CN101353156A - Method for preparing fluorine hydride from acidic mixture of inorganic fluoride and sulphuric acid - Google Patents
Method for preparing fluorine hydride from acidic mixture of inorganic fluoride and sulphuric acid Download PDFInfo
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- CN101353156A CN101353156A CNA2008100686612A CN200810068661A CN101353156A CN 101353156 A CN101353156 A CN 101353156A CN A2008100686612 A CNA2008100686612 A CN A2008100686612A CN 200810068661 A CN200810068661 A CN 200810068661A CN 101353156 A CN101353156 A CN 101353156A
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Abstract
The invention discloses a method for preparing hydrogen fluoride with an acid mixture of inorganic fluoride and sulfuric acid and relates to a fluoride. The hydrogen fluoride gas is prepared by controlling operating conditions of the reaction volatilization, or distillation separation, or rectification separation process of the acid mixture of the inorganic fluoride and the sulfuric acid in a conventional equipment space, especially the pressure condition and the temperature condition, and carrying out a heat and mass transfer process to cause the water and sulfuric acid and sulfate in the acid mixture to be kept on a liquid phase. When the hydrogen fluoride is purified, a 40% hydrofluoric acid or anhydrous hydrogen fluoride is prepared. The method is suitable for recovering and preparing the hydrogen fluorine from the fluorine of the fluorine-containing intermediate materials or 'three industrial wastes' with the fluorine produced in the processes of chemical industry, electronics industry, glass machining industry, aluminum alloy machining industry and the like to make hydrogen. The method is especially suitable for enterprises to recover the materials with fluorine separated from the phosphoric acid, phosphate fertilizer and other phosphate chemical products produced by the wet process and make the hydrogen fluoride, or for the comprehensive utilization of the 'three industrial wastes' with fluorine.
Description
Technical field
The present invention relates to fluorochemical, in particular to the recycling, the particularly method that reclaims with hydrofluoric form of the fluorochemical from the inorganic or organic materials of industries such as chemical industry, electron trade, glass processing and aluminium alloy processing.
Background technology
As everyone knows, in the production process of industries such as fluorine chemical industry, phosphorous chemical industry industry, electron trade, glass processing and aluminium alloy processing, waste gas, waste liquid, the waste residue that contains fluorine element can be produced, waste liquid or waste residue can be changed into by purification and washing to waste gas.These waste liquid, waste residues that contain fluorine element are all recycled efficiently at present, only carry out simple process for reaching environmental requirement.For example the phosphorous chemical industry industry maybe will contain the waste water of fluorine element with discharging with the back in the lime with the Sodium Silicofluoride product form recovery of low value; The sulfur waste acid of fluorine chemical industry fluorinated hydrogen is used for production of phosphate fertilizer to sell at a low price; The low concentration hydrofluoric acid that contains inorganic salt and organic compound of fluorine chemical industry discharging then directly send sewage works with in the alkaline matter with after efflux; Electron trade contain inorganic fluoride waste water also be with in the alkaline matter and after efflux.In addition, incomplete owing to organic fluoridation in the production process of fluorine chemical industry, need separate utilization again and contain more hydrogen fluoride composition in the intermediate material of feasible production organic fluoride, its hydrofluoric separation and recovery method has usually: high-temperature pressure distills recycling, 3. extracts recycling with alkaline material after 1. utilizing azeotrope distillation principle to adopt the High Temperature High Pressure rectifying separation to utilize, 2. extract with sulfuric acid.
At above-mentioned " three wastes " problem of inorganic fluorine element and the hydrogen fluoride Separation and Recovery problem in the fluorine chemical industry intermediate material of containing, lot of domestic and foreign scientific worker has proposed a series of technical schemes.Wherein have: by " a kind of liquid phase acid hydrolysis method of ammonium fluoride " (application number is 2006100511784) of Guizhou Provincial Inst. of Chemical Technology's proposition with the related prior art scheme of the present invention; " method that a kind of phosphate fertilizer byproduct comprehensive utilizes " that proposed by Tianjin chemical research institute and Yunnan Prov Sanhuan Chemical Co., Ltd (CN1554570); " the high-pure anhydrous hydrofluoric technology of a kind of preparation " that proposed by Sichuan University (CN1696050); " method of purifying hydrogen fluoride " that proposed by U.S. Honeywell Int Inc (CN1849261A); By Duo-fluoride Chemicals Co., Ltd. propose " a kind of method of producing hydrofluoric acid " (CN101077770) and " producing the method for hydrofluoric acid " (CN101077769); " a kind of technology of fluorine-containing sulphuric acid extraction hydrofluoric acid " that proposed by Ying Lierong (CN1180043).
