CN101671848B - Preparation method of high length-diameter ratio anhydrous calcium sulfate whisker - Google Patents
Preparation method of high length-diameter ratio anhydrous calcium sulfate whisker Download PDFInfo
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- CN101671848B CN101671848B CN2009100937583A CN200910093758A CN101671848B CN 101671848 B CN101671848 B CN 101671848B CN 2009100937583 A CN2009100937583 A CN 2009100937583A CN 200910093758 A CN200910093758 A CN 200910093758A CN 101671848 B CN101671848 B CN 101671848B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229940095564 anhydrous calcium sulfate Drugs 0.000 title claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 29
- YTGLSPCIFCDMGL-UHFFFAOYSA-N [Ca].[Ca].O Chemical compound [Ca].[Ca].O YTGLSPCIFCDMGL-UHFFFAOYSA-N 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000013543 active substance Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 230000004907 flux Effects 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 208000006558 Dental Calculus Diseases 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 claims description 5
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 5
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 47
- 235000011132 calcium sulphate Nutrition 0.000 abstract description 23
- 229940095672 calcium sulfate Drugs 0.000 abstract description 21
- 238000002156 mixing Methods 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 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 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000004568 cement Substances 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000005060 rubber Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000000919 ceramic Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000003049 inorganic solvent Substances 0.000 abstract 1
- 229910001867 inorganic solvent Inorganic materials 0.000 abstract 1
- 239000012779 reinforcing material Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 21
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000013067 intermediate product Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 description 5
- 235000011151 potassium sulphates Nutrition 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 241001131796 Botaurus stellaris Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010007247 Carbuncle Diseases 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- -1 pottery Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
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Abstract
A preparation method of high length-diameter ratio anhydrous calcium sulfate whisker belongs to the technical field of inorganic chemical material preparation. The method takes inorganic calcium salt and inorganic precipitant as raw materials and surfactant as dispersant, and includes the following steps: first preparing superfine calcium sulphate dihydrate precursor with good dispersion at the temperature of 10-90 DEG C; then adding the precursor into water solution containing shape control agent to conduct hydrothermal reaction for 0.5-10h at the temperature of 100-250 DEG C, and obtaining calcium sulfate hemihydrate whisker; mixing the calcium sulfate hemihydrate whisker with inorganic solvent; and roasting the mixture for 0.5-6h at the temperature 200-800 DEG C to obtain anhydrous calcium sulfate whisker with the length of 20-2000mum, the diameter of 0.5-20mum, the length-diameter ratio of 40-1000 and the main content greater than 95wt% after washing and drying. The technology is simple, the cost is low and the added value of the product is high. The prepared calcium sulfate whisker has large length-diameter ratio and regular shape and can be used as reinforcing material to be applied in industries such as plastics, rubber, ceramics, cement, papermaking and the like.
Description
Technical field
The present invention relates to a kind of preparation method of high length-diameter ratio anhydrous calcium sulfate whisker, belong to the inorganic chemical industry technical field of material.
Background technology
China is calcium resource big country, the existing secondary calcium resource that waits in a large number to utilize (as at the calcium chloride of inorganic chemical industry industry by-product, carbide slag etc.), abundant natural limestone resource is also arranged, vitriol and sulfuric acid resource are also very abundant and inexpensive, for development calcium sulfate crystal whiskers material provides good condition.
Whisker is a length-to-diameter ratio greater than 10 single crystal fibre, and its atomic structure is arranged high-sequential, and subsurface defect is less, is a kind of strengthening and toughening agent of good matrix material.Industrial crystal whisker products (silicon carbide) the earliest comes across 1962, because of price high (3000～5000 yuan/kilogram) makes its application limited.Cheap potassium titanate crystal whisker in the eighties in 20th century after Japan comes out, whisker is used and is just had breakthrough.The research and development of China's inorganic crystal whisker start from the nineties initial stage, and emphasis relates to systems such as silicon carbide, silicon nitride, all fails to obtain large-scale industrial application because of selling at exorbitant prices.
With other crystal whisker materials relatively, calcium sulfate crystal whiskers has characteristics such as physical strength is good, nontoxic, stable, inexpensive, can be used as strongthener and be used for fields such as urethane, plastics, cement, pottery, papermaking, so its controlled preparation comes into one's own in recent years day by day.
