CN100478273C - Technique for preparing waterless hydrogen fluoride on high purity - Google Patents
Technique for preparing waterless hydrogen fluoride on high purity Download PDFInfo
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- CN100478273C CN100478273C CNB2004100224812A CN200410022481A CN100478273C CN 100478273 C CN100478273 C CN 100478273C CN B2004100224812 A CNB2004100224812 A CN B2004100224812A CN 200410022481 A CN200410022481 A CN 200410022481A CN 100478273 C CN100478273 C CN 100478273C
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Abstract
A process for preparing high-purity anhydrous hydrogen fluoride from the fluorosilicic acid as industrial by-product and concentrated sulfuric acid features that the fluorosilicid acid is deposited out in salt mode and the traditional fluorespar approach is then used. The generated sulfate as by-product can be used as precipitant of fluorosilicic acid system.
Description
One, technical field
The technical field that the present invention uses is inorganic chemicals industry and chemical fertilizer industry.
Two, background technology
Anhydrous hydrogen fluoride (AHF) is a kind of colourless fuming liquid being lower than under 20 ℃, polymerization easily.Can corrode silicon-containing material, skin is had extremely strong burn power, heat release generates hydrofluoric acid when water-soluble.It is a kind of organic raw material fluorizating agent, is used for producing refrigerant " fluorine Lyons ", fluorine resin, organic fluoride and element fluorine.In petrochemical complex, be used as the liquid catalyst of aromatic hydrocarbons, fatty compounds alkylation to prepare stop bracket gasoline.When exploiting some mineral deposit, the raw material of the uranium hexafluoride that needs in extraction, nuclear industry and the Nuclear weapons production of corrosion stratum, rare elements and radioactive element etc.Aspect electrical isolation, be the basic raw material of producing sulfur hexafluoride.
At occurring in nature, fluorine mainly contains two kinds and has form: a kind of being present in the fluorite (Calcium Fluoride (Fluorspan)), what China's fluorite reserves had been verified has 1.3 hundred million tons, accounts for 60% of world saving, and reserves rank first in the world.But CaF
2Grade is greater than 65% rich ore, can be directly has only more than 3,000 ten thousand t as the reserves of metallurgical grade lump ore.Only account for more than 20 percent of single fluorite deposit total reserves, and in these class rich ore reserves CaF
2Grade but less than 1,000 ten thousand t, accounts for total reserves less than 10% greater than 80% higher-grade rich ore, and acid system with the ore deposit still less.At present, AHF production technique in the world mainly is raw material with the fluorite.Another and Rock Phosphate (72Min BPL) association.With the operational path of Wet-process Phosphoric Acid Production phosphate product, all there is the recovery problem of fluorine.The main industries that DAP or traditional MAP industry are the by-product fluorochemicals.The content of fluorine in phosphorus ore is generally～and 3.0%, in the production process of DAP, the amount that fluorine is generally overflowed from the phosphoric acid by wet process extraction accounts for 2～5% of total amount, and the fluorine that enters in the dihydrate gypsum accounts for 25～30%, and the fluorine that enters in the phosphoric acid accounts for 65～70%.The fluorine that enters in the Phosphoric Acid Concentration process in the gas phase accounts for 38～45% of total fluorine.We can calculate in the phosphorus ore per ton recuperable simple substance fluoride amount about 10.8kg, if the phosphoric acid plant ability is 300kt/a P thus
2O
5, then recuperable simple substance fluoride is 11kt/a.At present, the villiaumite that domestic Wet-process Phosphoric Acid Production producer reclaims is mainly Sodium Silicofluoride, aluminum fluoride and sodium aluminum fluoride etc., because these villiaumite market demands are little, does not have market outlook, and excessive inventory, causes unnecessary waste.If these fluorine are produced the wide anhydrous hydrogen fluoride of market purposes (AHF), then enrich and do not have the fluorite area to produce very high economic benefit at phosphorus ore.This technology does not also realize suitability for industrialized production at present.
The technological line of being produced AHF by silicofluoric acid may be summarized to be two kinds of methods: direct method and indirect method.Direct method was meant by silicofluoric acid one step produces silicon tetrafluoride and hydrogen fluoride, obtains AHF after the purification separation; Indirect method is meant silicofluoric acid is converted into the method that AHF is produced in regeneration behind other fluorochemical.
