CN1228476C - New method of rapid synthesis of basic bitter salt - Google Patents
New method of rapid synthesis of basic bitter salt Download PDFInfo
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- CN1228476C CN1228476C CN 03109842 CN03109842A CN1228476C CN 1228476 C CN1228476 C CN 1228476C CN 03109842 CN03109842 CN 03109842 CN 03109842 A CN03109842 A CN 03109842A CN 1228476 C CN1228476 C CN 1228476C
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- magnesium
- crystal whisker
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- magnesium sulfate
- sulfate crystal
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 88
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 43
- 239000013078 crystal Substances 0.000 claims abstract description 41
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 32
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 40
- 239000000725 suspension Substances 0.000 claims description 34
- 230000036571 hydration Effects 0.000 claims description 31
- 238000006703 hydration reaction Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010335 hydrothermal treatment Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 6
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 208000006558 Dental Calculus Diseases 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 3
- 230000016615 flocculation Effects 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 20
- 239000011777 magnesium Substances 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000003063 flame retardant Substances 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000000919 ceramic Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 43
- 239000000047 product Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OLZDXDPSDUSGIS-UHFFFAOYSA-N sulfinylmagnesium Chemical compound [Mg].S=O OLZDXDPSDUSGIS-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- 229910034327 TiC Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention discloses a preparation method of hydrated basic magnesium sulfate crystal whisker, which belongs to the field of preparation of an inorganic chemical industry material. In the present invention, magnesium salt resources which are the by-products of sea and lake salt chemical industry enterprises are used as raw materials. Firstly, a nanometer-level magnesium hydroxide precursor with strong solubility and high dispersivity is prepared by a quick mixing method at normal temperature; then, the nanometer-level magnesium hydroxide precursor is added into a water solution containing sulfate, a magnesium hydroxide solubilizer and a dispersant for quick hydrothermal reaction; the hydrated basic magnesium sulfate crystal whisker with homogeneous size, regular pattern and good dispersivity is directly prepared by filtration, washing and drying. The composition of the hydrated basic magnesium sulfate crystal whisker is 5Mg(OH)2. MgSO4.3H2O, the average length is from 5 to 50 mum, and the average diameter is from 0.1 to 2 mum. The preparation method has the advantages of simple technological process, low cost, little consumption, high added value and large temperature operating flexibility, and the preparation method is easy of industrialized popularization. The hydrated basic magnesium sulfate crystal whisker can be used as a reinforcing agent and a flame retardant for preparing high-strength composite materials, such as rubber, plastic, resin, ceramic, etc. The present invention provides a new approach for high utilization of magnesium resources in the sea and lake salt industry.
Description
Technical field
The invention belongs to the inorganic chemical industry technical field of material, particularly a kind of preparation method of hydration alkali magnesium sulfate crystal whisker.
Background technology
Whisker is a length-to-diameter ratio greater than 10, sectional area is less than 5 * 10
-4Cm
2The single crystal fibre material.Whisker atomic structure when crystallization is arranged high-sequential, and subsurface defect is less, so its intensity and modulus are the strengthening and toughening agent of the very excellent matrix material of a kind of mechanical property all near the theoretical value of its perfect crystal material.
Since U.S. telephone bell company in 1948 finds whisker first, prepared more than 100 kind of crystal whisker materials so far, comprise that metal whisker (as Sn, Fe, Cu, Te, Cd, Ni etc.) and nonmetal whisker are (as Si
3N
4, SiC, Al
2O
3, ZrO
2, AlN, TiO
2, TiC, NaCl, TiN and mullite etc.).Industrialization crystal whisker products (silicon carbide) the earliest comes across 1962, and (3000-5000 unit/kg) has limited its application because of price is high.Until cheap potassium titanate crystal whisker in the eighties in 20th century after Japan comes out, the application of whisker just has breakthrough.The research and development of China's inorganic crystal whisker start from the nineties initial stage, successively develop whiskers such as potassium titanate, calcium sulfate, but mostly fail to obtain large-scale industrial application owing to price is higher.
China is magnesium resource big country, a large amount of magnesite (reserves account for world's total reserves 1/3rd), rhombspar, brucite and seawater resources are not only arranged, and the salt lake magnesium resource is also extremely abundant, for the industry of development magnesium salts provides good condition.Be subjected to the restriction of technology and economic condition, the magnesium salts product of China (as magnesium oxide, sal epsom, magnesiumcarbonate and magnesium chloride etc.) primary products few with technology content mostly at present, that added value is low are sold.The magnesium resource that how highly to utilize China is the researcher urgent problem.