(Han Yuexin, Wang Zehong, Yuan Zhitao, Yu Fujia, seal ten thousand loyalties, Li Qiliang, Preparation methods of gypsum whiskers method, CN1598083A such as Han Yuexin, Li Wu; Among Li Wu, Li Shengli, Zhang Zhihong, Nie Feng, Wei Ming, the Lee, Preparation methods of gypsum whiskers technology, CN 1317430C) with main content greater than 95% plaster stone (CaSO
42H
2O) be raw material, at 70～250 ℃ of reaction 0.5～10h, obtaining length again after 200～400 ℃ of dryings is 10～200 μ m after fragmentation, emulsification, and diameter is the calcium sulfate crystal whiskers of 0.1～4 μ m.The deficiency of this method is that the emulsifying raw material power consumption is bigger, and product length is also limited.(Shi Peiyang, Liu Chengjun, Jiang Maofa such as Shi Peiyang, Zhang Jiakai, Malin's commentaries on classics.Utilize desulfurized gesso of flue gas to prepare the method for calcium sulfate crystal whiskers, CN 10313337A; Zhang Jiakai, Zhang Yushan, Cao Dongmei, Wang Yuqi are the calcium sulphate crystal whisker preparation method of raw material with the sea water bittern, CN 103139382A; Malin changes, peaceful flat, minister in ancient times mountain, Yang Min, Liu Tiancheng, Yang Yuehong, a kind of method of preparing calcium sulphate whiskers from ardealite, CN101311355A) be raw material with desulfurated plaster, sea water bittern and phosphogypsum respectively, the calcium sulfate crystal whiskers of adopt batch mixing, synthesize, drying means being prepared length 50～200 μ m, diameter 0.5～4 μ m.(Zhang Lianhong, Zhang Honglin, Jiang Linshi, Zhang Qiang, Yu Hongyan, Qiu Feng, beam carbuncle, Jiang Husheng, Li Changbo, State of Zhao is towering, phoenix is glad, Preparation methods of gypsum whiskers method, CN 1955345A for Zhang Lianhong, prince's pillow, Ye Ying etc.; Prince's pillow, Zheng Yunhui, Tian Yumei, Zhao Xu, Liu Yanhua, Zhou Bing, Guo Yupeng, sodium sulfate waste water liquid phase method in-situ preparing hydrophobicity calcium sulfate crystal whiskers, CN 101343773A) be that raw material adopts liquid phase method to prepare the sulfate hemihydrate calcium pyroborate earlier under lesser temps (＜110 ℃) with calcium oxide, sodium sulfate waste water respectively, making length at 200 ℃ of left and right sides drying and dehydratings again is that 30～50 μ m, diameter are that 1～2 μ m, length-to-diameter ratio are 30～50 calcium sulfate crystal whiskers.Wu Shandong etc. (Wu Shandong, force are levied, Zhang Jianhua, Wu Shanbin) are with containing Ca
2+And SO
4 2-The aqueous solution to be raw material prepare calcium sulfate crystal whiskers with synthetic-ageing method.(J.J.Eberl such as Eberl, E.Thelen, H.L.Heller, Method for the Manufacture ofCoated Calcium Sulfate Whisker Fibers, US patent 3961105) under 110～150 ℃ of hydrothermal conditions, handles the sulfate dihydrate calcium solution, obtain diameter 0.5～5 μ m, the sulfate hemihydrate calcium pyroborate of length-to-diameter ratio 1～100 obtains anhydrous calcium sulfate whisker after roasting.In addition, under normal temperature condition, all can the pattern of calcium sulfate crystal whiskers be exerted an influence (Peng Jiahui, Zhai Jindong, Wu Li, Zhang Jianxins such as citric acid, sodium laurylsulfonate, sodium polyacrylate, citric acid is to the influence of dihydrate gypsum crystal habit and crystal morphology, Southeast China University's journal, 2004,34 (3), 356-360; Ren Yinzhe, Wang Xiaodong, Wang Jianying, sodium laurylsulfonate and sodium polyacrylate be to the regulation and control of calcium sulfate pattern, Shanxi Normal University's journal (natural science edition), and 2005,19 (4), 53-56), but be unprofitable to the increase of length-to-diameter ratio.In a word, the weak point of aforesaid method is or energy consumption is big or length-to-diameter ratio is lower.
