CN104445074A - Method for preparing anhydrous hydrogen fluoride and coproducing silicon tetrafluoride by treating diluted hydrofluosilicic acid through solvent extraction method - Google Patents
Method for preparing anhydrous hydrogen fluoride and coproducing silicon tetrafluoride by treating diluted hydrofluosilicic acid through solvent extraction method Download PDFInfo
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- CN104445074A CN104445074A CN201410756767.7A CN201410756767A CN104445074A CN 104445074 A CN104445074 A CN 104445074A CN 201410756767 A CN201410756767 A CN 201410756767A CN 104445074 A CN104445074 A CN 104445074A
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- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/193—Preparation from silicon tetrafluoride, fluosilicic acid or fluosilicates
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Abstract
The invention relates to the technical field of chemical industry, and particularly relates to a method for preparing anhydrous hydrogen fluoride and coproducing silicon tetrafluoride by treating diluted hydrofluosilicic acid through a solvent extraction method. The method comprises the following process steps: (a) adding a mixed organic solvent formed from tertiary amine and a non-polar organic solvent to a fluosilicic acid solution, layering a system after the fluosilicic acid is extracted through the organic solvent at certain temperature to obtain an organic phase and a water phase, and separating to remove the lower water phase so as to obtain the fluosilicic acid organic phase; (b) heating the fluosilicic acid organic phase, and removing residual moisture contained in the fluosilicic acid organic phase; and (c) heating the fluosilicic acid organic phase with the moisture removed to boiling temperature for thermal decomposition to obtain a mixed gas of the anhydrous hydrogen fluoride and the silicon tetrafluoride, and then recovering the fluosilicic acid organic phase for recycling. The method disclosed by the invention has the advantages of simple process flow and high operating flexibility, can realize the recycling of the organic solvent through a continuous method or a discontinuous method and is more suitable for industrialized production.
Description
Technical field
The present invention relates to the production method of chemical field, particularly a kind of method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process.
Background technology
Be no matter need hydrogen fluoride all in a large number in inorganic or organic industry, hydrogen fluoride is the unique raw material manufacturing element fluorine, separately can be used for producing aerosol, metal cleaner, plastics blowing agent, tensio-active agent and tetrafluoroethylene.Hydrogen fluoride Chang Zuowei is containing the raw material of fluorine catalyst, and hydrogen fluoride itself also has very strong catalytic activity, can make catalyzer in organic compound alkylation, isomerization or polyreaction; Hydrogen fluoride or nuclear industry manufacture the basic raw material of uranium hexafluoride, and high-purity or ultrapure hydrogen fluoride is own to be applied in optics, microelectronics industry and fine chemistry industry.Because the product of fluorochemicals and demand increase year by year, hydrofluoric demand also correspondingly increases year by year.
Current silicon tetrafluoride is mainly used in, in electronics and semicon industry, being mainly used in the etching reagent of silicon nitride, and P-type dopant, epitaxial deposition diffuse si source etc., also can be used for preparing electronic-grade silane or silicon.In addition, SiF
4also be widely used in and prepare solar cell, silicofluoric acid and aluminum fluoride etc.Along with the develop rapidly of world's electronic industry, the demand of market to silicon tetrafluoride increases gradually.
But be limited to the national strategy management and control of fluorite, the main raw material-fluorite supply of producing hydrogen fluoride and silicon tetrafluoride be becoming tight day, find new fluorine resource imperative.And at phosphoric acid by wet process and a large amount of fluorochemicals of phosphatic fertilizer company by-product, these fluorochemicalss mainly exist with the form of rare silicofluoric acid.If rare silicofluoric acid can obtain efficiency utilization, the deficiency of fluorite just can be made up.
