preparation method of calcium sulfate whisker comprises the following specific steps:
s1, taking a proper amount of raw material calcium sulfate dihydrate, and drying at 80-110 ℃ for 1-4 hours after pretreatment;
s2, weighing a proper amount of dried raw materials, adding calcium sulfate dihydrate and organic acid into a round-bottom flask according to a certain solid-to-liquid ratio, magnetically stirring, adding an additive, heating to 115-125 ℃, condensing and refluxing for 1.5-3.5 h;
and S3, after the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 80-110 ℃ for 1-4 hours to obtain the product.
Further, in the above preparation method, the solid-to-liquid ratio in the step S2 is: 30-60 ml of organic acid is corresponding to each gram of calcium sulfate dihydrate.
Further, in the above preparation method, the organic acid in the step S2 is acetic acid, propionic acid or butyric acid.
Further, in the above preparation method, the rotational speed of the magnetic stirring in the step S2 is 20 to 200rpm.
Further, in the above preparation method, the additive in the step S2 is sulfuric acid, and the concentration of the sulfuric acid is 10-35%.
Further, in the preparation method, the addition amount of the sulfuric acid is that the volume ratio of the organic acid to the sulfuric acid is 120:1-500:1.
Further, the XRD pattern of the calcium sulfate whisker has a main characteristic peak at a position with a diffraction angle 2 theta of 25.436 degrees.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the scheme, solid waste calcium sulfate dihydrate is used as a raw material, calcium sulfate whiskers are prepared in a pure organic acid system, and the performance of the obtained product is superior to that of the calcium sulfate whiskers prepared in a traditional inorganic acid system. The anhydrous calcium sulfate whisker prepared in the pure organic acid system has simple preparation method and regular product morphology. In practical application, the calcium sulfate whisker is prepared in an acetic acid, propionic acid or butyric acid system, so that the corrosion degree of equipment is greatly reduced by organic acid, the organic acid can be recycled repeatedly, the production of waste liquid is reduced, and the production cost is reduced. The prepared calcium sulfate whisker has good quality and meets the industrial requirements.
Drawings
FIG. 1 is an X-ray diffraction pattern of calcium sulfate whiskers according to example 2;
FIG. 2 is a scanning electron microscope image of the calcium sulfate whisker described in example 2.
Detailed Description
The invention will be further described with reference to specific examples.
Example 1
The preparation process of the calcium sulfate whisker includes the following steps:
(1) Taking a proper amount of raw material calcium sulfate dihydrate, and drying at 100 ℃ for 1.5 hours after pretreatment;
(2) Weighing 4g of dried raw materials, weighing 120mL of acetic acid, adding the raw materials into a round-bottom flask, magnetically stirring at a speed of 100rmp, adding 1 mL of 20% sulfuric acid, heating to 120 ℃, condensing and refluxing for 2h;
(3) After the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 110 ℃ for 1h to obtain the product.
Example 2
The preparation process of the calcium sulfate whisker includes the following steps:
(1) Taking a proper amount of raw material calcium sulfate dihydrate, and drying at 100 ℃ for 1.5 hours after pretreatment;
(2) Weighing 4g of dried raw materials, weighing 120mL of propionic acid, adding into a round-bottom flask, magnetically stirring at a speed of 100rmp, adding 1 mL of 20% sulfuric acid, heating to 120 ℃, condensing and refluxing for 2h;
(3) After the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 110 ℃ for 1h. The product can be obtained.
Example 3
The preparation process of the calcium sulfate whisker includes the following steps:
(1) Taking a proper amount of raw material calcium sulfate dihydrate, and drying at 100 ℃ for 1.5 hours after pretreatment;
(2) Weighing 4g of dried raw materials, weighing 120mL of butyric acid, adding the raw materials into a round-bottom flask, wherein the magnetic stirring speed is 100rmp, adding 1 mL of 20% sulfuric acid, heating to 120 ℃, condensing and refluxing, and the reaction time is 2h;
(3) After the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 110 ℃ for 1h. The product can be obtained.