Strengthening the property of calcium sulfate crystal whiskers is closely related with its appearance structure.General length-to-diameter ratio is big more, it is good more to strengthen the property.Therefore, the calcium sulfate crystal whiskers that how to prepare high length-diameter ratio is the target that people pursue for a long time.It is reported, (Ye Ying, old snow firm, Lv Shuanshuan, Xia Meisheng such as Ye Ying, a kind of method for preparing calcium sulfate crystal whiskers from hundred cloud rocks, CN 101323974A) be that raw material adopts carry out microwave radiation heating, ageing, drying means to prepare the sulfate hemihydrate calcium pyroborate of length-to-diameter ratio 10～1000 with dolomite, the product pattern is comparatively responsive to the carry out microwave radiation heating mode, and the engineering amplification acquires a certain degree of difficulty.(D.R.Gareth such as Gareth, Kuang, E.G.Richard, J.H.Stephen, J.Hammond, H.R.Brian, Formation andMorphology of calcium Sulfate Nanoparticles and Nanowires in Water-in OilMicroemulsions, Langmuir, 1999,15 (6), 1993-2002; D.B.Kuang, A.W.Xu, Y.P.Fang, H.D.Qu, H.Q.Liu, Preparation of Inorganic Salts (CaCO
3, BaCO
3, CaSO
4) Nanowires inthe Triton X-100/Cyclohexane/Water Reverse Micelles, Journal of Crystal Growth, 2002,244,379-383; Y.Chen, Q.S.Wu, Facile Synthesis and Properties Research of SingleCrystal Calcium Sulfate Nanotube Through Reverse
Thermolysis conversion process how to control the sulfate hemihydrate calcium pyroborate is another key problem in technology of preparation anhydrous calcium sulfate whisker.In roasting process, the sulfate hemihydrate calcium pyroborate need gradate through steps such as hydroxyl condensation dehydration, crystal conversion and structure reformations and be anhydrous calcium sulfate whisker.The modes such as maturing temperature or heating rate of adopt adjusting can be slowed down pattern in the calcium sulphate hemihydrate pyrolysis dehydration to a certain extent and be destroyed that (Yuan Zhitao prints ten thousand loyalties for Han Yuexin, Wang Yubin, and calcining is to the influence of calcium sulfate crystal whiskers structure and stability, IM﹠amp; P minerals commonly used in chemical industry and processing, 2008,3,13-16), but the hole that can't avoid dewatering and produce, make that anhydrous calcium sulfate whisker product structure defective is more, pattern is not good enough, reinforced effects reduces.
In a word,, remain, limited the further industrial application of correlation technique in problem such as condition harshness or product pattern be not good enough though forefathers have carried out a few thing at the high length-diameter ratio calcium sulfate crystal whiskers aspect preparing.
Summary of the invention
Main purpose of the present invention is to seek a kind of novel method for preparing high length-diameter ratio anhydrous calcium sulfate whisker.Technical solution of the present invention is as follows: a kind of novel preparation method of high length-diameter ratio anhydrous calcium sulfate whisker is characterized in that this method is carried out as follows:
1) be raw material with inorganic calcium salt and inorganic precipitant, with the tensio-active agent is dispersion agent, in temperature is that 10～90 ℃, stirring velocity are under 50-500 rev/min the condition, the inorganic calcium salt solution that the inorganic precipitation agent solution is contained tensio-active agent with the speed adding of 1～20mL/min, reaction 0.5～2 hour is continued in the reinforced back that finishes, and obtains white milk-like slurry.Wherein, the volumetric molar concentration of inorganic calcium salt, precipitation agent is 0.1～5mol/L, and the tensio-active agent volumetric molar concentration is 0.001～0.5mol/L, and the mol ratio of inorganic calcium salt, precipitation agent, tensio-active agent is 1: 1～5: 0.01～0.1;
2) white milk-like slurry is filtered, washs, to filter back gained solid and concentration then is the morphology control agent aqueous solution of 0.005～5mol/L, make the suspension that solid holdup is 0.1～25wt%, this suspension is placed autoclave, and low whipping speed is that 50-500 rev/min, temperature are hydrothermal treatment consists 0.5～10 hour under 100～250 ℃ of conditions;
3) with the suspension filtered after the hydro-thermal reaction, washing, under 100 ℃～110 ℃ temperature condition dry 1～8 hour, obtain the sulfate hemihydrate calcium pyroborate;
4) the sulfate hemihydrate calcium pyroborate is mixed with inorganic flux, the speed with 1～25 ℃/min in air atmosphere is heated to 200～800 ℃ of roastings 0.5～6 hour, naturally cools to room temperature after reaction finishes; Wherein the weight ratio of sulfate hemihydrate calcium pyroborate and inorganic flux is 100: 0.1～10;
5) product of roasting being mixed with deionized water, make the suspension that solid holdup is 1～20wt%, is under 20 ℃～90 ℃ conditions in temperature, stirs 0.5～2 hour with 50～250 rev/mins speed; With this suspension filtered, washing, under 100 ℃～110 ℃ temperature condition dry 1～8 hour, promptly making length was 20～2000 μ m, and diameter is 0.5～20 μ m, and length-to-diameter ratio is 40～1000, main content is greater than the anhydrous calcium sulfate whisker of 95wt%.