At present countries in the world energetically the high added value magnesium of research and development be that product has flame retardant of magnesium hydroxide, alkali magnesium sulfate crystal whisker, magnesium borate crystal whisker, high-purity magnesium oxide, nano magnesia etc.In above-mentioned magnesium products, alkali magnesium sulfate crystal whisker is with its superior enhancing flame retardant properties and cheap relatively price and especially prominent.
The hydration alkali magnesium sulfate has a 5Mg (OH) with what the whisker form existed
2MgSO
43H
2O, Mg (OH)
22MgSO
43H
2O, 5Mg (OH)
2MgSO
42H
2O, 3Mg (OH)
2MgSO
48H
2O, 5Mg (OH)
2MgSO
4Deng.People have carried out many researchs to the preparation process of hydration alkali magnesium sulfate crystal whisker in recent years.Otaka etc. disclose the United States Patent (USP) that name is called " acrylic resin compositions " and have proposed usefulness Mg (OH) in US Patent 5326548
2And MgSO
4Be raw material, synthetic median size is that 0.3 μ m, length-to-diameter ratio are that 100 magnesium oxysulfide whisker adopts three-step approach to prepare anhydrous alkali magnesium sulfate (5Mg (OH) under hydrothermal condition
2MgSO
4): at first under hydrothermal condition, handle the suspension preparation Mg (OH) that contains sal epsom and magnesium hydroxide/magnesium oxide powder
22MgSO
43H
2The O precipitation makes it be converted into 5Mg (OH) 40 ℃ of following ageings then
2MgSO
48H
2The O whisker; Whisker promptly gets 5Mg (OH) after 170 ℃ of roastings
2MgSO
4Whisker.The whisker morphology that adopts the preparation of this method is rule (diameter 0.1-2.0 μ m, length 10-100 μ m) comparatively, but process is more numerous and diverse.Dong Dianquan etc. have reported that in " Preparation of Basic Magnesium Sulfate Whisker " of " functional materials; 1999,30 (5), 559-560 " mol ratio by controlled oxidation magnesium and sal epsom is 1.05: 1, prepare diameter 0.5-10 μ m at 170-200 ℃, the 5Mg (OH) of length 20-120 μ m
2MgSO
43H
2O whisker, the shortcoming of this method are that the homogeneity of whisker is relatively poor.Wei Zhongqing etc. are in that " 1-9) report is a raw material with sal epsom and magnesium hydroxide in " " physical and chemical performance of hydration alkali magnesium sulfate characterizes ", makes macrofiber shape 5Mg (OH) in 2-6 hour 130-170 ℃ of reaction for salt lake research, 1998,6 (2-3)
2MgSO
43H
2O whisker (diameter 0.8-1.2 μ m, length～200 μ m), but product has buckling phenomenon and fragment more.Because MgO and Mg (OH)
2Belong to micro-soluble material, with MgSO
4Speed is lower during solution reaction, and the transformation efficiency of reaction is lower, and purity is not high.People have inquired into the feasibility of the synthetic alkali magnesium sulfate crystal whisker of direct hydro-thermal again for this reason.Yi etc. disclose 130-150 ℃ of direct down the processing at " Preparation and Characterization of Magnesium HydroxideSulfate Hydrate Whiskers; Chemistry of Materials; 2000,12 (10), 2845-2852 " and have contained NH
3H
2O and MgSO
4Mixing solutions, synthesized 4.34Mg (OH)
2MgSO
4XH
2The O whisker, but product contains Mg (OH) mostly
2Impurity.Yue Tao etc. are at " the 5Mg (OH) of " Chinese Journal of Inorganic Chemistry, 2002,18 (3), 313-315 "
2MgSO
42H
2Morphological research in the O whisker growth process " middle explanation, under hydrothermal condition, make MgSO
4With the NaOH reaction, prepare the 5Mg (OH) that is sector structure
2MgSO
42H
2The O whisker.Gao Shiyang, Yue Tao, Zhu Lixia, Xia Shuping is at patent of invention: CN1346800A, in the novel method of whisker " preparation magnesium oxysulfide " with 35-45% sodium hydroxide: 20-30% sal epsom: the weight ratio of 5-10% sodium sulfate is 1: 812: 14, under 140-180 ℃, carried out hydro-thermal reaction 2-10 hour, and obtained the magnesium oxysulfide whisker.Owing to fail to solve the solubility problem of magnesium hydroxide, so speed of reaction is still slower, needed 2-10 hour can form whisker.In a word,, remaining in many problems aspect preparation technology or the product property, limiting the large-scale industrial application of alkali magnesium sulfate crystal whisker though many relevant alkali magnesium sulfate crystal whisker preparation methods' report is arranged at present.For this reason, main purpose of the present invention is intend to adopt normal temperature short mix mode to prepare good dispersity, nanometric magnesium hydroxide presoma that solvability is strong, it is synthetic to carry out hydro-thermal then in containing the hydro-thermal reaction solution of magnesium hydroxide solubilizing agent, so that a novel method of preparation alkali magnesium sulfate crystal whisker fast to be provided.
