CN103059057B - Silicon tetrafluoride, ethanol and magnesium prepare the method for tetraethyl silicate and magnesium fluoride - Google Patents
Silicon tetrafluoride, ethanol and magnesium prepare the method for tetraethyl silicate and magnesium fluoride Download PDFInfo
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- CN103059057B CN103059057B CN201210427565.9A CN201210427565A CN103059057B CN 103059057 B CN103059057 B CN 103059057B CN 201210427565 A CN201210427565 A CN 201210427565A CN 103059057 B CN103059057 B CN 103059057B
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Abstract
The present invention relates to chemical technology field, particularly a kind of method utilizing silicon tetrafluoride, ethanol and reactive magnesium to prepare tetraethyl silicate and magnesium fluoride, comprise following several step: ethanol and magnesium powder join in reactor by a.; B. the temperature of reaction system is increased to preset temperature reaction; C. after completion of the reaction, cooling, joins the ethanolic soln of the silicon tetrafluoride configured in reactor, until reaction system is in neutral; D. filter and solid-liquid is separated; E. solid ethanol steps d obtained carries out cleaning, drying obtains target product magnesium fluoride; F. filtrate steps d obtained carries out distillation removing ethanol, obtains high boiling tetraethyl silicate.The present invention is a kind of method that can utilize production of phosphate fertilizer by product silicon tetrafluoride efficiently.
Description
Technical field
The present invention relates to chemical technology field, particularly a kind of method utilizing silicon tetrafluoride gas, ethanol and magnesium powder to produce tetraethyl silicate and magnesium fluoride, especially to the method for fluorine, the comprehensive utilization of silicon resource high benefit in phosphatic fertilizer company by product.
Background technology
Tetraethyl silicate is colourless inflammable liquid, is a kind of silicoorganic compound, and tetraethoxy ratio is easier to polymerization, and what therefore market is sold is generally tetraethoxy and polymkeric substance thereof, usually according to SiO in product
2content, determine the different trades mark, specification has CP and AR two kinds.The ethyl polysilicate generated after hydrolysis is made up of the polymkeric substance of different polymerization degree, therefore its SiO
2content mean value represents, is followed successively by tetraethyl silicate-28, tetraethyl silicate-32, tetraethyl silicate-40, tetraethyl silicate-50 from low to high according to extent of polymerization.First two exists with linear structure, more stable, and tetraethyl silicate-50 is tridimensional network, less stable, generally need add stablizer during storage.Tetraethoxysilane is mainly used in high temperature resistant chemicals-resistant coating, and organic solvent precision casting binding agent, generates superfine silica powder after complete hydrolysis, for the manufacture of fluorescent material, also can be used as chemical reagent.
Magnesium fluoride is colourless crystallization or white powder.Lattice of rutile type, micro-have purple fluorescence, and atomic water-soluble (18 DEG C, 87 mg/L), are slightly soluble in diluted acid (particularly nitric acid).Magnesium fluoride is the meticulous derived product of one of fluorine chemical industry, also be a kind of important Inorganic Chemicals, can be used as the raw material producing special cermacis, glass, hot pressing crystal, as the fusing assistant of smelting magnesium and magnesium, as welding compound in welding, be coated with agent as pigment, also can be used for preparing the precise parts such as the fluorescent material in various eyeglass in opticinstrument and filter coating, negative ray screen.Along with the development of science and technology, day by day go deep in recent years to ultraviolet and infrared research, its application is more and more wider, and market will progressively increase the application demand of magnesium fluoride.
SiF
4it is the by product of phosphoric acid by wet process and production of phosphate fertilizer.At present, the SiF of China's phosphate fertilizer industry by-product
4all reclaim with the form of silicofluoric acid after absorbing with water, and to produce Sodium Silicofluoride byproduct, because manufacturer is numerous, supply exceed demand for product, Business Economic Benefit is low, part small business even abandons the recovery of silicofluoric acid, so not only causes valuable fluorine, the loss of silicon resource, simultaneously also havoc and contaminate environment.With regard to China's phosphate fertilizer industry to the traditional technology of the fluorine of by product, silicon resource comprehensive utilization and product specification, no matter adopt which kind of operational path, all there is added value of product low, range of product is few, the shortcoming of the low and environmental benefit difference of economic benefit.Phosphate fertilizer industry fails to accomplish that high benefit fully utilizes to traditional Application way of fluorine, silicon resource in by product.
Summary of the invention
The object of the invention is to overcome and existing irrational technological deficiency is utilized to silicon tetrafluoride, provide a kind of phosphatic fertilizer company by product silicon tetrafluoride that utilizes and react the tetraethyl silicate and magnesium fluoride of preparing high added value in ethanol with magnesium powder, and the waste of reluctant environmental pollution in process, can not be produced, a kind of method of production of phosphate fertilizer by product silicon tetrafluoride can be utilized efficiently.