In above-mentioned preparation method, described inorganic calcium salt is any in calcium chloride, nitrocalcite, calcium oxide, lime carbonate and the carbide slag; Described inorganic precipitant is any in sulfuric acid, sodium sulfate, vitriolate of tartar, sodium pyrosulfate and the sal enixum; Described tensio-active agent is any in cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, sodium oleate, potassium laurate and the ethylene glycol; Described morphology control agent is any in sodium-chlor, Repone K, sodium sulfate, vitriolate of tartar, iron protochloride, ferrous sulfate and the ethylenediamine tetraacetic acid (EDTA); Described inorganic flux is any in sodium-chlor, Repone K, ammonium chloride, sodium hydroxide and the potassium hydroxide.
The present invention proposes a kind of novel method for preparing high length-diameter ratio anhydrous calcium sulfate whisker, this invention has following characteristics and high-lighting effect: 1. adopting inorganic calcium salt is the calcium source, with vitriol or sulfuric acid is inorganic precipitant, the synthetic finely disseminated ultra-fine terra alba presoma under the normal temperature condition that acts on by tensio-active agent, the presoma of small particle size, high dispersive helps promoting follow-up hydrothermal conversion (dissolving-reaction-crystallization) process, preparation high length-diameter ratio whisker.2. in the hydrothermal growth process, add the morphology control agent, utilize the direction of growth and the speed of growth of its selective adsorption effect control hydrothermal product, promote the one-dimensional growth of sulfate hemihydrate calcium pyroborate.3. the mode of taking to add inorganic flux is carried out roasting, utilizes the material transfer speed in the melting media acceleration calcium sulphate hemihydrate dehydration, reaches structure and reforms and the hole purpose that disappears, and prepares high length-diameter ratio anhydrous calcium sulfate whisker thus.Technology of the present invention is simple, and is with low cost, and the added value of product height is easy to industry and promotes.The calcium sulfate crystal whiskers length-to-diameter ratio of utilizing the present invention to prepare is big, pattern is regular, uniform particle diameter, degree of crystallinity height, good dispersion, can be used as strongthener and is used for industries such as plastics, rubber, pottery, cement, papermaking.Similar technology is not appeared in the newspapers both at home and abroad as yet.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the pattern of normal temperature product (a) in the embodiments of the invention 3, hydrothermal product (b) and product of roasting (c).
Fig. 3 is the X-ray powder diffraction spectrogram of normal temperature product (a) in the embodiments of the invention 3, hydrothermal product (b) and product of roasting (c).
Embodiment
The invention provides a kind of high length-diameter ratio Preparation methods of gypsum whiskers method.With inorganic calcium salt and inorganic precipitant is raw material, is dispersion agent with the tensio-active agent, at first the finely disseminated ultra-fine terra alba presoma of preparation under normal temperature condition; Under hydrothermal condition, utilize the one dimension oriented growth of the selective adsorption effect promotion calcium sulphate hemihydrate of morphology control agent then; Realize that with flux roasting mode disappear hole and structure of shrinkage cavity reform again, obtain thus that length-to-diameter ratio is big, pattern evenly rule, high, the finely disseminated calcium sulfate crystal whiskers of degree of crystallinity.Concrete steps are as follows:
1) be raw material with inorganic calcium salt and inorganic precipitant, with the tensio-active agent is dispersion agent, in temperature is that 10～90 ℃, stirring velocity are under 50～500 rev/mins the condition, the inorganic calcium salt solution that the inorganic precipitation agent solution is contained tensio-active agent with the speed adding of 1～20mL/min, reaction 0.5～2 hour is continued in the reinforced back that finishes, and obtains white emulsus suspension slurry.Wherein, the volumetric molar concentration of inorganic calcium salt, precipitation agent is 0.1～5mol/L, and the tensio-active agent volumetric molar concentration is 0.001～0.5mol/L, and the mol ratio of inorganic calcium salt, precipitation agent, tensio-active agent is 1: 1～5: 0.01～0.1;