Summary of the invention
The objective of the invention is to propose to quicken the magnesium hydroxide dissolving, improve the preparation method of a kind of hydration alkali magnesium sulfate crystal whisker of hydro-thermal reaction speed, it is characterized in that: the magnesium salts resource with sea lake salt chemical enterprise by-product is a raw material, at first prepare high-dispersion nano level magnesium hydroxide presoma by the normal temperature synthesis method, then its adding is contained in the aqueous solution of vitriol, magnesium hydroxide solubilizing agent and dispersion agent and carry out quick hydro-thermal reaction, more after filtration, washing, dry directly preparation size is even, pattern is regular, the hydration alkali magnesium sulfate crystal whisker of good dispersity; Its preparation method is as follows:
1. be raw material with inorganic water-soluble magnesium salt, mineral alkali is a precipitation agent, under 25-90 ℃, the whipped state of 150800rpm, carry out the liquid-phase precipitation reaction, generate the high-dispersion magnesium hydroxide presoma of median size 10-100 nanometer, wherein the w/v concentration of inorganic water-soluble magnesium salt is 3-30%, and the w/v concentration of precipitation agent is 3-30%;
2. add water-soluble flocculant in suspension, add-on is the 0.1-1% of magnesium hydroxide weight, standing sedimentation after the dispersed with stirring;
3. with suspension filtered, washing, then solid being put into any that contain vitriol that w/v concentration is 3-30%, sulfuric acid, nitric acid, ethylenediamine tetraacetic acid (EDTA) and oxalic acid that w/v concentration is 0.1-20% is Sodium hexametaphosphate 99, the ethanol of 0.1-10%, any aqueous solution as dispersion agent of Sodium dodecylbenzene sulfonate as magnesium hydroxide solubilizing agent and w/v concentration, the w/v concentration of making solid holdup is the suspension of 1-25%, dispersed with stirring;
4. the suspension that 3. step is prepared places autoclave, carries out hydrothermal treatment consists in 100-250 ℃ under the 50-700rpm whipped state, and the time is 0.5-2 hour;
5. will can make the hydration alkali magnesium sulfate crystal whisker after the suspension filtered after the hydrothermal treatment consists, washing, the drying.
Described inorganic water-soluble magnesium salt is any in magnesium chloride or the sal epsom;
Described precipitation agent is any in sodium hydroxide, potassium hydroxide or the ammonium hydroxide;
Described flocculation agent is any in polyacrylamide, starch, the polyaluminium sulfate;
Described vitriol is any in sodium sulfate, vitriolate of tartar, ammonium sulfate or the sal epsom;
The normal temperature that the invention has the beneficial effects as follows employing synthesizes-hydro-thermal reaction technology, put forward, in water-heat process, add the solubleness of measure increase magnesium hydroxide in the aqueous solution such as magnesium hydroxide solubilizing agent by preparation high-dispersion nano level magnesium hydroxide forerunner, improve hydro-thermal reaction speed, reduce the process energy consumption; Improve the homogeneity of hydrothermal treatment consists system by adding dispersion agent simultaneously, make preparation whisker size homogeneous, good dispersity and can be in than large-temperature range (100-250 ℃) stable existence.Guaranteed the low distinguishing feature of pattern, structure, purity, homogeneity, energy consumption of hydration alkali magnesium sulfate crystal whisker.Hydration alkali magnesium sulfate crystal whisker with this method preparation is formed 5Mg (OH)
2MgSO
43H
2O, length 5-50 μ m, diameter 0.1-2.0 μ m, hydration alkali magnesium sulfate crystal whisker content is greater than 95%.Product of the present invention can be used for industries such as plastics, rubber, resin and pottery, as strengthening and the fire retardant use.This technical matters is simple, with low cost, added value is high, has bigger industrial promotional value.