At present, the Technology that the rare silicofluoric acid of phosphate fertilizer by-product utilizes has following four aspects:
(1) with the rare silicofluoric acid of phosphate fertilizer by-product, sodium salt for raw material direct production Sodium Silicofluoride, the subject matter that this route exists is that 1. Sodium Silicofluoride is due to the reason such as application market and price change, its product marketing and productivity effect big rise and fall, Sodium Silicofluoride value of the product is not high; 2. process 1 ton of Sodium Silicofluoride by by-product 12 tons of waste water, owing to containing sodium ion, phosphatic fertilizer company recycle is more difficult, and cost of water treatment is higher.
(2) aluminum fluoride is produced, by-product silica gel with the rare silicofluoric acid of phosphate fertilizer by-product for raw material and aluminium hydroxide react; The Sodium Silicofluoride of phosphate fertilizer by-product is that raw material and sodium carbonate react and produces Sodium Fluoride, by-product silica gel; Sodium Fluoride and aluminum fluoride synthetic cryolite.Mainly there is following problem in these routes: 1. the silicon of silicofluoric acid and Sodium Silicofluoride is converted into silica gel, in the silica gel of by-product Sodium Fluoride and aluminum fluoride content higher, be difficult to effective utilization; If process stored up by silica gel, very large pressure certainly will be caused to environment.Therefore, in these routes, silicon resource does not only obtain efficiency utilization, also becomes the bottleneck suppressing its development; 2. Sodium Fluoride, the aluminum fluoride solubleness in water is little, silicon-dioxide is insoluble, and three kinds of physical property of the Earth's materials are close, are difficult to find efficient manner to realize being separated of Sodium Fluoride and silicon-dioxide and aluminum fluoride and silicon-dioxide, the quality of Sodium Fluoride, aluminum fluoride and sodium aluminum fluoride can be had influence on.
(3) with the rare silicofluoric acid of phosphate fertilizer by-product, ammonia for raw material production Neutral ammonium fluoride and white carbon black, Neutral ammonium fluoride and sulfuric acid reaction generate hydrofluoric acid and ammonium sulfate.The subject matter that this route exists is: if the silicon 1. in silicofluoric acid is all converted into white carbon black, white carbon black inferior quality, affect its price and purposes; If silicon is partially converted into white carbon black, be partially converted into silica gel, there is the problem that silica gel utilizes; 2. ammonium sulfate utilizes difficulty, often produce 1 ton of hydrofluoric acid meeting by-product, 3.4 tons of ammonium sulfate, and ammonium sulfate market capacity is limited, if ammonium sulfate can not find effective utilization ways, can restrict the economy of this operational path.
(4) silicofluoric acid of phosphate fertilizer by-product and sulfuric acid reaction, produces hydrogen fluoride and silicon tetrafluoride, and silicon tetrafluoride use water absorbs and generates silicofluoric acid and silica gel, silicofluoric acid circulation and sulfuric acid reaction; Mainly there is following problem in this route: is finally converted into silica gel after the silicon cycling 1. in this route, the silicofluoric acid that silica gel is residual and hydrogen fluoride higher, it utilizes the development that govern this technique; 2. in the process of silicofluoric acid and sulfuric acid reaction, the fluorine atom of 1/3rd is converted into hydrofluoric acid, and the fluorine atom of 2/3rds gets back to silicofluoric acid again by two steps conversions, needs iterative cycles the fluorine in silicofluoric acid all could be changed into hydrofluoric acid.
Present method obtains anhydrous hydrogen fluoride and silicon tetrafluoride gas mixture by extraction, dehydration and thermolysis three easy steps.Gas mixture is by directly obtaining the anhydrous hydrogen fluoride of market demand after separation, silicon tetrafluoride gas can be used as the raw material of production HIGH-PURITY SILICON simultaneously.
Summary of the invention
The object of the invention is to overcome the existing defect utilizing phosphoric acid by wet process and phosphatic fertilizer company to utilize the rare silicofluoric acid technology of by-product, a kind of a kind of method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process of cost-effective, simple to operate, applicable suitability for industrialized production is provided.
