CN104129817A - Method for preparing anhydrous cobalt chloride by using solvent displacement method - Google Patents
Method for preparing anhydrous cobalt chloride by using solvent displacement method Download PDFInfo
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- CN104129817A CN104129817A CN201410294456.3A CN201410294456A CN104129817A CN 104129817 A CN104129817 A CN 104129817A CN 201410294456 A CN201410294456 A CN 201410294456A CN 104129817 A CN104129817 A CN 104129817A
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- CN
- China
- Prior art keywords
- cobalt chloride
- solvent
- chloride
- anhydrous cobalt
- anhydrous
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002904 solvent Substances 0.000 title claims abstract description 18
- 238000011549 displacement method Methods 0.000 title claims abstract 5
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 229940097267 cobaltous chloride Drugs 0.000 claims description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000007614 solvation Methods 0.000 description 11
- 238000000605 extraction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000002889 sympathetic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparing anhydrous cobalt chloride by using a solvent displacement method, and relates to a preparation method for an inorganic salt. The method comprises the main steps of (1) carrying out preliminary dehydration of CoCl2.6H2O at a medium low temperature, so that four molecules of crystal water can be dehydrated to obtain CoCl2.2H2O; (2) adding an organic solvent in CoCl2.2H2O and displacing water molecules by using the organic solvent; (3) dehydrating through azeotropic distillation to obtain solvated anhydrous cobalt chloride; and (4) drying the solvated anhydrous cobalt chloride in a tube furnace under a nitrogen atmosphere and distilling the solvent out to obtain anhydrous cobalt chloride. The purity of the prepared anhydrous cobalt chloride is higher than 99%; and a recovery rate is over 99%. The process of the method is simple, and convenient for operation; process parameters can be controlled easily; and the method has no special requirements for equipment and is suitable for large-scale production.
Description
Technical field
The present invention relates to inorganic chemicals industry field.
Background technology
Waterless cobaltous chloride is a kind of important fine chemical material, and the application of cobalt chloride is mainly included in instrument manufacturing and is used as and produces weather gauge, specific gravity hydrometer, dry wet indicator etc.Ceramic industry is as tinting material.Coatings industry is for the manufacture of paint drier.In livestock industry for configuring mixed feed.Brewery industry is as Beer Foam Stabilizers.National defense industry is for the manufacture of poison gas cover.In chemical reaction, be used as catalyzer.Point folding chemistry in for spot analysis zinc, haploid breeding, in addition, also for the manufacture of sympathetic ink, paper of cobalt chloride,test, discolour silica gel etc.Also be used as the absorption agent of ammonia.At present domesticly do not produce on a large scale, the production research of industrialization waterless cobaltous chloride is subject to the attention of China's chemical engineering industry always.
Cobalt chloride crystal is at room temperature stable, loses crystal water and become blueness after being heated, and becomes again redness in malaria again.Therefore the preparation of the waterless cobaltous chloride more complicated that seems.The production method of prior art is that cobalt chloride hexahydrate is directly carried out to thermal dehydration, this method length consuming time, and energy consumption is large, and can there is hydrolysis and then generate cobalt oxide black solid in cobalt chloride in heat-processed simultaneously.Patent CN 102357308 A reports adopt air are heated, entering spray-drying chamber and cobalt chloride solution with rotating state carries out heat exchange and prepares waterless cobaltous chloride, the needed number of devices of this method is many, and complicated, needs higher temperature (230-280 DEG C) simultaneously.CN 101041473 A reports carry out heat exchange by hydrogen and chlorine high-temperature gas and the cobalt chloride producing of burning, and need electromagnetic catalysis, this method complicated operation, require high to equipment performance, operational danger is large, chlorine gas leakage can pollute surrounding enviroment, to having relatively high expectations of equipment.
Summary of the invention
The deficiency existing for prior art, the object of the present invention is to provide a kind of operating process equipment simple, and safety and environmental protection, the solvent exchange that energy consumption is low are prepared the method for waterless cobaltous chloride.