Silicon tetrafluoride of the present invention reacts the method preparing tetraethyl silicate and magnesium fluoride in ethanol and comprises following several step with magnesium powder: ethanol and magnesium powder join in reactor by a.; B. the temperature of reaction system is increased to preset temperature reaction; C. after completion of the reaction, cooling, joins the ethanolic soln of the silicon tetrafluoride configured in reactor, until reaction system is in neutral; D. filter and solid-liquid is separated; E. solid ethanol steps d obtained carries out cleaning, drying obtains target product magnesium fluoride; F. filtrate steps d obtained carries out distillation removing ethanol, obtains high boiling tetraethyl silicate.
In step a, the granular size of magnesium powder is 5-270 order.
In step b, temperature of reaction is 20-80 DEG C, and the reaction times is 1-4 h.
In step c, the ethanolic soln mass percent of silicon tetrafluoride is 10%-30%, in and the time be 0.5-4 h.
In step f, distillation pressure is 0.1-1 bar, and temperature is 35-80 DEG C.
Principle of the present invention is described according to following equation and illustrates:
Novelty of the present invention is to adopt brand-new chemical principle, simple single stage method can be used prepare the product of two kinds of high added values---tetraethyl silicate and magnesium fluoride, operational path is novel, 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 remaining ethanol can recycle, and discharges, do not have environmental pollution without waste.
Economic worth of the present invention is to extend the industrial chain that phosphatic fertilizer company utilizes fluorine silicon resource, and single stage method obtains two kinds of high value-added products simultaneously, has accomplished to utilize the comprehensive high-efficiency of fluorine silicon resource.
The present invention, owing to being in water-less environment, can directly obtain the anhydrous magnesium fluoride being equivalent to the high-quality that dry process goes out.
New process of the present invention can adopt existing technology and realize through the unit equipment that large-scale industrial production is verified.
Embodiment
The method that silicon tetrafluoride of the present invention, ethanol and magnesium prepare tetraethyl silicate and magnesium fluoride is described in detail in following embodiment, but is not limited to embodiment.
Embodiment 1
The magnesium powder of 100 mL ethanol and 3.0 g, 38 microns of sizes is joined in reactor, after stirring 2 h at 78 DEG C, by massfraction be 22% silicon tetrafluoride ethanolic soln 29.6 g join in reactor, until reaction system is in neutral, after stir about 2 h, reaction system filtered, filter cake washing with alcohol again drying obtains magnesium fluoride, washings and filtrate remove the complete ethanol of unreacted under being incorporated in reduced pressure, obtain tetraethyl silicate.
Embodiment 2
The magnesium powder of 100 mL ethanol and 3.0 g, 38 microns of sizes is joined in reactor, after stirring 1.5 h at 78 DEG C, by massfraction be 22% silicon tetrafluoride ethanolic soln 29.6 g join in reactor, until reaction system is in neutral, after stir about 4 h, reaction system filtered, filter cake washing with alcohol again drying obtains magnesium fluoride, washings and filtrate remove the complete ethanol of unreacted under being incorporated in reduced pressure, obtain tetraethyl silicate.
Embodiment 3
The magnesium powder of 100 mL ethanol and 3.0 g, 5 microns of sizes is joined in reactor, after stirring 2 h at 40 DEG C, by massfraction be 10% silicon tetrafluoride ethanolic soln 65.1 g join in reactor, until reaction system is in neutral, after stir about 4 h, reaction system filtered, filter cake washing with alcohol again drying obtains magnesium fluoride, washings and filtrate remove the complete ethanol of unreacted under being incorporated in reduced pressure, obtain tetraethyl silicate.
Embodiment 4
The magnesium powder of 100 mL ethanol and 3.0 g, 5 microns of sizes is joined in reactor, after stirring 2 h at 50 DEG C, by massfraction be 15% silicon tetrafluoride ethanolic soln 43.4 g join in reactor, until reaction system is in neutral, after stir about 3 h, reaction system filtered, filter cake washing with alcohol again drying obtains magnesium fluoride, washings and filtrate remove the complete ethanol of unreacted under being incorporated in reduced pressure, obtain tetraethyl silicate.
Embodiment 5
The magnesium powder of 100 mL ethanol and 3.0 g, 18 microns of sizes is joined in reactor, after stirring 2 h at 65 DEG C, by massfraction be 15% silicon tetrafluoride ethanolic soln 43.4 g join in reactor, until reaction system is in neutral, after stir about 3 h, reaction system filtered, filter cake washing with alcohol again drying obtains magnesium fluoride, washings and filtrate remove the complete ethanol of unreacted under being incorporated in reduced pressure, obtain tetraethyl silicate.
