CN103059058A - Method for preparing ethyl silicate and calcium fluoride from silicon tetrafluoride, ethanol and calcium chloride - Google Patents
Method for preparing ethyl silicate and calcium fluoride from silicon tetrafluoride, ethanol and calcium chloride Download PDFInfo
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- CN103059058A CN103059058A CN2012104275964A CN201210427596A CN103059058A CN 103059058 A CN103059058 A CN 103059058A CN 2012104275964 A CN2012104275964 A CN 2012104275964A CN 201210427596 A CN201210427596 A CN 201210427596A CN 103059058 A CN103059058 A CN 103059058A
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Abstract
The invention relates to the technical field of chemical industry and in particular relates to a method for preparing ethyl silicate and calcium fluoride by utilizing reactions of silicon tetrafluoride, calcium chloride and ethanol. The method comprises the following steps of: a. adding prepared ethanol solution of silicon tetrafluoride to ethanol solution of calcium chloride prepared in advance; b. stirring the solution at room temperature to fully complex silicon tetrafluoride, calcium chloride and ethanol; c. beginning heating to enable the reaction temperature to reach the preset temperature; d. after reaction is completed, cooling the solution, adding ammonia to neutralize the solution and separating solid from liquid through filtration; e. washing the solid obtained before neutralization in step d with ethanol and water and drying the washed solid to obtain the target product calcium fluoride; and f. distilling the filtrate obtained in step d to remove ethanol, thus obtaining ethyl silicate with high boiling point. The method can be used for producing by-product silicon tetrafluoride by efficiently utilizing phosphate fertilizers.
Description
Technical field
The present invention relates to chemical technology field, particularly a kind of is the method for raw material production tetraethyl silicate and Calcium Fluoride (Fluorspan) by silicon tetrafluoride and calcium chloride, ethanol.
Background technology
Tetraethyl silicate is the important intermediate in the organosilicon industry, is mainly used in the insulating material of electronic industry, heat-resistant paint, the coating of chemically-resistant effect, opticglass treatment agent, condensing agent, tackiness agent etc.At present, up to the present the preparation method of positive silicon ester is mainly the silicon tetrachloride alcoholysis method.It is raw material that this method adopts silicon tetrachloride and alcohols, and its technique can be divided into intermittence, semicontinuous, continuous.Because this method can produce the hydrogen chloride gas of contaminate environment from silicon and chlorine.
Calcium Fluoride (Fluorspan) is the main component of fluorite mineral, is the main source of fluorine element, can be used for producing the important chemical reagent such as hydrogen fluoride, fluorine gas, fluorochemical, and annual production reaches 500,000 tons.In industrial and laboratory, all take Calcium Fluoride (Fluorspan) as waste hydrogen fluoride, be used as dehydration or dehydrogenation catalyst in the organic chemical reactions.In Iron And Steel Industry, make fusing assistant, can reduce fusing point, increase the flowability of slag.Can be used for making pottery in the ceramic industry, be used as the component of vitreous enamel etc.Also can be used for electronics, instrument, opticinstrument manufacturing.In addition, also be used for the manufacturing of welding electrode welding component and glass, glass fibre.The Calcium Fluoride (Fluorspan) sterling can be done to dewater, the catalyzer of dehydrogenation reaction.Synthetic pure calcium fluoride mono crystal can be used as the infrared light material.
At present, the method for synthetic Calcium Fluoride (Fluorspan) is with calcium carbonate or calcium hydroxide hydrofluoric acid dissolution, and gained solution is concentrated, or adds fluorion in calcium saline solution, obtains the gelatinous precipitate of Calcium Fluoride (Fluorspan), can get through refining.Patent CN101891231A has announced a kind of preparation method of Calcium Fluoride (Fluorspan), and it is raw material that the method adopts nitrocalcite and Neutral ammonium fluoride, and the Calcium Fluoride (Fluorspan) purity that obtains is very high.
But the fluorite reserve-production ratio of present main fluorine source descends, and main fluorite consumer nation and regional fluorite resource are increasingly exhausted, China's upstream fluorite resource also begin anxiety, China to fluorite outlet strengthen control, the fluorite price is progressively soaring.Therefore extremely be necessary to look for new approach, keep away the fluorite method and with other resources production anhydrous hydrogen fluorides.One of approach is the by product SiF that strengthens phosphoric acid by wet process and production of phosphate fertilizer
4Effective utilization, production high added value silicon ester and fluorochemical, thus make fluorine, the silicon resource of phosphate fertilizer industry obtain utilizing fully efficiently.
Summary of the invention
The object of the invention is to be phosphate fertilizer by-product SiF
4A kind of novel process that traditional water absorbs the production silicofluoric acid that is different from is provided, has namely passed through SiF
4The reaction of gas, calcium chloride and ethanol, preparation tetraethyl silicate and Calcium Fluoride (Fluorspan), wherein the Calcium Fluoride (Fluorspan) substitute that can be used as fluorite is used for producing anhydrous hydrogen fluoride.