The present invention adopts following technical scheme for this reason:
Solvent exchange legal system is for a method for waterless cobaltous chloride,
1, the water molecules in low hydrated cobalt chloride is replaced and obtained solvation waterless cobaltous chloride, then it is dried and obtains waterless cobaltous chloride in nitrogen atmosphere, the hydrolysis of the cobalt chloride having caused while having avoided water to exist.Key step comprises the following steps:
At step 1:50-150 DEG C, carry out CoCl
26H
2the preliminary hydro-extraction of O, thus this step can be taken off the crystal water of 4 molecules and obtained CoCl
22H
2o;
Step 2: by CoCl
22H
2o is to adding ethanol, Virahol, and n-propyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, sec-butyl alcohol, amylalcohol, primary isoamyl alcohol, low-carbon alcohol and the acetonitriles such as 3-amylalcohol, in the organic solvents such as propionitrile, mechanical stirring is mixed fully, with organic solvent, water is replaced;
Step 3: carry out azeotropic distillation dehydration, obtain solvation waterless cobaltous chloride;
Step 4: under nitrogen protection, the waterless cobaltous chloride of solvation is dried in tube furnace, steams solvent, obtain waterless cobaltous chloride;
2, in step 1, Heating temperature is 120 DEG C, heat-up time 120min;
3, described in step 2 organic solvent be ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, sec-butyl alcohol, amylalcohol, primary isoamyl alcohol, 3-amylalcohol etc. and low-carbon alcohol and acetonitrile, the organic solvents such as propionitrile, the low hydrated cobalt chloride obtaining in the first step is added in organic solvent, be uniformly mixed fully, organic solvent is replaced fully to water;
4, in step 3, carry out altogether the dehydration of normal pressure azeotropic distillation, carry out azeotropic distillation dehydration as entrainer with organic solvent, the amount of organic solvent used be low hydrated cobalt chloride quality 1-5 doubly, rectifying reflux ratio is 5:1-10:1;
5, in step 4 in drying process, need to protect with nitrogen, the Heating temperature of tube furnace is 100 DEG C, and be 120min time of drying, and the flow velocity of nitrogen is 50mL/min.
The technical program technique is simple, easy to operate, and without high-temperature operation, processing parameter is easily controlled, and to equipment, without particular requirement, safety non-pollution, is easy to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is process flow sheet prepared by waterless cobaltous chloride.
Embodiment
Example one: (1) takes 500g cobalt chloride hexahydrate CoCl
26H
2o, puts into 120 DEG C of heating 120min of baking oven, obtains two hydrated cobalt chloride CoCl
22H
2o;
(2) two hydrated cobalt chlorides that the first step obtained join in dehydrated alcohol, stir fully, the water molecules in low hydrated cobalt chloride are cemented out with ethanol, and the consumption of ethanol is 1 times of two hydrated cobalt chloride quality;
(3) material obtaining in second step is carried out to azeotropic distillation, Heating temperature is 150 DEG C, and reflux ratio is that 10:1 carries out extraction liquid of top of the tower, until tower top temperature while reaching 78.5 DEG C, stops extraction, azeotropic distillation finishes, then unnecessary ethanol is steamed to recovery, obtain solvation waterless cobaltous chloride;
(4) the solvation waterless cobaltous chloride obtaining in the 3rd step is put into tube furnace, in nitrogen atmosphere, carry out 100 DEG C of heating 120min ethanol is steamed, obtain waterless cobaltous chloride, the m=270g that weighs, the purity of cobalt chloride is 99.1%.
Example two: (1) takes 500g cobalt chloride hexahydrate, puts into 120 DEG C of heating 120min of baking oven, obtains two hydrated cobalt chlorides;
(2) two hydrated cobalt chlorides that the first step obtained join in anhydrous n-propyl alcohol, stir fully, the water molecules in low hydrated cobalt chloride are cemented out with n-propyl alcohol, and the consumption of n-propyl alcohol is 3 times of two hydrated cobalt chloride quality;
(3) material obtaining in second step is carried out to azeotropic distillation, Heating temperature is 150 DEG C, and reflux ratio is that 8:1 carries out extraction liquid of top of the tower, until tower top temperature while reaching 97.2 DEG C, stops extraction, azeotropic distillation finishes, then unnecessary n-propyl alcohol is steamed to recovery, obtain solvation waterless cobaltous chloride;
(4) the solvation waterless cobaltous chloride obtaining in the 3rd step is put into tube furnace, in nitrogen atmosphere, 100 DEG C of heating 120min steam n-propyl alcohol, obtain waterless cobaltous chloride, the m=270.5g that weighs, and the purity of cobalt chloride is 99.5%.