Embodiment 6
The magnesium powder of 100 mL ethanol and 3.0 g, 75 microns of sizes is joined in reactor, after 78 DEG C of stirred at ambient temperature 4 h, by massfraction be 15% silicon tetrafluoride ethanolic soln 43.4 g join in reactor, until reaction system is in neutral, after stir about 3 h, reaction system filtered, filter cake washing with alcohol again drying obtains magnesium fluoride, washings and filtrate remove the complete ethanol of unreacted under being incorporated in reduced pressure, obtain tetraethyl silicate.
Embodiment 7
The magnesium powder of 100 mL ethanol and 3.0 g, 5 microns of sizes is joined in reactor, after stirring 2 h at 65 DEG C, be that silicon tetrafluoride ethanolic soln 32.5 g of 20 % joins in reactor by massfraction, until reaction system is in neutral, after stir about 3 h, reaction system filtered, filter cake washing with alcohol again drying obtains magnesium fluoride, washings and filtrate remove the complete ethanol of unreacted under being incorporated in reduced pressure, obtain tetraethyl silicate.
Embodiment 8
The magnesium powder of 100 mL ethanol and 3.0 g, 38 microns of sizes is joined in reactor, after stirring 4 h at 65 DEG C, be that silicon tetrafluoride ethanolic soln 21.7 g of 30 % joins in reactor by massfraction, until reaction system is in neutral, after stir about 3 h, reaction system filtered, filter cake washing with alcohol again drying obtains magnesium fluoride, washings and filtrate remove the complete ethanol of unreacted under being incorporated in condition of normal pressure, obtain tetraethyl silicate.
Claims (2)
1. silicon tetrafluoride, ethanol and magnesium prepare a method for tetraethyl silicate and magnesium fluoride, it is characterized in that, step is:
A. ethanol and magnesium powder are joined in reactor;
B. the temperature of reaction system is risen to predetermined temperature of reaction 20-80 DEG C, the reaction times is 1-4 h;
C. after completion of the reaction, cooling, by the silicon tetrafluoride configured---ethanolic soln joins in reactor, until reaction system is in neutral, the ethanolic soln mass percent of described silicon tetrafluoride is 10%-30%, in and the time be 0.5-4 h;
D. reaction product is carried out solid-liquid separation;
E. solid ethanol steps d obtained carries out cleaning, drying obtains target product magnesium fluoride;
F. filtrate steps d obtained carries out distillation removing ethanol, and obtain high boiling tetraethyl silicate, described distillation pressure is 0.1-1 bar, and temperature is 35-80 DEG C.
2. prepare the method for tetraethyl silicate and magnesium fluoride by a kind of silicon tetrafluoride according to claim 1, ethanol and magnesium, it is characterized in that, in step a, the granular size of magnesium powder is 5-270 order.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210427565.9A CN103059057B (en) | 2012-11-01 | 2012-11-01 | Silicon tetrafluoride, ethanol and magnesium prepare the method for tetraethyl silicate and magnesium fluoride |
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| CN201210427565.9A CN103059057B (en) | 2012-11-01 | 2012-11-01 | Silicon tetrafluoride, ethanol and magnesium prepare the method for tetraethyl silicate and magnesium fluoride |
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| CN103059057B true CN103059057B (en) | 2015-09-30 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB738703A (en) * | 1953-07-07 | 1955-10-19 | Kali Chemie Ag | Process for the production of esters or thioesters of inorganic acids |
| GB753709A (en) * | 1953-08-05 | 1956-07-25 | Kali Chemie Ag | Method of producing silicic acid esters |
| GB763250A (en) * | 1953-11-10 | 1956-12-12 | Pennsylvania Salt Mfg Co | Preparation of inorganic fluorine compounds |
| US2814635A (en) * | 1953-08-05 | 1957-11-26 | Kali Chemie Ag | Process of producing silicic 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 |
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2012
- 2012-11-01 CN CN201210427565.9A patent/CN103059057B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB738703A (en) * | 1953-07-07 | 1955-10-19 | Kali Chemie Ag | Process for the production of esters or thioesters of inorganic acids |
| GB753709A (en) * | 1953-08-05 | 1956-07-25 | Kali Chemie Ag | Method of producing silicic acid esters |
| US2814635A (en) * | 1953-08-05 | 1957-11-26 | Kali Chemie Ag | Process of producing silicic acid esters |
| GB763250A (en) * | 1953-11-10 | 1956-12-12 | Pennsylvania Salt Mfg Co | Preparation of inorganic fluorine compounds |
| 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》.2007,第14卷(第5期),第8-10、54页. * |
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