A kind of method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process of the present invention, is characterized in that, the steps include:
A) in silicate fluoride solution, add the mixed organic solvents formed by tertiary amine and non-polar organic solvent, system layering after organic solvent extraction silicofluoric acid, obtains organic phase and aqueous phase at a certain temperature, is separated removing lower floor aqueous phase, obtains rare silicofluoric acid organic phase;
B) heat silicofluoric acid organic phase, remove moisture remaining in organic phase;
C) the silicofluoric acid organic phase removing moisture is heated to boiling temperature, carries out the mixed gas that thermolysis obtains anhydrous hydrogen fluoride and silicon tetrafluoride, regeneration is reclaimed organic phase and is returned recycle.
Tertiary amine described in step a comprises positive three heptyl amices, Trioctylamine, positive TNA trinonylamine or positive tridecylamine, and non-polar organic solvent comprises normal heptane, octane, n-nonane, n-decane, decane, n-undecane, n-dodecane, n-tridecane or n-tetradecane.
Tertiary amine used in step a and the volume ratio of non-polar solvent are 0.2:1-1.2:1, and the volume of mixed organic solvents and rare silicofluoric acid is in a ratio of 3:1-2:1, and the mass concentration of rare silicofluoric acid is 5%-18%.
Extraction temperature in step a is 40-90 DEG C.
The temperature removing residual water-content in step b is 110-130 DEG C, and system pressure is-0.02 ~-0.04MPa.
The temperature of organic phase thermolysis in step c is 170-220 DEG C, and the pressure of thermolysis system is-0.01 ~-0.03 MPa.
Prepared a method for anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process, it is characterized in that, the steps include:
1) organic solvent 1600 g of to be rare silicofluoric acid 1000 g of 6% and the volume ratio of decane and trioctylamine by massfraction be 0.2:1 at 60 DEG C with stir about 20 min, leave standstill 10 min phase-splittings again, separation obtains organic phase and aqueous phase, and in organic phase, the concentration of water is 6%.
2) by organic phase at 120 DEG C, underpressure distillation under-0.03 MPa, the moisture in removing organic phase, after dehydration, the concentration of organic phase water is 0.1%.
3) organic phase after dehydration is heated to 180 DEG C of boilings under-0.01 MPa, carries out thermolysis 6 hours, obtain the gas mixture of anhydrous hydrogen fluoride and silicon tetrafluoride.
The present invention and sulfuric acid process conventional are at present decomposed silicofluoric acid and are produced compared with hydrofluoric technique, compare tool and have the following advantages:
(1) after the silicofluoric acid in organic solvent extraction silicate fluoride solution, just lower layer of water can be removed mutually by simple filtration, aqueous phase can be cycled to used in the tail gas absorption of the techniques such as phosphoric acid by wet process, reaches recycling of water resources, reduces water resource waste;
(2) sulfuric acid process needs to process with a large amount of vitriol oils, moisture that silicofluoric acid is with and washing tail gas water, filter cake wash water enter in sulfuric acid in a large number, produce a large amount of dilute sulphuric acid, consider the utilization of dilute sulphuric acid, set up supporting Large-scale Fertilizer Plant, or dilute sulphuric acid is concentrated, but need a large amount of energy consumption, and this technique is owing to reusing organic solvent as extraction agent, raw material is only rare silicofluoric acid, thus without the need to process by product and waste produce;
(3), in this technique, because organic solvent is relatively more thorough, therefore not high to the concentration requirement of silicofluoric acid to the extraction of rare silicofluoric acid, thus the difficulty of silicofluoric acid preparation technology is reduced; This and sulfuric acid process require that in silicate fluoride solution, silicofluoric acid concentration is more high better different.
(4) after organic solvent extraction silicofluoric acid, because oil-aqueous phase separation is simple, thoroughly, the water remained in oil phase is little, and the gas mixture of the hydrogen fluoride that thermolysis obtains and silicon tetrafluoride just can obtain anhydrous hydrogen fluoride by simple separation.Therefore, this technique is a kind of economy, efficient, eco-friendly method silicofluoric acid being decomposed into anhydrous hydrogen fluoride and silicon tetrafluoride, and not only technical process is simple, turndown ratio is large, and agents useful for same can be recycled, realize by continuous processing or interrupter method, be relatively applicable to suitability for industrialized production.