Description of drawings
Fig. 1 be used to prepare the normal temperature of hydration alkali magnesium sulfate crystal whisker synthetic-process flow diagram of hydro-thermal reaction.
Fig. 2 is the electromicroscopic photograph of the synthetic magnesium hydroxide of gained normal temperature among the embodiment 2.
Fig. 3 is the electromicroscopic photograph of gained hydration alkali magnesium sulfate crystal whisker among the embodiment 2.
Fig. 4 is the XRD diffraction spectrogram of gained hydration alkali magnesium sulfate crystal whisker among the embodiment 2.
Fig. 5 is the electromicroscopic photograph of gained hydration alkali magnesium sulfate crystal whisker among the embodiment 4.
Fig. 6 is the XRD diffraction spectrogram of gained hydration alkali magnesium sulfate crystal whisker among the embodiment 4.
Embodiment
The present invention is a kind of preparation method of hydration alkali magnesium sulfate crystal whisker, with the inorganic water-soluble magnesium salt (magnesium chloride, sal epsom) from the high-magnesium brine of sea lake salt chemical enterprise by-product is main raw material, under precipitation agent (sodium hydroxide, potassium hydroxide, ammonium hydroxide) and whipped state (200-700rpm) condition, carry out precipitin reaction, the high-dispersion nano magnesium hydroxide presoma suspension of generation median size 10-100 nanometer in 25-90 ℃; In above-mentioned suspension, add micro-flocculation agent (polyacrylamide, starch, polyaluminium sulfate) to improve solid-liquid separation effect, filter, after the washing gained solid is suspended in again and contains vitriol (sodium sulfate, vitriolate of tartar, ammonium sulfate, sal epsom), magnesium hydroxide solubilizing agent (sulfuric acid, nitric acid, ethylenediamine tetraacetic acid (EDTA), oxalic acid) and dispersion agent (Sodium hexametaphosphate 99, ethanol, Sodium dodecylbenzene sulfonate) in the aqueous solution, in 100-250 ℃ of scope, above-mentioned suspension is carried out quick hydrothermal treatment consists (0.5-2 hour), hydrothermal product after filtration, washing, drying can make size evenly, the pattern rule, the hydration alkali magnesium sulfate crystal whisker product of good dispersity.Its concrete operations step (as shown in Figure 1) is as follows:
1. configuration concentration is the inorganic water soluble magnesium salts solution of 3-30% (w/v) respectively, the precipitant solution of 3-30% (w/v), the flocculant solution of 0.1-10% and hydro-thermal reaction solution (containing 3-30% (w/v) vitriol, 0.1-20% (w/v) magnesium hydroxide solubilizing agent and 0.1-10% dispersion agent).
2. magnesium salt solution and precipitant solution are warming up to 25-90 ℃ respectively, progressively precipitant solution are added magnesium salt solution then under whipped state (150-800rpm), the adding speed of solution is 1-30ml/min.
3. in above-mentioned suspension, add flocculant solution, stir the back standing sedimentation.
4. with suspension filtered, washing, then with solid dispersed in the aqueous solution that contains 3-30% (w/v) vitriol, 0.1-20% (w/v) magnesium hydroxide solubilizing agent and 0.1-10% (w/v) dispersion agent, make the suspension that solid holdup is 1-25%, dispersed with stirring.
5. above-mentioned suspension is placed autoclave, carry out hydrothermal treatment consists under 100-250 ℃, whipped state (50-700rpm), the time is 0.5-2 hour.
6. with the suspension filtered after the hydrothermal treatment consists, use deionized water wash, then under air atmosphere in 105 ℃ of dryings 4 hours, make mean length 5-50 μ m, mean diameter 0.1-2.0 μ m, hydration alkali magnesium sulfate crystal whisker content greater than 95% product.