2) white cream is filtered, washs, to filter back solid and volumetric molar concentration then is the morphology control agent aqueous solution of 0.005～5mol/L, make the suspension that solid holdup is 0.1～25wt%, this suspension is placed autoclave, and low whipping speed is that 50～500 rev/mins, temperature are hydrothermal treatment consists 0.5～10 hour under 100～250 ℃ of conditions;
3) with the suspension filtered after the hydro-thermal reaction, washing, drying is 1～8 hour under 100 ℃～110 ℃ temperature condition, obtains the sulfate hemihydrate calcium pyroborate;
4) the sulfate hemihydrate calcium pyroborate is mixed with inorganic flux, the speed with 1～25 ℃/min in air atmosphere is heated to 200～800 ℃ of roastings 0.5～6 hour, naturally cools to room temperature after reaction finishes; Wherein the weight ratio of sulfate hemihydrate calcium pyroborate and inorganic flux is 100: 0.1～10;
5) product of roasting being mixed with deionized water, make the suspension that solid holdup is 1～20wt%, is under 20 ℃～90 ℃ conditions in temperature, stirs 0.5～2 hour with 50～250 rev/mins of speed; With this suspension filtered, washing, under 100 ℃～110 ℃ temperature condition dry 1～8 hour, promptly making length is 20～2000 μ m, diameter is 0.5～20 μ m, length-to-diameter ratio is 40～1000, main content is greater than the anhydrous calcium sulfate whisker of 95wt%.
Described inorganic calcium salt is any in calcium chloride, nitrocalcite, calcium oxide, lime carbonate and the carbide slag; Described inorganic precipitant is any in sulfuric acid, sodium sulfate, vitriolate of tartar, sodium pyrosulfate and the sal enixum; Described tensio-active agent is any in cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, sodium oleate, potassium laurate and the ethylene glycol; Described morphology control agent is any in sodium-chlor, Repone K, sodium sulfate, vitriolate of tartar, iron protochloride, ferrous sulfate and the ethylenediamine tetraacetic acid (EDTA); Described inorganic flux is any in sodium-chlor, Repone K, ammonium chloride, sodium hydroxide and the potassium hydroxide.
Further specify the present invention below by specific embodiment.
Preparation contains the mixing solutions 100mL of 0.1mol/L calcium chloride and 0.001mol/L cetyl trimethylammonium bromide, 0.1mol/L sulphuric acid soln 100mL.In temperature is that 10 ℃, stirring velocity are under 50 rev/mins the condition, and sulphuric acid soln is added the mixing solutions that contains calcium chloride and cetyl trimethylammonium bromide with the speed of 20mL/min, and reaction 0.5 hour is continued in the reinforced back that finishes, and obtains white milk-like slurry; To put into autoclave after above-mentioned dope filtration, the washing, adding volumetric molar concentration is the sodium chloride solution of 0.005mol/L, regulate solid holdup to 0.1wt%, in temperature is that 100 ℃, stirring velocity are hydro-thermal reaction 10 hours under 50 rev/mins the condition, cooling, filter, washing, dry (105 ℃, 4 hours), obtain sulfate hemihydrate calcium pyroborate intermediate product.The sulfate hemihydrate calcium pyroborate is mixed with sodium-chlor, controlling the two weight ratio is 100: 0.1, mixture is placed retort furnace, kept 6 hours after being warming up to 200 ℃ with the speed of 1 ℃/min, naturally cool to room temperature then, be mixed and made into the suspension that solid holdup is 1wt% with appropriate amount of deionized water, in temperature is under 20 ℃ of conditions, with 50 rev/mins speed agitator treatings 0.5 hour, filter, washing, dry (105 ℃, 4 hours), obtain mean length and be 2000 μ m, mean diameter and be 2 μ m, length-to-diameter ratio and be 1000, the anhydrous calcium sulfate whisker of main content 98wt%.