Example 4
The preparation process of the calcium sulfate whisker includes the following steps:
(1) Taking a proper amount of raw material calcium sulfate dihydrate, and drying at 100 ℃ for 1.5 hours after pretreatment;
(2) Weighing 4g of dried raw materials, weighing 120mL of butyric acid, adding the raw materials into a round-bottom flask, wherein the magnetic stirring speed is 20rmp, adding 1 mL of 20% sulfuric acid, heating to 120 ℃, condensing and refluxing, and the reaction time is 2h;
(3) After the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 110 ℃ for 1h to obtain the product.
Example 5
The preparation process of the calcium sulfate whisker includes the following steps:
(1) Taking a proper amount of raw material calcium sulfate dihydrate, and drying at 100 ℃ for 1.5 hours after pretreatment;
(2) Weighing 4g of dried raw materials, weighing 120mL of butyric acid, adding the raw materials into a round-bottom flask, wherein the magnetic stirring speed is 200rmp, adding 1 mL of 20% sulfuric acid, heating to 120 ℃, condensing and refluxing, and the reaction time is 2h;
(3) After the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 110 ℃ for 1h to obtain the product.
Example 6
The preparation process of the calcium sulfate whisker includes the following steps:
(1) Taking a proper amount of raw material calcium sulfate dihydrate, and drying at 100 ℃ for 1.5 hours after pretreatment;
(2) Weighing 4g of dried raw materials, weighing 240mL of butyric acid, adding the raw materials into a round-bottom flask, wherein the magnetic stirring speed is 100rmp, adding 1 mL of 20% sulfuric acid, heating to 120 ℃, condensing and refluxing, and the reaction time is 2h;
(3) After the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 110 ℃ for 1h. The product can be obtained.
Example 7
The preparation process of the calcium sulfate whisker includes the following steps:
(1) Taking a proper amount of raw material calcium sulfate dihydrate, and drying at 100 ℃ for 1.5 hours after pretreatment;
(2) Weighing 4g of dried raw materials, weighing 120mL of butyric acid, adding the raw materials into a round-bottom flask, wherein the magnetic stirring speed is 100rmp, adding 0.24 mL of 20% sulfuric acid, heating to 120 ℃, condensing and refluxing for 2h;
(3) After the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 110 ℃ for 1h. The product can be obtained.
Comparative example 1 (without admixture)
The preparation process of the calcium sulfate whisker includes the following steps:
(1) Taking a proper amount of raw material calcium sulfate dihydrate, and drying at 100 ℃ for 1.5 hours after pretreatment;
(2) Weighing 4g of dried raw materials, weighing 120mL of butyric acid, adding the raw materials into a round-bottom flask, heating to 120 ℃ at a magnetic stirring speed of 100rmp, and condensing and refluxing for 2h;
(3) After the reaction is finished, washing and suction filtering the obtained product with boiled water, and drying at 110 ℃ for 1h. The product can be obtained.
TABLE 1 calcium sulfate whisker aspect ratio test results
Examples 1, 2, 3 are for comparison and the effect of different organic acids was investigated; the aspect ratios of the calcium sulfate whiskers prepared by different organic acid systems are different, because the crystal growth and the dispersion degree of the calcium sulfate whiskers are different in the recrystallization process of the different organic acid systems, the organic acid selected in the embodiment 2 is propionic acid, the obtained calcium sulfate whiskers have an X-ray diffraction pattern shown in a graph 1, the XRD pattern of the calcium sulfate whiskers has main characteristic peaks at diffraction angles 2 theta of 25.436 degrees, and other peaks at the positions of diffraction angles 2 theta of 31.367 degrees, 38.640 degrees and 40.815 degrees, and the obtained calcium sulfate whiskers have a scanning electron microscope graph shown in a graph 2, so that the aspect ratio of the prepared calcium sulfate whiskers is 100:1.