Enumerate several embodiment below with further understanding content of the present invention.
Embodiment 1:
Preparation 30% (w/v) magnesium chloride solution 100ml, 20% (w/v) potassium hydroxide solution 100ml, the polyacrylamide solution 5ml of 0.1% (w/v), hydro-thermal reaction solution (containing 30% sodium sulfate, 20% sulfuric acid and 10% Sodium hexametaphosphate 99) 100ml.25 ℃, stir under (800rpm) state magnesium chloride solution joined potassium hydroxide solution, it is 30ml/min that magnesium chloride adds speed.Make the magnesium hydroxide presoma suspension that median size is 10 nanometers behind reinforced the finishing.In gained suspension, add polyacrylamide solution, stirred after 10 minutes standing sedimentation 30 minutes.With gained suspension cooling, filter, put into hydro-thermal reaction solution with behind the deionized water wash 3 times, stir (300rpm) dispersion and be placed on high-pressure hydrothermal reaction kettle in 30 minutes, under whipped state (700rpm) in 100 ℃ of hydrothermal treatment consists 0.5 hour.Cool off then, filter, with deionized water wash 3 times, in 105 ℃ of dryings 4 hours, obtaining mean length was the hydration alkali magnesium sulfate (5Mg (OH) of 5 μ m, diameter 0.1 μ m, main content 96% in air atmosphere
2MgSO
43H
2O) whisker.
Embodiment 2:
Preparation 10% (w/v) Adlerika 100ml, 5% (w/v) sodium hydroxide solution 100ml, the starch solution 5ml of 1% (w/v), hydro-thermal reaction solution (containing 10% vitriolate of tartar, 5% nitric acid and 1% Sodium hexametaphosphate 99) 100ml.40 ℃, stir under (500rpm) state Adlerika joined sodium hydroxide solution, it is 15ml/min that sal epsom adds speed.Make the high-dispersion magnesium hydroxide presoma suspension that median size is 60 nanometers behind reinforced the finishing.In gained suspension, add starch solution, stirred after 10 minutes standing sedimentation 30 minutes.With gained suspension cooling, filter, put into hydro-thermal reaction solution with behind the deionized water wash 3 times, stir (300rpm) dispersion and be placed on autoclave in 30 minutes, under whipped state (200rpm) in 200 ℃ of hydrothermal treatment consists 1 hour.Cool off then, filter, with deionized water wash 3 times, in 105 ℃ of dryings 4 hours, obtaining mean length was the hydration alkali magnesium sulfate (5Mg (OH) of 18 μ m, diameter 0.8 μ m, main content 98% in air atmosphere
2MgSO
43H
2O) whisker.Fig. 2 represents the electromicroscopic photograph of the synthetic magnesium hydroxide of gained normal temperature among the embodiment 2, and Fig. 3 is the pattern of embodiment 2 products obtained therefroms, and Fig. 4 is the XRD diffracting spectrum of embodiment 2 products obtained therefroms.
Embodiment 3:
Preparation 3% (w/v) magnesium chloride solution 100ml, 3% (w/v) solution of ammonium hydroxide 100ml, the polyaluminum sulfate aluminum solutions 5ml of 0.5% (w/v), hydro-thermal reaction solution (containing 3% ammonium sulfate, 0.1% b diammonium edta and 0.1% ethanol) 100ml.90 ℃, stir under (150rpm) state magnesium chloride solution joined sodium hydroxide solution, it is 1ml/min that magnesium chloride adds speed.Make the high-dispersion magnesium hydroxide presoma suspension that median size is 100 nanometers behind reinforced the finishing.In gained suspension, add polyacrylamide solution, stirred after 10 minutes standing sedimentation 30 minutes.With gained suspension cooling, filter, put into hydro-thermal reaction solution with behind the deionized water wash 3 times, stir (300rpm) dispersion and be placed on autoclave in 30 minutes, under whipped state (50rpm) in 250 ℃ of hydrothermal treatment consists 2 hours.Cool off then, filter, with deionized water wash 3 times, in 105 ℃ of dryings 4 hours, obtaining mean length was the hydration alkali magnesium sulfate (5Mg (OH) of 50 μ m, mean diameter 2.0 μ m, main content 97% in air atmosphere
2MgSO
43H
2O) whisker.