Embodiment 2
Preparation contains the mixing solutions 100mL of 5mol/L nitrocalcite and 0.5mol/L Sodium dodecylbenzene sulfonate, 5mol/L potassium sulfate solution 100mL.In temperature is that 90 ℃, stirring velocity are under 500 rev/mins of conditions, and potassium sulfate solution is added the mixing solutions that contains nitrocalcite and Sodium dodecylbenzene sulfonate with the speed of 1mL/min, and reaction 2 hours is continued in the reinforced back that finishes, and obtains white milk-like slurry; To put into autoclave after above-mentioned dope filtration, the washing, add volumetric molar concentration and regulate solid holdup to 20wt% for the 5mol/L Klorvess Liquid, in temperature is that 250 ℃, stirring velocity are hydro-thermal reaction 0.5 hour under 500 rev/mins of conditions, cooling, filter, washing, dry (105 ℃, 4 hours), obtain sulfate hemihydrate calcium pyroborate intermediate product.The sulfate hemihydrate calcium pyroborate is mixed with Repone K, controlling the two weight ratio is 100: 10, mixture is placed retort furnace, kept 0.5 hour after being warming up to 800 ℃ with 25 ℃/min speed, naturally cool to room temperature then, be mixed and made into the suspension that solid holdup is 20wt% with appropriate amount of deionized water, in temperature is under 90 ℃, with 250 rev/mins of speed agitator treatings 2 hours, filter, washing, dry (105 ℃, 4 hours), obtain mean length and be 800 μ m, mean diameter and be 2 μ m, length-to-diameter ratio and be 400, the anhydrous calcium sulfate whisker of main content 98.5wt%.
Embodiment 3
Preparation contains the mixing solutions 100mL of 3mol/L calcium chloride and 0.04mol/L potassium laurate, 0.1mol/L metabisulfite solution 100mL.In temperature is that 25 ℃, stirring velocity are under 100 rev/mins the condition, and metabisulfite solution is added the mixing solutions that contains calcium chloride and potassium laurate with 1mL/min speed, and reaction 1.5 hours is continued in the reinforced back that finishes, and obtains white milk-like slurry; To put into autoclave after above-mentioned dope filtration, the washing, add volumetric molar concentration and regulate solid holdup to 10wt% for the 0.005mol/L metabisulfite solution, in temperature is that 135 ℃, stirring velocity are hydro-thermal reaction 2 hours under 150 rev/mins of conditions, cooling, filter, washing, dry (105 ℃, 4 hours), obtain sulfate hemihydrate calcium pyroborate intermediate product.The sulfate hemihydrate calcium pyroborate is mixed with ammonium chloride, controlling the two weight ratio is 100: 5, mixture is placed retort furnace, kept 2 hours after being warming up to 350 ℃ with the speed of 5 ℃/min, naturally cool to room temperature then, be mixed and made into the suspension that solid holdup is 10wt% with appropriate amount of deionized water, be under 40 ℃ the condition in temperature, with 150 rev/mins of speed agitator treatings 1.5 hours, filter, washing, dry (105 ℃, 4 hours), obtain mean length and be 1000 μ m, mean diameter and be 10 μ m, length-to-diameter ratio and be 100, the anhydrous calcium sulfate whisker of main content 98wt%.Fig. 2 is the shape appearance figure of normal temperature product (a), hydrothermal product (b) and product of roasting (c), and Fig. 3 is the X-ray powder diffraction spectrogram of normal temperature product (a), hydrothermal product (b) and product of roasting (c).
Embodiment 4
Preparation contains the mixing solutions 100mL of 1mol/L calcium oxide and 0.1mol/L Sodium palmityl sulfate, 5mol/L potassium sulfate solution 100mL.In temperature is that 60 ℃, stirring velocity are under 50 rev/mins of conditions, and potassium sulfate solution is added the mixing solutions that contains calcium oxide and Sodium palmityl sulfate with the speed of 10mL/min, and reaction 1 hour is continued in the reinforced back that finishes, and obtains white milk-like slurry; To put into autoclave after above-mentioned dope filtration, the washing, add volumetric molar concentration and regulate solid holdup to 25wt% for the 1mol/L potassium sulfate solution, in temperature is that 220 ℃, stirring velocity are hydro-thermal reaction 1 hour under 100 rev/mins of conditions, cooling, filter, washing, dry (105 ℃, 4 hours), obtain sulfate hemihydrate calcium pyroborate intermediate product.The sulfate hemihydrate calcium pyroborate is mixed with sodium hydroxide, controlling the two weight ratio is 100: 5, mixture is placed retort furnace, kept 4 hours after being warming up to 500 ℃ with the speed of 10 ℃/min, naturally cool to room temperature then, be mixed and made into the suspension that solid holdup is 15wt% with appropriate amount of deionized water, in temperature is under 60 ℃, with 100 rev/mins of speed agitator treatings 1 hour, filter, washing, dry (110 ℃, 1 hour), obtain mean length and be 20 μ m, mean diameter and be 0.5 μ m, length-to-diameter ratio and be 40, the anhydrous calcium sulfate whisker of main content 97.5wt%.