Accompanying drawing explanation
The method utilizing organic bases process silicate fluoride solution to prepare hydrogen fluoride and white carbon black of the present invention, but be not limited to embodiment.
Fig. 1 is present invention process schema.
Embodiment
The method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process of the present invention, the steps include:
A) in silicate fluoride solution, add the mixed organic solvents formed by tertiary amine and non-polar organic solvent, system layering after organic solvent extraction silicofluoric acid, obtains organic phase and aqueous phase at a certain temperature, is separated removing lower floor aqueous phase, obtains silicofluoric acid organic phase;
B) heat silicofluoric acid organic phase, remove moisture remaining in organic phase;
C) the silicofluoric acid organic phase removing moisture is heated to boiling temperature, carries out the mixed gas that thermolysis obtains anhydrous hydrogen fluoride and silicon tetrafluoride, regeneration is reclaimed organic phase and is returned recycle.
Tertiary amine described in step a comprises positive three heptyl amices, Trioctylamine, positive TNA trinonylamine, positive tridecylamine, and non-polar organic solvent comprises normal heptane, octane, n-nonane, n-decane, decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane.
Tertiary amine used in step a and the volume ratio of non-polar solvent are 0.2:1-1.2:1, and the volume of mixed organic solvents and rare silicofluoric acid is in a ratio of 3:1-2:1, and the mass concentration of rare silicofluoric acid is 5%-18%.
Extraction temperature in step a is 40-90 DEG C.
The temperature removing residual water-content in step b is 110-130 DEG C, and system pressure is-0.02 ~-0.04MPa.
The temperature of organic phase thermolysis in step c is 170-220 DEG C, and the pressure of thermolysis system is-0.01 ~-0.03 MPa.The method preparing anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process of the present invention is described in detail in following embodiment, but is not limited to embodiment.
embodiment 1
Extraction process: by massfraction be 6% rare silicofluoric acid 1000 g and organic solvent (volume ratio of decane and trioctylamine is 0.2:1) 1600 g at 60 DEG C with stir about 20 min, leave standstill 10 min phase-splittings again, separation obtains organic phase and aqueous phase, percentage extraction is 99%, and in organic phase, the concentration of water is 6%.
Dewatering process: by organic phase at 120 DEG C, underpressure distillation under-0.03 MPa, the moisture in removing organic phase, after dehydration, the concentration of organic phase water is 0.1%.
Thermal decomposition process: the organic phase after dehydration is heated to 180 DEG C of boilings under-0.01 MPa, and carry out thermolysis, obtain the gas mixture of anhydrous hydrogen fluoride and silicon tetrafluoride, the rate of decomposition in 6 h is 94%.
embodiment 2
Extraction process: by massfraction be 12% rare silicofluoric acid 1000 g and organic solvent (volume ratio of n-undecane and trioctylamine is 1:1) 2000 g at 80 DEG C with stir about 20 min, leave standstill 10 min phase-splittings again, separation obtains organic phase and aqueous phase, percentage extraction is 99%, and in organic phase, the concentration of water is 4%.
Dewatering process: by organic phase at 130 DEG C, underpressure distillation under-0.02 MPa, the moisture in removing organic phase, after dehydration, the concentration of organic phase water is 0.1%.
Thermal decomposition process: the organic phase after dehydration is heated to 190 DEG C of boilings under-0.02 MPa, and carry out thermolysis, obtain the gas mixture of anhydrous hydrogen fluoride and silicon tetrafluoride, the rate of decomposition in 4 h is 96%.
embodiment 3
Extraction process: by massfraction be 18% rare silicofluoric acid 1000 g and organic solvent (volume ratio of n-dodecane and trioctylamine is 1.2:1) 2400 g at 90 DEG C with stir about 20 min, leave standstill 10 min phase-splittings again, separation obtains organic phase and aqueous phase, percentage extraction is 99%, and in organic phase, the concentration of water is 3%.