Embodiment 4:
Preparation 10% (w/v) Adlerika 100ml, 25% (w/v) sodium hydroxide solution 100ml, the polyacrylamide solution 5ml of 5% (w/v), hydro-thermal reaction solution (containing 5% sal epsom, 10% oxalic acid and 4% Sodium dodecylbenzene sulfonate) 100ml.60 ℃, stir under (400rpm) state Adlerika joined sodium hydroxide solution, it is 10ml/min that sal epsom adds speed.Make the high-dispersion magnesium hydroxide presoma suspension that median size is 50 nanometers behind reinforced the finishing.In gained suspension, add polyacrylamide solution, stirred after 10 minutes standing sedimentation 30 minutes.With gained suspension cooling, filter, put into hydro-thermal reaction solution with behind the deionized water wash 3 times, stir (300rpm) dispersion and be placed on autoclave in 30 minutes, under whipped state (450rpm) in 160 ℃ of hydrothermal treatment consists 1.5 hours.Cool off then, filter, with deionized water wash 3 times, in 105 ℃ of dryings 4 hours, obtaining mean length was the hydration alkali magnesium sulfate (5Mg (OH) of 10 μ m, mean diameter 0.5 μ m, main content 96.5% in air atmosphere
2MgSO
43H
2O) whisker.Fig. 5 is the pattern of embodiment 4 products obtained therefroms, and Fig. 6 is the XRD diffracting spectrum of embodiment 4 products obtained therefroms.
Embodiment 5:
Preparation 20% (w/v) Adlerika 100ml, 15% (w/v) solution of ammonium hydroxide 100ml, the polyacrylamide solution 5ml of 6% (w/v), hydro-thermal reaction solution (containing 10% sodium sulfate, 2% sulfuric acid and 3% Sodium hexametaphosphate 99) 100ml.80 ℃, stir under (500rpm) state Adlerika joined solution of ammonium hydroxide, it is 15ml/min that sal epsom adds speed.Make the high-dispersion magnesium hydroxide presoma suspension that median size is 30 nanometers behind reinforced the finishing.In gained suspension, add polyacrylamide solution, stirred after 10 minutes standing sedimentation 30 minutes.With gained suspension cooling, filter, put into hydro-thermal reaction solution with behind the deionized water wash 3 times, stir (300rpm) dispersion and be placed on autoclave in 30 minutes, under whipped state (250rpm) in 120 ℃ of hydrothermal treatment consists 1 hour.Cool off then, filter, with deionized water wash 3 times, in 105 ℃ of dryings 4 hours, obtaining mean length was the hydration alkali magnesium sulfate (5Mg (OH) of 8.0 μ m, mean diameter 0.4 μ m, main content 95.5% in air atmosphere
2MgSO
43H
2O) whisker.
Above-mentioned used industrial chemicals is the commercial goods.
Claims (5)
1. the preparation method of a hydration alkali magnesium sulfate crystal whisker, it is characterized in that: the magnesium salts resource with sea lake salt chemical enterprise by-product is a raw material, and the method for preparing the hydration alkali magnesium sulfate crystal whisker is as follows:
1. be raw material with inorganic water-soluble magnesium salt, mineral alkali is a precipitation agent, under 25-90 ℃, the whipped state of 150-800rpm, carry out the liquid-phase precipitation reaction, generate the high-dispersion magnesium hydroxide presoma of median size 10-100 nanometer, wherein the w/v concentration of inorganic water-soluble magnesium salt is 3-30%, and the w/v concentration of precipitation agent is 3-30%;
2. add water-soluble flocculant in suspension, add-on is the 0.1-1.0% of magnesium hydroxide weight, standing sedimentation after the dispersed with stirring;
3. with suspension filtered, washing, then solid is put into contain the vitriol that w/v concentration is 3-30%, a kind of of sulfuric acid, nitric acid, ethylenediamine tetraacetic acid (EDTA) and oxalic acid that w/v concentration is 0.1-20% is a kind of aqueous solution as dispersion agent of Sodium hexametaphosphate 99, ethanol and the Sodium dodecylbenzene sulfonate of 0.1-10% as magnesium hydroxide solubilizing agent and w/v concentration, making solid holdup is the suspension of 1-25% for w/v concentration, dispersed with stirring;
4. the suspension that 3. step is prepared places autoclave, under the 50-700rpm whipped state, carries out hydrothermal treatment consists in 100-250 ℃, and the time is 0.5-2 hour;
5. will can make the hydration alkali magnesium sulfate crystal whisker after the suspension filtered after the hydrothermal treatment consists, washing, the drying.