Examples 3, 4, 5 are for comparison and the effect of different magnetic stirring speeds is investigated; the comparison shows that the aspect ratio of the calcium sulfate whisker with the rotating speed of 100rmp is 80:1; the low rotation speed causes smaller length-diameter ratio of the calcium sulfate whisker, because the calcium sulfate whisker is aggregated together in the recrystallization process, the calcium sulfate whisker cannot be effectively dispersed; the larger rotating speed causes smaller length-diameter ratio of the calcium sulfate whisker, because the calcium sulfate whisker is excessively dispersed in the recrystallization process, and the growth of crystals is affected.
Example 6 and example 3 were compared to investigate the effect of the amount of organic acid added; example 6 the amount of organic acid added was large and the aspect ratio was slightly reduced because the large amount of organic acid added affected the crystal dispersion of the calcium sulfate whiskers during recrystallization.
In examples 3, 7 and 1, the influence of the addition amount of the additive is explored, the aspect ratio of the calcium sulfate whisker prepared by the comparative example 1 without adding the additive sulfuric acid is 20:1, the aspect ratio of the calcium sulfate whisker prepared by the examples 3 and 7 with the additive sulfuric acid is increased, a small amount of sulfuric acid is added to promote the crystal growth in the recrystallization process of the calcium sulfate whisker, and the aspect ratio of the calcium sulfate whisker prepared by the example 3 with more additive is 80:1.
As can be seen from the table, the length-diameter ratio of the calcium sulfate whisker is different along with the addition of different organic acids and the different dosage of the additive, and when the organic acid is propionic acid, the length-diameter ratio of the calcium sulfate whisker is the largest, and in practical application, the length-diameter ratio of the calcium sulfate whisker can be adjusted according to the requirements.
The above examples merely represent a few embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (2)
1. A preparation method of calcium sulfate whisker is characterized in that,
the method specifically comprises the following steps:
s1, taking a proper amount of raw material calcium sulfate dihydrate, and drying at 80-110 ℃ for 1-4 hours after pretreatment;
s2, adding calcium sulfate dihydrate and organic acid into a round-bottom flask according to a certain solid-to-liquid ratio, adding an additive, magnetically stirring, heating to 115-125 ℃, condensing and refluxing for 1.5-3.5 h;
the solid-to-liquid ratio in the step S2 is 30-60 milliliters of organic acid corresponding to each gram of calcium sulfate dihydrate;
the organic acid in the step S2 is acetic acid, propionic acid or butyric acid;
the additive in the step S2 is sulfuric acid, and the concentration of the sulfuric acid is 10-35%; the adding amount of the sulfuric acid is that the volume ratio of the organic acid to the sulfuric acid is 120:1-500:1;
and S3, after the reaction is finished, washing and suction-filtering the obtained product with boiled water, and drying at 80-110 ℃ for 1-4 hours to obtain the product.
2. The method for producing calcium sulfate whiskers according to claim 1, wherein the rotational speed of the magnetic stirring in step S2 is 20 to 200rpm.
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| CN105603505A (en) * | 2016-01-06 | 2016-05-25 | 昆明理工大学 | Method for hydrothermal synthesis of high-draw-ratio calcium sulfate whiskers with ardealite |
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| CN101168852A (en) * | 2007-08-31 | 2008-04-30 | 武善东 | Mass production method for calcium sulfate whisker |
| CN102352535A (en) * | 2011-09-22 | 2012-02-15 | 东莞上海大学纳米技术研究院 | Method for preparing calcium sulfate crystal whiskers from desulfurized gypsum under normal pressure |
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| Title |
|---|
| 常压酸水体系制备无水硫酸钙晶须及形貌调控;马小玲等;非金属矿;第44卷(第1期);81-83 * |
| 高镁磷尾矿制备二水硫酸钙晶须的研究探讨;潘益等;非金属矿;第42卷(第6期);第98-101页 * |
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