Of the present invention take silicon tetrafluoride, calcium chloride and ethanol as the raw material production tetraethyl silicate and the method for coproduction Calcium Fluoride (Fluorspan) comprise that following several step: a. joins the silicon tetrafluoride ethanolic soln that configures in the prewired calcium chloride ethanolic soln that makes; B. at room temperature stir, make silicon tetrafluoride and calcium chloride, the abundant complexing of ethanol; C. begin to heat up and make reaction reach preset temperature; D. react complete after, add the ammonia neutralization after the cooling, filter solid-liquid separated; E. the solid that steps d is obtained with the second alcohol and water clean, drying obtains target product Calcium Fluoride (Fluorspan); F. the filtrate distillation that steps d is obtained is removed ethanol, obtains high boiling tetraethyl silicate.
Among the step a, the ethanolic soln concentration of silicon tetrafluoride is 10%-30%.
Among the step b, churning time is 0.5-3 h.
Among the step c, preset temperature is 50-80 ℃, and the reaction times is 0.5-5 h.
Principle of the present invention is described and illustrates according to following equation:
Novelty of the present invention is to adopt simple single stage method efficiently the fluorine in the silicon tetrafluoride, silicon to be separated, and obtain two kinds of reaction product---tetraethyl silicate and Calcium Fluoride (Fluorspan), the ammonium chloride of by-product can be made fertilizer, step is simple, economical rationality has high environmental value and economic worth.
Environmental value of the present invention is that silicon tetrafluoride can react completely, and ethanol can recycle, and environment is not polluted.
Economic worth of the present invention has been to extend the industrial chain that phosphatic fertilizer company utilizes the fluorine silicon resource, and single stage method has been accomplished the comprehensive high-efficiency utilization to the fluorine silicon resource, has found simultaneously the substitute of fluorite ore.
New process of the present invention can adopt existing technology and realize through the unit equipment of large-scale industrial production checking.
Embodiment
Of the present invention take silicon tetrafluoride, calcium chloride and ethanol as the raw material production tetraethyl silicate and the method for coproduction Calcium Fluoride (Fluorspan) will in following embodiment, be described in detail, but be not limited to embodiment.
Embodiment 1
It is in 13.3% the silicon tetrafluoride ethanolic soln that 141 g Calcium Chloride Powder Anhydrouss are joined 546 g massfractions, after being stirred to the calcium chloride solid under the room temperature and dissolving fully, stirs 0.5 h.1.5 h are reacted in intensification under reflux state.React complete after, stopped heating after reaction flask is cooled to room temperature, adds ammonia and is neutralized to neutrality, vacuum filtration obtains solid and filtrate.With solid with absolute ethanol washing after washings and filtrate merge, then underpressure distillation obtains high boiling tetraethyl silicate.Solid continues to wash with water post-drying, obtains target product Calcium Fluoride (Fluorspan).
Embodiment 2
It is in 10% the silicon tetrafluoride ethanolic soln that 141 g Calcium Chloride Powder Anhydrouss are joined 726 g massfractions, after being stirred to the calcium chloride solid under the room temperature and dissolving fully, stirs 1.5 h.Be warming up to 60 ℃ of lower reaction 1 h.React complete after, stopped heating after reaction flask is cooled to room temperature, adds ammonia and is neutralized to neutrality, vacuum filtration obtains solid and filtrate.With solid with absolute ethanol washing after washings and filtrate merge, then underpressure distillation obtains high boiling tetraethyl silicate.Solid continues to wash with water post-drying, obtains target product Calcium Fluoride (Fluorspan).
Embodiment 3
It is in 24% the silicon tetrafluoride ethanolic soln that 141 g Calcium Chloride Powder Anhydrouss are joined 303 g massfractions, after being stirred to the calcium chloride solid under the room temperature and dissolving fully, stirs 1.5 h.1 h is reacted in intensification under reflux state.React complete after, stopped heating after reaction flask is cooled to room temperature, adds ammonia and is neutralized to neutrality, vacuum filtration obtains solid and filtrate.With solid with absolute ethanol washing after washings and filtrate merge, then underpressure distillation obtains high boiling tetraethyl silicate.Solid continues to wash with water post-drying, obtains target product Calcium Fluoride (Fluorspan).
Embodiment 4
It is in 24% the silicon tetrafluoride ethanolic soln that 141 g Calcium Chloride Powder Anhydrouss are joined 303 g massfractions, after being stirred to the calcium chloride solid under the room temperature and dissolving fully, stirs 3 h.Be warming up to 70 ℃ of lower reaction 0.5 h.React complete after, stopped heating after reaction flask is cooled to room temperature, adds ammonia and is neutralized to neutrality, vacuum filtration obtains solid and filtrate.With solid with absolute ethanol washing after washings and filtrate merge, then underpressure distillation obtains high boiling tetraethyl silicate.Solid continues to wash with water post-drying, obtains target product Calcium Fluoride (Fluorspan).