The shortcoming of prior art scheme is: because its reaction volatilization; or fractionation by distillation; or the working pressure of rectifying separation technological process and temperature is all higher and material residence time in equipment is longer; requirement to device structure and material is very harsh; therefore device structure and Material Selection scope have greatly been dwindled; and also there is short and processing safety in work-ing life drawback such as low in equipment; particularly for Neutral ammonium fluoride; Sodium Fluoride; Potassium monofluoride; the reacting by heating volatilization of fluorochemical salt such as magnesium fluoride and vitriolic acidic mixture; or the fractionation by distillation technological process, under existing industrial technology level conditions, also there are not suitable device structure and material to satisfy its requirement of massive production.
Therefore; improve reaction volatilization or the structure of fractionation by distillation or rectifying separation process conditions and equipment and the interoperability of material of acidic mixture; and further improve the reliability of operation of equipment and work-ing life to satisfy requirement of massive production, be that fluorine element reclaims link and is badly in need of the key technical problem that solves.
Summary of the invention
The object of the present invention is to provide a kind of technology method that volatilization or fractionation by distillation or rectifying separation go out hydrogen fluoride gas that from inorganic fluoride and vitriolic acidic mixture, reacts; to overcome the shortcoming that prior art exists, satisfy requirement of massive production.
To achieve these goals, thus the contriver has finished the present invention by a large amount of investigative tests, simultaneous test and condition test.The process characteristic that the contriver provided is: the reaction by control inorganic fluoride and vitriolic acidic mixture in the conventional equipment space is volatilized or fractionation by distillation or rectifying separation process conditions, particularly controlled temperature condition and pressure condition make water and sulfuric acid, vitriol in the acidic mixture stay liquid phase and prepare hydrogen fluoride gas through the heat and mass technological process.
Above-mentioned inorganic fluoride is Neutral ammonium fluoride or Sodium Fluoride or Potassium monofluoride or magnesium fluoride or hydrogen fluoride; Described inorganic fluoride with before sulfuric acid mixes be gaseous state or liquid or solid-state; Content with fluorine ionometer in the described inorganic fluoride composition is 0.5%～95%; Described sulfuric acid concentration is with H
2SO
4Count 50%～104.5%, and available its acid anhydrides---sulphur trioxide is replaced.
Above-mentioned inorganic fluoride and vitriolic acidic mixture be by sulfuric acid with obtain simple mixing of inorganic fluoride, or the intermediate material thorough mixing by sulfuric acid and fluorinated hydrogen, through washing or absorb or extraction and obtaining, or form by the useless vitriolic of fluorinated hydrogen that produces in the control fluorine chemical industry technological process and to obtain, or obtain by sulfuric acid and silicofluoric acid or silicofluoride thorough mixing, decomposition, conversion.
The reaction volatilization of above-mentioned acidic mixture or the process conditions of fractionation by distillation or rectifying separation are respectively:
1. be Neutral ammonium fluoride for inorganic fluoride, or Sodium Fluoride, or Potassium monofluoride, or during magnesium fluoride, described inorganic fluoride and vitriolic acidic mixture are that the sulfuric acid with the liquid material of fluoride or solid materials and finite concentration and weight mixes and obtains, and the mol ratio of controlling this acidic mixture main component is a fluorochemical: sulfuric acid: water=1: 1～10: 0～10, described acidic mixture is reacted volatilization, or fractionation by distillation, or rectifying separation operation, and controlling its operating procedure condition is: 80～180 ℃ of temperature of charge, the gas phase absolute pressure less than 0.08MPa or vacuum tightness be-0.02～-0.1MPa, residence time of material 2～120min.