Example three: (1) takes 500g cobalt chloride hexahydrate, puts into 120 DEG C of heating 120min of baking oven, obtains two hydrated cobalt chlorides;
(2) two hydrated cobalt chlorides that the first step obtained join in anhydrous isopropyl alcohol, stir fully, the water molecules in low hydrated cobalt chloride are cemented out with Virahol, and the consumption of Virahol is 4 times of two hydrated cobalt chloride quality;
(3) material obtaining in second step is carried out to azeotropic distillation, Heating temperature is 150 DEG C, and reflux ratio is that 6:1 carries out extraction liquid of top of the tower, until tower top temperature while reaching 82.4 DEG C, stops extraction, azeotropic distillation finishes, then unnecessary Virahol is steamed to recovery, obtain solvation waterless cobaltous chloride;
(4) the solvation waterless cobaltous chloride obtaining in the 3rd step is put into tube furnace, in nitrogen atmosphere, 100 DEG C of heating 120min steam Virahol, obtain waterless cobaltous chloride, the m=270.0g that weighs, and the purity of cobalt chloride is 99.6%.
Example four: (1) takes 500g cobalt chloride hexahydrate, puts into 120 DEG C of heating 120min of baking oven, obtains two hydrated cobalt chlorides;
(2) two hydrated cobalt chlorides that the first step obtained join in acetonitrile, stir fully, the water molecules in low hydrated cobalt chloride are cemented out with acetonitrile, and the consumption of acetonitrile is 5 times of two hydrated cobalt chloride quality;
(3) material obtaining in second step is carried out to azeotropic distillation, Heating temperature is 150 DEG C, and reflux ratio is that 5:1 carries out extraction liquid of top of the tower, until tower top temperature while reaching 76 DEG C, stops extraction, azeotropic distillation finishes, then unnecessary acetonitrile is steamed to recovery, obtain solvation waterless cobaltous chloride;
(4) the solvation waterless cobaltous chloride obtaining in the 3rd step is put into tube furnace, in nitrogen atmosphere, carry out 100 DEG C of heating 120min acetonitrile is steamed, obtain waterless cobaltous chloride, the m=271.1g that weighs, the purity of cobalt chloride is 99.4%.
Claims (9)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410294456.3A CN104129817B (en) | 2014-06-27 | 2014-06-27 | A kind of solvent displacement prepares the method for waterless cobaltous chloride |
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|---|---|---|---|
| CN201410294456.3A CN104129817B (en) | 2014-06-27 | 2014-06-27 | A kind of solvent displacement prepares the method for waterless cobaltous chloride |
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| Publication Number | Publication Date |
|---|---|
| CN104129817A true CN104129817A (en) | 2014-11-05 |
| CN104129817B CN104129817B (en) | 2016-04-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960678A (en) * | 2021-02-06 | 2021-06-15 | 昆明铂生金属材料加工有限公司 | Method for removing crystal water and purifying crude silver tetrafluoroborate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254942A (en) * | 2008-04-07 | 2008-09-03 | 昆明理工大学 | Preparation method of high-purity anhydrous indium trichloride |
-
2014
- 2014-06-27 CN CN201410294456.3A patent/CN104129817B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254942A (en) * | 2008-04-07 | 2008-09-03 | 昆明理工大学 | Preparation method of high-purity anhydrous indium trichloride |
Non-Patent Citations (1)
| Title |
|---|
| 李国顺等: "CoC12•6H2O的脱水步骤及有关的动力学", 《山西大学学报》, no. 3, 31 December 1987 (1987-12-31), pages 73 - 78 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960678A (en) * | 2021-02-06 | 2021-06-15 | 昆明铂生金属材料加工有限公司 | Method for removing crystal water and purifying crude silver tetrafluoroborate |
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|---|---|
| CN104129817B (en) | 2016-04-20 |
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Granted publication date: 20160420 Termination date: 20200627 |