Dewatering process: by organic phase at 110 DEG C, underpressure distillation under-0.04 MPa, the moisture in removing organic phase, after dehydration, the concentration of organic phase water is 0.1%.
Thermal decomposition process: the organic phase after dehydration is heated to 204 DEG C of boilings under-0.02 MPa, and carry out thermolysis, obtain the gas mixture of anhydrous hydrogen fluoride and silicon tetrafluoride, the rate of decomposition in 3.5 h is 97%.
embodiment 4
Extraction process: by massfraction be rare silicofluoric acid 1000 g of 14 % and organic solvent (volume ratio of n-dodecane and tridecylamine is 1:1) 2000 g at 90 DEG C with stir about 20 min, leave standstill 10 min phase-splittings again, separation obtains organic phase and aqueous phase, percentage extraction is 99%, and in organic phase, the concentration of water is 3%.
Dewatering process: by organic phase at 120 DEG C, underpressure distillation under-0.03 MPa, the moisture in removing organic phase, after dehydration, the concentration of organic phase water is 0.1%.
Thermal decomposition process: the organic phase after dehydration is heated to 204 DEG C of boilings under-0.02 MPa, and carry out thermolysis, obtain the gas mixture of anhydrous hydrogen fluoride and silicon tetrafluoride, the rate of decomposition in 4 h is 94%.
Embodiment 5
Extraction process: by massfraction be rare silicofluoric acid 1000 g of 10 % and organic solvent (volume ratio of n-dodecane and trioctylamine is 1:1) 1800 g at 70 DEG C with stir about 20 min, leave standstill 10 min phase-splittings again, separation obtains organic phase and aqueous phase, percentage extraction is 99%, and in organic phase, the concentration of water is 3%.
Dewatering process: by organic phase at 120 DEG C, underpressure distillation under-0.03 MPa, the moisture in removing organic phase, after dehydration, the concentration of organic phase water is 0.1%.
Thermal decomposition process: the organic phase after dehydration is heated to 204 DEG C of boilings under-0.02 MPa, and carry out thermolysis, obtain the gas mixture of anhydrous hydrogen fluoride and silicon tetrafluoride, the rate of decomposition in 3 h is 97%.
Claims (7)
1. prepared a method for anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process, it is characterized in that, the steps include:
A) in silicate fluoride solution, add the mixed organic solvents formed by tertiary amine and non-polar organic solvent, system layering after organic solvent extraction silicofluoric acid, obtains organic phase and aqueous phase at a certain temperature, is separated removing lower floor aqueous phase, obtains rare silicofluoric acid organic phase;
B) heat silicofluoric acid organic phase, remove moisture remaining in organic phase;
C) the silicofluoric acid organic phase removing moisture is heated to boiling temperature, carries out the mixed gas that thermolysis obtains anhydrous hydrogen fluoride and silicon tetrafluoride, regeneration is reclaimed organic phase and is returned recycle.
2. the method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process according to claim 1, it is characterized in that, tertiary amine described in step a comprises positive three heptyl amices, Trioctylamine, positive TNA trinonylamine or positive tridecylamine, and non-polar organic solvent comprises normal heptane, octane, n-nonane, n-decane, decane, n-undecane, n-dodecane, n-tridecane or n-tetradecane.
3. the method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process according to claim 1, it is characterized in that, tertiary amine used in step a and the volume ratio of non-polar solvent are 0.2:1-1.2:1, the volume of mixed organic solvents and rare silicofluoric acid is in a ratio of 3:1-2:1, and the mass concentration of rare silicofluoric acid is 5%-18%.
4. the method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process according to claim 1, is characterized in that, the extraction temperature in step a is 40-90 DEG C.
5. the method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process according to claim 1, is characterized in that, the temperature removing residual water-content in step b is 110-130 DEG C, and system pressure is-0.02 ~-0.04MPa.