Embodiment 5
It is in 24% the silicon tetrafluoride ethanolic soln that 141 g Calcium Chloride Powder Anhydrouss are joined 303 g massfractions, after being stirred to the calcium chloride solid under the room temperature and dissolving fully, stirs 1.5 h.1 h is reacted in intensification under reflux state.React complete after, stopped heating after reaction flask is cooled to room temperature, adds ammonia and is neutralized to neutrality, pressure filtration obtains solid and filtrate.With solid with absolute ethanol washing after washings and filtrate merge, then air distillation obtains high boiling tetraethyl silicate.Solid continues to wash with water post-drying, obtains target product Calcium Fluoride (Fluorspan).
Embodiment 6
It is in 30% the silicon tetrafluoride ethanolic soln that 141 g Calcium Chloride Powder Anhydrouss are joined 242 g massfractions, after being stirred to the calcium chloride solid under the room temperature and dissolving fully, stirs 1 h.Be warming up to 50 ℃ of lower reaction 5 h.React complete after, stopped heating after reaction flask is cooled to room temperature, adds ammonia and is neutralized to neutrality, pressure filtration obtains solid and filtrate.With solid with absolute ethanol washing after washings and filtrate merge, then air distillation obtains high boiling tetraethyl silicate.Solid continues to wash with water post-drying, obtains target product Calcium Fluoride (Fluorspan).
Claims (4)
1. a silicon tetrafluoride, ethanol and calcium chloride prepare the method for tetraethyl silicate and Calcium Fluoride (Fluorspan), and step is:
A. the silicon tetrafluoride ethanolic soln that configures is joined in the prewired calcium chloride ethanolic soln that makes;
B. under agitation make silicon tetrafluoride and calcium chloride, the abundant complexing of ethanol;
C. the b complex system is warming up to predetermined temperature of reaction;
D. react complete after, add the ammonia neutralization after the cooling, carry out again solid-liquid separation;
E. with the solid that obtains in the steps d with the second alcohol and water wash, drying obtains target product Calcium Fluoride (Fluorspan);
F. the filtrate distillation that steps d is obtained is removed ethanol, obtains high boiling tetraethyl silicate.
2. by method claimed in claim 1, step a silicon tetrafluoride---ethanolic soln concentration is 10%-30%.
3. by method claimed in claim 1, among the step b, churning time is 0.5-3 h.
4. by method claimed in claim 1, among the step c, predetermined temperature of reaction is 50-80 ℃, and the reaction times is 0.5-5 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012104275964A CN103059058A (en) | 2012-11-01 | 2012-11-01 | Method for preparing ethyl silicate and calcium fluoride from silicon tetrafluoride, ethanol and calcium chloride |
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| CN2012104275964A CN103059058A (en) | 2012-11-01 | 2012-11-01 | Method for preparing ethyl silicate and calcium fluoride from silicon tetrafluoride, ethanol and calcium chloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588209A (en) * | 2013-11-01 | 2014-02-19 | 青岛星火化工技术有限公司 | Method for recovery and comprehensive utilization of SiF4 gas |
| CN105198915A (en) * | 2015-09-21 | 2015-12-30 | 太仓市金锚新材料科技有限公司 | Esterification preparing method for ethyl silicate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2814635A (en) * | 1953-08-05 | 1957-11-26 | Kali Chemie Ag | Process of producing silicic acid esters |
| US3055926A (en) * | 1959-03-11 | 1962-09-25 | Ici Ltd | Manufacture of organic orthosilicates |
| DE2609767B1 (en) * | 1976-03-09 | 1977-04-07 | Swarovski & Co | Process for the production of orthosilicic acid esters |
| CN102516280A (en) * | 2011-12-08 | 2012-06-27 | 云南省化工研究院 | Method for preparing orthosilicic acid ester and fluoride through silicon tetrafluoride alcoholysis |
-
2012
- 2012-11-01 CN CN2012104275964A patent/CN103059058A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2814635A (en) * | 1953-08-05 | 1957-11-26 | Kali Chemie Ag | Process of producing silicic acid esters |
| US3055926A (en) * | 1959-03-11 | 1962-09-25 | Ici Ltd | Manufacture of organic orthosilicates |
| DE2609767B1 (en) * | 1976-03-09 | 1977-04-07 | Swarovski & Co | Process for the production of orthosilicic acid esters |
| CN102516280A (en) * | 2011-12-08 | 2012-06-27 | 云南省化工研究院 | Method for preparing orthosilicic acid ester and fluoride through silicon tetrafluoride alcoholysis |
Non-Patent Citations (1)
| Title |
|---|
| 薛河南，等: "我国磷肥副产氟硅酸的综合利用", 《氟化工》, vol. 14, no. 5, 31 October 2007 (2007-10-31) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588209A (en) * | 2013-11-01 | 2014-02-19 | 青岛星火化工技术有限公司 | Method for recovery and comprehensive utilization of SiF4 gas |
| CN103588209B (en) * | 2013-11-01 | 2015-06-24 | 青岛星火化工技术有限公司 | Method for recovery and comprehensive utilization of SiF4 gas |
| CN105198915A (en) * | 2015-09-21 | 2015-12-30 | 太仓市金锚新材料科技有限公司 | Esterification preparing method for ethyl silicate |
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Application publication date: 20130424 |