Direct method is produced AHF technology and is comprised: U.S.Pat.No.3,969,485 (patented July 13,1976), in silicate fluoride solution, add sulfuric acid, make silicofluoric acid resolve into silicon tetrafluoride and hydrogen fluoride, the gas (comprising a large amount of water vapors) that adopts sulfuric acid absorption to produce, the sulfuric acid that absorbs hydrogen fluoride and water obtains AHF through distillation and with behind the vitriol oil absorption water; Silicon tetrafluoride behind the purifying at high temperature generates ultra-fine white carbon black and AHF with steam reaction.The shortcoming of this technology is before adding sulfuric acid, and the concentration of silicate fluoride solution need be controlled at more than 40%, like this, in concentrated silicofluoric acid process, have a large amount of silicofluoric acid to be decomposed to form silicon tetrafluoride and hydrogen fluoride, the two and water vapor enter gas phase together, cause damage; Add sulfuric acid in silicofluoric acid, silicofluoric acid decomposes not exclusively; Need a large amount of vitriol oils to handle silicate fluoride solution in addition, absorb silicon tetrafluoride, hydrogen fluoride and the water vapor that distills out for the first time, the dry hydrogen fluoride that distills out for the second time etc.
U.S.Pat.No.4,008,130 (patented February 15,1977) adopts the distillatory method to produce AHF, but its precondition is will form needs distillatory system to control to 36%H
2SiF
6, about 10% HF and 54%H
2O, this system is the three-phase azeotropic mixture; This mixture decomposes generation white carbon black of gas phase and hydrogen fluoride under high temperature (1000～1600 ℃) flame.The shortcoming of this technology is that the aqueous hydrogen fluoride corrodibility that at high temperature generates is serious, and the superfine white carbon black of Sheng Chenging is difficult to collect simultaneously.
U.S.Pat.No.4,114,158 (patented March 13,1979), at high temperature the pyrolysis silicofluoric acid makes it generate white carbon black and hydrogen fluoride, and behind the collection white carbon black, solution is rare hydrofluoric acid and silicate fluoride solution.Equally, U.S.Pat.No.4,389,293 (patented June 21,1983), also adopt electroosmose process that this solution is handled, make HF wherein enter the hydrofluoric acid chamber rare hydrofluoric acid and silicate fluoride solution, the concentration of hydrofluoric acid solution reaches more than 46%, distills then, handles and obtain AHF.The shortcoming of this technology is that aqueous hydrogen fluoride solution corrodibility is serious under the high temperature, and material is difficult to choose, and energy consumption is higher, and the aqueous hydrogen fluoride that distillation forms needs a large amount of vitriol oils to carry out drying.
U.S.Pat.No.3,218,124 (patented Nov.16,1965) and U.S.Pat.No.3,257,167, (patented June 21,1966) decomposes silicate fluoride solution with sulfuric acid, make it generate hydrogen fluoride and silicon tetrafluoride, after the separation, generate anhydrous hydrogen fluoride, the silicon tetrafluoride circulation generates silicofluoric acid.The shortcoming of this technology is the filtered through silica gel difficulty that the silicon tetrafluoride hydrolysis generates, industrial can't the realization.
U.S.Pat.No.4,036,938, the pyrolysis silicate fluoride solution makes it form silicon-dioxide and rare hydrofluoric acid solution, and this solution can obtain AHF through vitriolization.The shortcoming of this patent is that a certain amount of silicofluoric acid is arranged in the solution, and the AHF purity of generation is limited, simultaneously, needs a large amount of vitriol oils.
Russ P USSR No.174,610 adopt electroosmose process to carry dense silicate fluoride solution, add the vitriol oil then and make silicofluoric acid wherein resolve into silicon tetrafluoride and hydrogen fluoride.
Indirect method is produced AHF technology and is comprised: U.S.Pat.No.3, a kind of technology has been introduced in 087,787 (patented Apr.30,1963), the heating Sodium Silicofluoride decomposes it and generates Sodium Fluoride and silicon tetrafluoride, and silicon tetrafluoride adopts the method for high temperature pyrolysis to produce white carbon black and aqueous hydrogen fluoride.The shortcoming of this technology is that the Sodium Silicofluoride thermal degradation is not easy control, and purity is not high owing to the incomplete decomposing of Sodium Silicofluoride for the Sodium Fluoride of generation, and the high temperature pyrolysis of same silicon tetrafluoride also exists corrosion and recovery problem.