Embodiment 5
Preparation contains the mixing solutions 100mL of 2mol/L lime carbonate and 0.02mol/L sodium oleate, 4mol/L sodium bisulfate 100mL.In temperature is that 40 ℃, stirring velocity are under 250 rev/mins of conditions, and sodium bisulfate is added the mixing solutions that contains lime carbonate and sodium oleate with the speed of 15mL/min, and reaction 1 hour is continued in the reinforced back that finishes, and obtains white milk-like slurry; To put into autoclave after this dope filtration, the washing, add the 0.01mol/L solution of ferrous chloride and regulate solid holdup to 5wt%, in temperature is that 160 ℃, stirring velocity are hydro-thermal reaction 6 hours under 200 rev/mins of conditions, cooling, filter, washing, dry (105 ℃, 4 hours), obtain sulfate hemihydrate calcium pyroborate intermediate product.The sulfate hemihydrate calcium pyroborate is mixed with sodium-chlor, controlling the two weight ratio is 100: 0.1, mixture is placed retort furnace, kept 3 hours after being warming up to 400 ℃ with 1 ℃/min speed, naturally cool to room temperature then, be mixed and made into the suspension that solid holdup is 10wt% with appropriate amount of deionized water, in temperature is under 80 ℃, with 80 rev/mins speed agitator treatings 1 hour, filter, washing, dry (105 ℃, 4 hours), being mixed and made into the suspension that solid holdup is 5wt% with appropriate amount of deionized water then, was under 30 ℃ of conditions in temperature, with 120 rev/mins speed agitator treatings 1 hour, filter, washing, drying, obtaining mean length is 1000 μ m, mean diameter is 20 μ m, length-to-diameter ratio is 50, the anhydrous calcium sulfate whisker of main content 97wt%.
Embodiment 6
Preparation contains the mixing solutions 100mL of 2mol/L calcium chloride and 0.5mol/L ethylene glycol, 5mol/L potassium hydrogen sulfate solution 100mL.In temperature is that 20 ℃, stirring velocity are under 100 rev/mins the condition, and potassium hydrogen sulfate solution is added the mixing solutions that contains calcium chloride and ethylene glycol with the speed of 8mol/min, and reaction 2 hours is continued in the reinforced back that finishes, and obtains white milk-like slurry; To put into autoclave after above-mentioned dope filtration, the washing, add volumetric molar concentration and regulate solid holdup to 5wt% for the 0.05mol/L copperas solution, in temperature is that 180 ℃, stirring velocity are hydro-thermal reaction 3 hours under 150 rev/mins the condition, cooling, filter, washing, dry (105 ℃, 4 hours), obtain sulfate hemihydrate calcium pyroborate intermediate product.The sulfate hemihydrate calcium pyroborate is mixed with sodium hydroxide, controlling the two weight ratio is 100: 8, mixture is placed retort furnace, kept 3 hours after being warming up to 350 ℃ with the speed of 15 ℃/min, naturally cool to room temperature then, be mixed and made into the suspension that solid holdup is 1wt% with appropriate amount of deionized water, in temperature is under 50 ℃ of conditions, with 150 rev/mins speed agitator treatings 1.5 hours, filter, washing, dry (105 ℃, 3 hours), obtaining mean length is 1600 μ m, mean diameter is 8 μ m, length-to-diameter ratio is 200, the anhydrous calcium sulfate whisker of main content 96.5wt%.
Embodiment 7
Preparation contains the mixing solutions 100mL of 1mol/L carbide slag and 0.05mol/L cetyl trimethylammonium bromide, 3mol/L sulphuric acid soln 100mL.In temperature is that 15 ℃, stirring velocity are under 50 rev/mins the condition, and sulphuric acid soln is added the mixing solutions that contains carbide slag and cetyl trimethylammonium bromide with the speed of 10mL/min, and reaction 1 hour is continued in the reinforced back that finishes, and obtains white milk-like slurry; To put into autoclave after above-mentioned dope filtration, the washing, add volumetric molar concentration and regulate solid holdup to 12wt% for the 0.02mol/L edta solution, in temperature is that 140 ℃, stirring velocity are hydro-thermal reaction 10 hours under 80 rev/mins the condition, cooling, filter, washing, dry (100 ℃, 8 hours), obtain sulfate hemihydrate calcium pyroborate intermediate product.The sulfate hemihydrate calcium pyroborate is mixed with potassium hydroxide, controlling the two weight ratio is 100: 0.1, mixture is placed retort furnace, kept 6 hours after being warming up to 200 ℃ with the speed of 1 ℃/min, naturally cool to room temperature then, be mixed and made into the suspension that solid holdup is 4wt% with appropriate amount of deionized water, in temperature is under 30 ℃ of conditions, with 150 rev/mins speed agitator treatings 1.5 hours, filter, washing, dry (105 ℃, 4 hours), obtain mean length and be 500 μ m, mean diameter and be 2 μ m, length-to-diameter ratio and be 50, the anhydrous calcium sulfate whisker of main content 95wt%.