2. according to the preparation method of the described hydration alkali magnesium sulfate crystal whisker of claim 1, it is characterized in that: described inorganic water-soluble magnesium salt is a kind of in magnesium chloride or the sal epsom.
3. according to the preparation method of the described hydration alkali magnesium sulfate crystal whisker of claim 1, it is characterized in that: described precipitation agent is a kind of in sodium hydroxide, potassium hydroxide or the ammonium hydroxide.
4. according to the preparation method of the described hydration alkali magnesium sulfate crystal whisker of claim 1, it is characterized in that: described flocculation agent is a kind of in polyacrylamide, starch, the polyaluminium sulfate.
5. according to the preparation method of the described hydration alkali magnesium sulfate crystal whisker of claim 1, it is characterized in that: described vitriol is a kind of in sodium sulfate, vitriolate of tartar, ammonium sulfate or the sal epsom.
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| CN1322049C (en) * | 2004-10-20 | 2007-06-20 | 大连圣迈化学有限公司 | Thermoplastic halogen-free few-smoke flame-proof cable sheath material and machining process |
| CN100393919C (en) * | 2006-05-31 | 2008-06-11 | 东北大学 | Method for magnesium hydroxide whisker using giobertite as material |
| CN101768783B (en) * | 2010-01-26 | 2012-07-04 | 大连理工大学 | Brucite based method for preparing basic magneislum |
| CN101956234A (en) * | 2010-10-09 | 2011-01-26 | 中国科学院青海盐湖研究所 | Method for preparing basic magnesium sulfate whiskers by recycling mother liquor |
| CN102206860B (en) * | 2011-05-23 | 2013-07-10 | 华东理工大学 | Method for preparing magnesium borate whisker with high length-to-diameter ratio by pelletization |
| CN103088400B (en) * | 2012-12-27 | 2015-10-28 | 清华大学 | A kind of method adopting alcohols-hydrothermal method to prepare high-purity magnesium oxide whisker |
| CN103834997B (en) * | 2014-03-10 | 2017-01-25 | 常州碳酸钙有限公司 | Method for preparing calcium carbonate whisker from saccharose by assisting hydrothermal process |
| CN105603504A (en) * | 2014-11-21 | 2016-05-25 | 合肥杰事杰新材料股份有限公司 | Method for preparing needle-like basic magnesium sulfate whiskers by ultrasonic assistance |
| CN104746131B (en) * | 2015-03-26 | 2017-05-17 | 岭南师范学院 | Method for preparing alkaline brucite crystal whisker by directly adding bittern into alkali liquid |
| CN104805495A (en) * | 2015-04-15 | 2015-07-29 | 中国科学院广州地球化学研究所 | Method for preparing basic magnesium sulfate whiskers from byproduct slurry of flue gas desulfurization with magnesium method |
| CN104988576B (en) * | 2015-07-14 | 2018-01-16 | 中国科学院青海盐湖研究所 | The preparation method of alkali magnesium sulfate crystal whisker |
| CN106006898B (en) * | 2016-07-14 | 2019-02-01 | 胡大苇 | It is a kind of using wheat bran as sewage treatment flocculating agent of raw material and preparation method thereof |
| CN107201542A (en) * | 2017-06-08 | 2017-09-26 | 青海大学 | A kind of preparation method of alkali magnesium sulfate crystal whisker |
| CN109797435A (en) * | 2017-11-17 | 2019-05-24 | 华东理工大学 | A kind of new method of low cost synthesis alkali magnesium sulfate crystal whisker |
| CN109137084B (en) * | 2018-09-10 | 2021-06-18 | 昆明理工大学 | Method for producing calcium sulfate dihydrate crystal whisker by salting-out method |
| CN109930204B (en) * | 2019-04-24 | 2021-01-01 | 广西大学 | Preparation method of in-situ hydrophobically modified basic magnesium sulfate whisker |
| CN114134574B (en) * | 2021-11-26 | 2023-03-07 | 山西大学 | High-length-diameter-ratio basic magnesium sulfate whisker and preparation method thereof |
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