When 2. being hydrogen fluoride for inorganic fluoride, described inorganic fluoride and vitriolic acidic mixture are the gas material of fluorinated hydrogen or liquid material are mixed with the sulfuric acid of finite concentration and weight and to obtain, and this acidic mixture is uniform liquid state or the gas material of fluorinated hydrogen and the heterogeneous admixture of sulphuric acid soln in gas-liquid mass transfer (contact) equipment.And control that the mol ratio of sulfuric acid and water is a sulfuric acid in this acidic mixture: water=1: 0.1～8, described acidic mixture is carried out fractionation by distillation or rectifying separation operation, and controlling its operating procedure condition is: 40 ℃～180 ℃ of temperature of charge, the gas phase absolute pressure less than 0.08MPa or vacuum tightness be-0.02～-0.1MPa, residence time of material 2～120min.
3. for the Separation and Recovery of useless vitriolic Separation and Recovery of the fluorinated hydrogen in the fluorine chemical industry technological process and fluorinated hydrogen intermediate material, described inorganic fluoride and vitriolic acidic mixture are respectively that to make its mol ratio that meets sulfuric acid and water by the useless vitriolic composition of fluorinated hydrogen in the control fluorine chemical industry technological process be sulfuric acid: water=1: 0.1～8 obtain; Or by carrying out thorough mixing with the sulfuric acid of finite concentration and weight and the intermediate material of fluorinated hydrogen, wash or absorb or extract with intermediate material fluorinated hydrogen, make hydrogen fluoride enter sulphuric acid soln and obtain, and control that the mol ratio of sulfuric acid and water is a sulfuric acid in this acidic mixture: water=1: 0.1～8.Described acidic mixture is carried out the operation of fractionation by distillation or rectifying separation, and controls its operating procedure condition and be: 40～180 ℃ of temperature of charge, the gas phase absolute pressure less than 0.08MPa or vacuum tightness be-0.02～-0.1MPa, residence time of material 2～120min.
4. reclaim silicofluoric acid or silicofluoride system hydrogen fluoride for fluorine chemical industry or phosphorous chemical industry industry, described inorganic fluoride and vitriolic acidic mixture are with finite concentration and the sulfuric acid of weight and the liquid material or the solid materials thorough mixing of fluorine-containing silicic acid or silicofluoride, decompose, transform and get, and control this mixing, decompose, the mol ratio of sulfuric acid and water is a sulfuric acid in the acidic mixture that transforms and get: water=1: 0.1～8, described acidic mixture is carried out fractionation by distillation or rectifying separation operation, and controlling its operating procedure condition is: 40 ℃～180 ℃ of temperature of charge, the gas phase absolute pressure less than 0.08MPa or vacuum tightness be-0.02～-0.1MPa, residence time of material 2～120min.
In the said process, temperature condition keep or control method comprises one of following method respectively:
1. adopt interchanger that raw material or acidic mixture are carried out heat exchange to keep reaction volatilization or fractionation by distillation or rectifying separation temperature condition;
2. do not join interchanger in addition, and utilize the heat of high temperature raw material or hot mixture self and the heat of gasification of hydrogen fluoride and moisture to volatilize or fractionation by distillation or rectifying separation temperature condition to keep reaction;
3. utilize high temperature intermediate material and sulfuric acid directly to contact and carry out mass transfer and conduct heat volatilizing or fractionation by distillation or rectifying separation temperature condition to keep reaction;
In the said process, the control of pressure condition is to adopt reciprocating vacuum pump or liquid-ring vacuum pump or liquid-jet vacuum pump or rotary-vane vaccum pump or Roots vaccum pump to keep the pressure of reaction volatilization or fractionation by distillation or rectifying separation.
Above-mentioned volatilization or fractionation by distillation or the rectifying separation apparatus operating space of reacting adopted and can be satisfied working pressure and provide less than the reactor of the conventional structure of 40 ℃～180 ℃ of 0.08MPa, service temperature or vaporizer or evaporator room or various tower.
The above-mentioned equipment material that contacts with material is a kind of in graphite, fluoroplastics, resol, the nickelalloy.
Above-mentioned technological process adopts the continuous production operation or is interrupted production operation.
The above-mentioned hydrogen fluoride gas that is prepared by acidic mixture adopts mature technology to purify, and can be made into 40% hydrofluoric acid product or anhydrous hydrogen fluoride product.