Israel's patent 891276 has been introduced a kind of method, generates Potassium monofluoride and ammonium fluoride by precipitation silicofluoride and ammoniacal liquor reaction, and reaction formula is as follows:
K
2SiF
6+4NH
3+2H
2O＝＝2KF+4NH
4F+SiO
2…………(1)
4KF+4NH
4F＝＝4KHF
2+3NH
3↑………………………(2)
4KHF
2＝＝4KF+4HF↑……………………………………(3)
The disadvantage of this technology is that the precipitation silicofluoride transforms in ammoniacal liquor not exclusively, and the Potassium monofluoride of generation and Neutral ammonium fluoride concentration are very rare, need the big water gaging of evaporation, and in addition, the pyrolysis of potassium hydrogen fluoride is incomplete.
U.S.Pat.No.3,787,304 adopt alkaline solution to handle silicate fluoride solution, make it generate fluoride salt and silicon-dioxide, and after the filtration, fluoride salt solution carries out electrodialysis, regenerates alkaline solution and hydrofluoric acid solution, and hydrofluoric acid is handled through distillation and is obtained AHF.The shortcoming of this technology is that power consumption is bigger, and industrialization is uneconomical.
Germany Hanover technology is to utilize ammoniacal liquor to decompose silicofluoric acid to make it generate Neutral ammonium fluoride and silicon-dioxide, and after the filtration, solution adds equimolar Potassium monofluoride and generates potassium hydrogen fluoride; Potassium hydrogen fluoride and Sodium Fluoride reaction generate sodium bifluoride and Potassium monofluoride, and the pyrolysis sodium bifluoride generates Sodium Fluoride and AHF, and the reaction equation of this technology is as follows:
H
2SiF
6+6NH
3+2H
2O＝＝6NH
4F+SiO
2…………(1)
6NH
4F+6KF＝＝6KHF
2+6NH
3↑…………………(2)
6KHF
2+6NaF＝＝6NaHF
2+6KF……………………(3)
The shortcoming of this technology is: a large amount of ammoniacal liquor is arranged in first reaction soln, and filtration difficulty needs a large amount of wash water washing leaching cakes simultaneously; Second step, equimolar proportioning was difficult to control, after reaction is finished, had a large amount of ammoniacal liquor to exist in the solution, and it is abominable to filter environment, needs a large amount of wash water washing leaching cakes; Be entrained with a large amount of Potassium monofluorides behind the three-step reaction in the filter cake, need wash, simultaneously filtration difficulty.
Also the handlebar silicofluoric acid is converted into Calcium Fluoride (Fluorspan), produces the operational path of AHF according to traditional method Calcium Fluoride (Fluorspan) and sulfuric acid reaction.Its reaction formula is as follows:
H
2SiF
6+3Ca(OH)
2＝＝3CaF
2+SiO
2+4H
2O………(1)
CaF
2+H
2SO
4＝＝CaSO
4+HF↑……………………(2)
The shortcoming of this technology is that being separated on the engineering of the first step reaction had any problem; In addition, the calcium sulfate industrial value of generation is very low.
Basic raw material of the present invention be the chemical industry by-product silicofluoric acid and with its can sedimentary salt, as soluble salts such as sodium, potassium, calcium.Precipitation silicofluoride and sulfuric acid (or corresponding hydrosulfate) reaction directly generates highly purified vitriol, and vitriol can be used as byproduct and sells, and also can return the silicofluoric acid system and generate precipitation silicofluoride and sulfuric acid, and sulfuric acid is recycled to the phosphoric acid extraction system.
Three, summary of the invention
The objective of the invention is provides a kind of high-purity anhydrous hydrogen fluoride preparation method at the deficiencies in the prior art.Be characterized in utilizing the silicofluoric acid of chemical industry by-product as raw material, with reacting by metallic cation sedimentary with it, generate highly purified precipitation silicofluoride, the precipitation silicofluoride and the vitriol oil at high temperature react, can very high vitriol, silicon tetrafluoride and the hydrogen fluoride of direct production purity.Vitriol can be used as byproduct and sells, and also can be recycled to the silicofluoric acid system and continue to generate precipitation silicofluoride and dilute sulphuric acid, and dilute sulphuric acid enters phosphoric acid extraction system decomposition phosphorus ore; Silicon tetrafluoride in the gas phase and hydrogen fluoride obtain anhydrous hydrogen fluoride through condensation separation, and silicon tetrafluoride is recycled to the silicofluoric acid absorption system or directly makes white carbon black of gas phase and anhydrous hydrogen fluoride.
Purpose of the present invention by following technical measures realize, wherein said raw material umber except that specified otherwise, be parts by weight.