6. the method being prepared anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process according to claim 1, it is characterized in that, the temperature of organic phase thermolysis in step c is 170-220 DEG C, and the pressure of thermolysis system is-0.01 ~-0.03 MPa.
7. prepared a method for anhydrous hydrogen fluoride coproduction silicon tetrafluoride by the rare silicofluoric acid of solvent extration process, it is characterized in that, the steps include:
1) organic solvent 1600 g of to be rare silicofluoric acid 1000 g of 6% and the volume ratio of decane and trioctylamine by massfraction be 0.2:1 at 60 DEG C with stir about 20 min, leave standstill 10 min phase-splittings again, separation obtains organic phase and aqueous phase, and in organic phase, the concentration of water is 6%;
2) by organic phase at 120 DEG C, underpressure distillation under-0.03 MPa, the moisture in removing organic phase, after dehydration, the concentration of organic phase water is 0.1%;
3) organic phase after dehydration is heated to 180 DEG C of boilings under-0.01 MPa, carries out thermolysis 6 hours, obtain the gas mixture of anhydrous hydrogen fluoride and silicon tetrafluoride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366643A (en) * | 2015-12-18 | 2016-03-02 | 云南省化工研究院 | Method for preparing fluoride salt co-production white carbon black by extracting dilute luosilicic acid through solvent |
| CN105502435A (en) * | 2015-12-18 | 2016-04-20 | 云南天安化工有限公司 | Method for preparing ammonium fluoride from tertiary amine-fluosilicate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003183871A (en) * | 2001-12-14 | 2003-07-03 | Mitsubishi Materials Corp | Electrolytic refining method for producing high-purity tin, and apparatus therefor |
| CN102951611A (en) * | 2012-12-24 | 2013-03-06 | 贵州省化工研究院 | Method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises |
| CN103466642A (en) * | 2013-09-17 | 2013-12-25 | 云天化集团有限责任公司 | Method for preparing hydrogen fluoride (HF) and white carbon black by treating fluosilicic acid (H2SiF6) via organic alkali |
| US20140341795A1 (en) * | 2010-10-02 | 2014-11-20 | Silichem Llc | Fluorspar/Iodide Process for Reduction, Purification, and Crystallization of Silicon |
-
2014
- 2014-12-11 CN CN201410756767.7A patent/CN104445074B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003183871A (en) * | 2001-12-14 | 2003-07-03 | Mitsubishi Materials Corp | Electrolytic refining method for producing high-purity tin, and apparatus therefor |
| US20140341795A1 (en) * | 2010-10-02 | 2014-11-20 | Silichem Llc | Fluorspar/Iodide Process for Reduction, Purification, and Crystallization of Silicon |
| CN102951611A (en) * | 2012-12-24 | 2013-03-06 | 贵州省化工研究院 | Method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises |
| CN103466642A (en) * | 2013-09-17 | 2013-12-25 | 云天化集团有限责任公司 | Method for preparing hydrogen fluoride (HF) and white carbon black by treating fluosilicic acid (H2SiF6) via organic alkali |
Non-Patent Citations (1)
| Title |
|---|
| 汞长生等: "《现代化学工业》", 30 June 2008, 华中科技大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366643A (en) * | 2015-12-18 | 2016-03-02 | 云南省化工研究院 | Method for preparing fluoride salt co-production white carbon black by extracting dilute luosilicic acid through solvent |
| CN105502435A (en) * | 2015-12-18 | 2016-04-20 | 云南天安化工有限公司 | Method for preparing ammonium fluoride from tertiary amine-fluosilicate |
| CN105502435B (en) * | 2015-12-18 | 2017-09-22 | 云南天安化工有限公司 | A kind of method that ammonium fluoride is prepared by tertiary amine fluosilicic acid |
| CN105366643B (en) * | 2015-12-18 | 2018-04-10 | 云南省化工研究院 | A kind of method that dilute fluosilicic acid of solvent extraction prepares fluoride salt co-producing white carbon black |
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