Claims (6)
1. the preparation method of a high length-diameter ratio anhydrous calcium sulfate whisker is characterized in that, this method is carried out as follows:
1) be raw material with inorganic calcium salt and inorganic precipitant, with the tensio-active agent is dispersion agent, in temperature is 10～90 ℃, stirring velocity is under 50-500 rev/min the condition, speed with 1～20mL/min contains the adding of inorganic precipitation agent solution in the inorganic calcium salt solution of tensio-active agent, reaction 0.5～2 hour is continued in the reinforced back that finishes, obtain white emulsus suspension slurry, wherein, the volumetric molar concentration of inorganic calcium salt and inorganic precipitant is 0.1～5mol/L, the tensio-active agent volumetric molar concentration is 0.001～0.5mol/L, inorganic calcium salt, the mol ratio of precipitation agent and tensio-active agent is 1: 1～5: 0.01～0.1;
2) white emulsus suspension slurry is filtered, washs, to filter back gained solid and volumetric molar concentration then is the morphology control agent aqueous solution of 0.005～5mol/L, make the suspension that solid holdup is 0.1～25wt%, this suspension is placed autoclave, and low whipping speed is that 50～500 rev/mins, temperature are hydrothermal treatment consists 0.5～10 hour under 100～250 ℃ of conditions;
3) with the suspension filtered after the hydro-thermal reaction, washing, drying is 1～8 hour under 100 ℃～110 ℃ temperature condition, obtains the sulfate hemihydrate calcium pyroborate;
4) the sulfate hemihydrate calcium pyroborate is mixed with inorganic flux, the speed with 1～25 ℃/min in air atmosphere is heated to 200～800 ℃, and constant temperature calcining 0.5～6 hour naturally cools to room temperature after reaction finishes; Wherein the weight ratio of sulfate hemihydrate calcium pyroborate and inorganic flux is 100: 0.1～10;
5) product of roasting being mixed with deionized water, make the suspension that solid holdup is 1～20wt%, is under 20 ℃～90 ℃ the condition in temperature, stirs 0.5～2 hour with 50～250 rev/mins speed; With this suspension filtered, washing, under 100 ℃～110 ℃ temperature condition dry 1～8 hour, promptly making length is 20～2000 μ m, diameter is 0.5～20 μ m, length-to-diameter ratio is 40～1000, main content is greater than the anhydrous calcium sulfate whisker of 95wt%.
2. the preparation method of a kind of high length-diameter ratio anhydrous calcium sulfate whisker according to claim 1, it is characterized in that: described inorganic calcium salt is any in calcium chloride, nitrocalcite, calcium oxide, lime carbonate and the carbide slag.
3. the preparation method of a kind of high length-diameter ratio anhydrous calcium sulfate whisker according to claim 1 and 2, it is characterized in that: described inorganic precipitant is any in sulfuric acid, sodium sulfate, vitriolate of tartar, sodium pyrosulfate and the sal enixum.
4. the preparation method of a kind of high length-diameter ratio anhydrous calcium sulfate whisker according to claim 1 and 2, it is characterized in that: described tensio-active agent is any in cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, sodium oleate, potassium laurate and the ethylene glycol.
5. the preparation method of a kind of high length-diameter ratio anhydrous calcium sulfate whisker according to claim 1 and 2, it is characterized in that: described morphology control agent is any in sodium-chlor, Repone K, sodium sulfate, vitriolate of tartar, iron protochloride, ferrous sulfate and the ethylenediamine tetraacetic acid (EDTA).
6. the preparation method of a kind of high length-diameter ratio anhydrous calcium sulfate whisker according to claim 1 and 2, it is characterized in that: inorganic flux is any in sodium-chlor, Repone K, ammonium chloride, sodium hydroxide and the potassium hydroxide.
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