With the silicofluoric acid and the vitriol oil is the high-purity anhydrous hydrofluoric method of raw material production:
1. generate the precipitation silicofluoride with soluble metal ion salt and silicofluoric acid reaction, the concentration of silicofluoric acid is 5～25%, and the concentration of soluble metal ion salt is controlled at 10～100%, and the liquid-solid ratio of system is controlled at 3.0～15.0, temperature of reaction is 0～60 ℃, and the time is 15～60 minutes.Preferred silicofluoric acid concentration is 10～18%, and the concentration of soluble metal ion salt is 80～100%, and temperature of reaction is 35～50 ℃, and the time is 30～50 minutes, and liquid-solid ratio is 3.0～8.0.After reaction is finished, filtration washing, filtrate is acidic solution, filter cake is the precipitation silicofluoride;
2. the precipitation silicofluoride with sulfuric acid and moisture content is that vitriol is produced in 1.0009,0.9784,0.9889 or 0.9905 reaction in molar ratio, and discharges silicon tetrafluoride and hydrogen fluoride, and the calcination reaction temperature is 200～700 ℃, and the time is 30～90 minutes.Preferred calcination reaction temperature is 350～550 ℃, 30～50 minutes time;
3. according to the requirement of second, the present invention also can adopt the precipitation silicofluoride and corresponding hydrosulfate reaction of production, and reaction conditions is with the requirement of second.
4. according to the requirement of article one, the soluble metal ion salt of indication of the present invention is to react and sedimentary metal ion with silicofluoric acid, for example can be sylvite such as Repone K, vitriolate of tartar, saltpetre or Potassium ethanoate, also can be sodium salts such as sodium-chlor, sodium sulfate, SODIUMNITRATE or sodium-acetate.
5. according to article one, second and the 3rd 's requirement, if vitriol is sold as byproduct, precipitate the mother liquor behind the silicofluoric acid so, according to the purposes difference, can by-product sulfuric acid, acids such as hydrochloric acid, nitric acid or acetic acid.
6. according to article one, second and the 3rd 's requirement, if the vitriol circulation, precipitates the mother liquor behind the silicofluoric acid so as precipitation agent, can the by-product dilute sulphuric acid, for phosphate production enterprise, dilute sulphuric acid can enter phosphoric acid extraction system decomposition phosphorus ore.
7. according to second and the 3rd 's requirement, the vitriol that the present invention generates in reaction process can be used as production marketing, also can be recycled to the precipitation agent of silicofluoric acid system as silicofluoric acid.
8. according to second and the 3rd 's requirement, the present invention's escaping gas in reaction process generates anhydrous hydrogen fluoride through refrigerated separation, and the noncondensable gas water absorbs and generates the silicofluoric acid recycle, perhaps prepares other fluorine-containing product and white carbon black.
The present invention has following advantage:
The present invention compared with prior art, can be the high-purity anhydrous hydrogen fluoride of raw material production with the silicofluoric acid and the vitriol oil, the present invention changes the direct conventional art that sulfuric acid is driven silicofluoric acid that adds in silicate fluoride solution, at first silicofluoric acid is precipitated out, utilizes traditional fluorite to make the operational path of anhydrous hydrogen fluoride, product purity height, steady quality, easy to control, technological process is simple, and product cost is lower; Purge process of the present invention is simple, has alleviated the corrosion of equipment, has reduced the repair expense of product.The present invention simultaneously can reclaim various acids and the corresponding sulfate product of by-product with the mother liquor of producing the precipitation silicofluoride flexibly.The vitriol that generates behind precipitation silicofluoride and the strong sulfuric acid response can return the silicofluoric acid system again as precipitation agent, and the sulfuric acid that this technology reclaims can enter phosphoric acid extraction system decomposition phosphorus ore.
Four, description of drawings
Fig. 1 is high-purity anhydrous hydrofluoric preparation technology's FB(flow block)
Five, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can be according to some nonessential improvement and adjustment in the content of the invention described above.
Embodiment 1
Get 5000 kilogram 15% silicofluoric acid, adding 816 kilograms of purity is 95% Repone K, and temperature of reaction is 40 ℃, and 1 hour time, liquid-solid ratio is controlled at 4.3.After-filtration is finished in reaction, 1077 kilograms of filter cake dry weights, and filtrate contains hydrogenchloride 8.1%.
1077 kilograms of precipitation potassium silicofluorides were calcined 40 minutes at 500 ℃ times with after 490 kilogram of 98% sulfuric acid mixes.Generate 874 kilograms of vitriolate of tartar, purity is 97.6%; The gas that generates obtains 176 kilograms of anhydrous hydrogen fluorides-5 ℃ of following condensations 3 hours through separation, and product purity is 99.93%.The silicon tetrafluoride circulation manufacturing silicofluoric acid that is dissolved in the water, silicofluoric acid weight is 5040 kilograms, concentration is 10%.
Embodiment 2
Get 2000 kilogram 15% silicofluoric acid, adding 380 kilograms of purity is 94.6% vitriolate of tartar, and temperature of reaction is 40 ℃, and 1 hour time, liquid-solid ratio is controlled at 4.1.After-filtration, 439.6 kilograms of filter cake dry weights, filtrate sulfur acid 10.5% are finished in reaction.
439.6 the kilogram potassium silicofluoride was calcined 1 hour at 450 ℃ times with after 195.5 kilogram of 98% sulfuric acid mixes.Generate 358.7 kilograms of vitriolate of tartar, purity is 95.2%; The gas that generates obtains 73.8 kilograms of anhydrous hydrogen fluorides-5 ℃ of following condensations 2 hours through separation, and product purity is 99.96%.The silicon tetrafluoride circulation manufacturing silicofluoric acid that is dissolved in the water, silicofluoric acid weight is 1506 kilograms, concentration is 13.3%.
Embodiment 3
Get 5000 kilogram 15% silicofluoric acid, adding 750 kilograms of purity is 98.2% sodium sulfate, and temperature of reaction is 40 ℃, and 1 hour time, liquid-solid ratio is controlled at 6.0.After-filtration, 764.2 kilograms of filter cake dry weights, filtrate sulfur acid 10.2% are finished in reaction.
764.2 the kilogram Sodium Silicofluoride was calcined 1 hour at 450 ℃ times with after 402 kilogram of 98% sulfuric acid mixes.Generate 581 kilograms of sodium sulfate, purity is 97.34%; The gas that generates obtains 151.4 kilograms of anhydrous hydrogen fluorides 0 ℃ of following condensation 3 hours through separation, and product purity is 99.98%.The silicon tetrafluoride circulation manufacturing silicofluoric acid that is dissolved in the water, silicofluoric acid weight is 3680 kilograms, concentration is 11.2%.
Embodiment 4
Method according to embodiment 2,13.3% the silicofluoric acid 1506 kilograms (adding 550 kilogram 15% silicofluoric acid in addition) that to be 358.7 kilograms of purity that generate 95.2% vitriolate of tartar generate with embodiment 2 reacts, temperature of reaction is 40 ℃, and 1 hour time, liquid-solid ratio is controlled at 4.1.After-filtration, 433.1 kilograms of filter cake dry weights, filtrate sulfur acid 9.78% are finished in reaction.
433.1 the kilogram potassium silicofluoride was calcined 1 hour at 450 ℃ times with after 195.0 kilogram of 98% sulfuric acid mixes.Generate 343.4 kilograms of vitriolate of tartar, purity is 98.7%; The gas that generates obtains 70.16 kilograms of anhydrous hydrogen fluorides-5 ℃ of following condensations 2 hours through separation, and product purity is 99.95%.The silicon tetrafluoride circulation manufacturing silicofluoric acid that is dissolved in the water, silicofluoric acid weight is 1902.6 kilograms, concentration is 10.6%.
Claims (8)
1. one kind prepares high-pure anhydrous hydrofluoric method, it is characterized in that this method is is that 5～25% silicofluoric acid and concentration are that 10～100% soluble metal ion salt is raw material with concentration earlier, the liquid-solid ratio of the hierarchy of control is 3.0～15.0, generated sedimentary silicofluoride in 15～60 minutes in 0～60 ℃ of following reaction of temperature, be that intermediate and sulfuric acid or hydrosulfate are at high temperature emitted hydrogen fluoride and silicon tetrafluoride gas behind the calcination reaction with the precipitation silicofluoride again, obtain high-pure anhydrous hydrogen fluoride after drying, purification, the separation.
2. the high-pure anhydrous hydrofluoric method of preparation according to claim 1, it is characterized in that sulfuric acid is 1.0009,0.9784,0.9889 or 0.9905 with the mol ratio that precipitates silicofluoride in this method, the temperature of its calcination reaction is 200～700 ℃, and the time is 30～90 minutes.
3. the high-pure anhydrous hydrofluoric method of preparation according to claim 1 and 2, it is characterized in that silicofluoric acid concentration used in this method is 10～18%, the soluble metal ion salt concn is 80～100%, the liquid-solid ratio of the hierarchy of control is 3.0～8.0, temperature of reaction is 35～50 ℃, and the time is 30～50 minutes.
4. the high-pure anhydrous hydrofluoric method of preparation according to claim 1 and 2 is characterized in that the calcining temperature that this method adopts is 350～550 ℃, 30～50 minutes time.
5. the high-pure anhydrous hydrofluoric method of preparation according to claim 3 is characterized in that the calcining temperature that this method adopts is 350～550 ℃, 30～50 minutes time.
6. the high-pure anhydrous hydrofluoric method of preparation according to claim 1 and 2 is characterized in that the used soluble metal ion salt of this method is any in Repone K, vitriolate of tartar, saltpetre, Potassium ethanoate, sodium-chlor, sodium sulfate, SODIUMNITRATE or the sodium-acetate.
7. the high-pure anhydrous hydrofluoric method of preparation according to claim 5 is characterized in that soluble metal ion salt used in this method is any in Repone K, vitriolate of tartar, saltpetre, Potassium ethanoate, sodium-chlor, sodium sulfate, SODIUMNITRATE or the sodium-acetate.
8. the high-pure anhydrous hydrofluoric method of preparation according to claim 1 and 2, it is characterized in that this method will precipitate escaping gas process refrigerated separation generation anhydrous hydrogen fluoride in silicofluoride and sulfuric acid or the hydrosulfate reaction process, the noncondensable gas water absorbs and generates the silicofluoric acid recycle, perhaps prepares other fluorine-containing product and white carbon black with it.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214926B (en) * | 2007-12-28 | 2010-04-07 | 华陆工程科技有限责任公司 | Technique for producing anhydrous hydrofluoric acid |
| CN101734665B (en) * | 2009-12-23 | 2011-10-19 | 中国科学院南京土壤研究所 | Extracting agent for removing impurity phosphorus contained in fluosilicic acid and application method thereof |
| CN101948114A (en) * | 2010-10-13 | 2011-01-19 | 云南省化工研究院 | Method for preparing silicon tetrafluoride and anhydrous hydrogen fluoride from sodium fluosilicate acidified by sulfuric acid |
| CN102557043B (en) * | 2011-12-28 | 2014-07-16 | 中国化学赛鼎宁波工程有限公司 | Method for preparing silicon tetrafluoride and anhydrous hydrogen fluoride by taking sodium fluorosilicate as raw material |
| CN102556973B (en) * | 2012-02-22 | 2013-10-23 | 中南大学 | Method for producing hydrofluoric acid from fluorite as raw material |
| CN105947984A (en) * | 2016-05-20 | 2016-09-21 | 同济大学 | Production process for recycling and producing anhydrous hydrogen fluoride from high-concentration wastewater containing fluoride |
| CN106865500B (en) * | 2017-04-05 | 2019-03-15 | 张旭 | A kind of cycle production process preparing hydrogen fluoride with fluosilicic acid |
| CN107601434A (en) * | 2017-11-07 | 2018-01-19 | 衢州市鼎盛化工科技有限公司 | A kind of method and apparatus that hydrogen fluoride is prepared by fluosilicic acid |
| CN111252770A (en) * | 2020-04-26 | 2020-06-09 | 贵州瓮福蓝天氟化工股份有限公司 | Method for removing chlorine from fluosilicic acid |
| CN112158850A (en) * | 2020-09-27 | 2021-01-01 | 湖北祥云(集团)化工股份有限公司 | Method for preparing anhydrous silicon tetrafluoride and hydrogen fluoride mixed gas by using phosphorus ore associated fluorine |
| CN112897466A (en) * | 2020-10-27 | 2021-06-04 | 贵州省化工研究院 | Method for producing anhydrous hydrogen fluoride by using fluosilicic acid in phosphoric acid |
| CN112174143A (en) * | 2020-10-27 | 2021-01-05 | 贵州省化工研究院 | Method for producing silicon tetrafluoride by using fluorine-containing phosphoric acid |
| CN112320821A (en) * | 2020-10-27 | 2021-02-05 | 贵州省化工研究院 | Method for producing high-purity potassium fluoride by using fluosilicic acid in phosphoric acid |
| CN113800470B (en) * | 2021-10-11 | 2023-05-02 | 金宏气体股份有限公司 | Device and process for preparing hydrogen fluoride by ammonification method |
| CN113816339A (en) * | 2021-10-13 | 2021-12-21 | 中国科学院过程工程研究所 | Method for preparing anhydrous hydrogen fluoride from sodium fluoride |
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