The present invention is applicable to that fluorine-containing intermediate material in the industry technological processs such as coming from chemical industry, electron trade, glass processing industry, aluminium alloy processing or the fluorine element in fluorine-containing " three wastes " reclaim system hydrogen fluoride, is specially adapted to adopt the isolated fluorine-containing material of enterprise of Wet-process phosphoric acid (WPPA), phosphate fertilizer and other phosphorus chemical product to reclaim system hydrogen fluoride or fluorine-containing " three wastes " are fully utilized.
Embodiment
Embodiment 1: take by weighing NH respectively
4The solid Neutral ammonium fluoride 80g of F content 95%, H
2SO
4The vitriol oil 320g of content 96%; With two kinds of raw materials simultaneously or successively add lentamente and promptly obtain Neutral ammonium fluoride and vitriolic acidic mixture in the reactor, controlling reactor space gas phase absolute pressure 0.02MPa or vacuum tightness-0.08MPa, control Neutral ammonium fluoride and vitriolic acidic mixture temperature are that 120 ℃～130 ℃ and insulation reaction are distilled stopped reaction behind the 30min.Reaction, fractionation by distillation volatilize the gaseous mixture of 43g hydrogen fluoride and water altogether, residue raffinate 357g.After testing, the evaporation rate of HF is 97.1%.
Embodiment 2: take by weighing the solid Sodium Fluoride 88g of NaF content 98% respectively, H
2SO
4The vitriol oil 320g of content 96%; With two kinds of raw materials simultaneously or successively add lentamente and promptly obtain Sodium Fluoride and vitriolic acidic mixture in the reactor, controlling reactor space gas phase absolute pressure 0.01MPa or vacuum tightness-0.09MPa, control Sodium Fluoride and vitriolic acidic mixture temperature are that 140 ℃～150 ℃ and insulation reaction are distilled stopped reaction behind the 60min.Reaction, fractionation by distillation volatilize the gaseous mixture of 47g hydrogen fluoride and water altogether, residue raffinate 361g.After testing, the evaporation rate of HF is 98.4%.
Embodiment 3: take by weighing the hydrofluoric acid 93g of HF content 40% respectively, H
2SO
4The vitriol oil 214.5g of content 96%; With two kinds of raw materials simultaneously or successively add lentamente and promptly obtain hydrogen fluoride and vitriolic acidic mixture in the reactor, control 90 ℃～100 ℃ of this hydrogen fluoride and vitriolic acidic mixture temperature, controlling reactor space gas phase absolute pressure 0.01～0.02MPa or vacuum tightness-0.08～-0.09MPa, and stopped reaction behind the insulation distillation 60min.Fractionation by distillation volatilizes the gaseous mixture of 38.5g hydrogen fluoride and water altogether, residue raffinate 269g.After testing, the evaporation rate of HF is 94.5%.
Embodiment 4: take by weighing H respectively
2SiF
6The silicofluoric acid 100g of content 45%, H
2SO
4The vitriol oil 225g of content 98%; With two kinds of raw materials simultaneously or successively add lentamente in the reactor and make SiF by the prior art thermal degradation
4Can transform after the volatilization and obtain hydrogen fluoride and vitriolic acidic mixture, this acidic mixture is 285.5g altogether, contains HF3.9%, H
2SO
4Content 77.2%, H
2O content 18.9%.Controlling this acidic mixture temperature is 80～90 ℃, space reactor gas phase absolute pressure 0.01～0.02MPa or vacuum tightness-0.08～-0.09MPa, and stop behind the insulation distillation 90min.Fractionation by distillation volatilizes the gaseous mixture of 11g hydrogen fluoride and water altogether, residue raffinate 274.5g.After testing, the evaporation rate of HF is 93.4%.
Claims (10)
1 prepares hydrofluoric method from inorganic fluoride and vitriolic acidic mixture, it is characterized in that this method is that the reaction by control inorganic fluoride and vitriolic acidic mixture is volatilized or fractionation by distillation or rectifying separation process conditions in the conventional equipment space, particularly controlled temperature condition and pressure condition make water and sulfuric acid, vitriol in the acidic mixture stay liquid phase and prepare hydrogen fluoride gas through the heat and mass technological process.
2 the method for claim 1 is characterized in that described inorganic fluoride is Neutral ammonium fluoride or Sodium Fluoride or Potassium monofluoride or magnesium fluoride or hydrogen fluoride; Described inorganic fluoride with before sulfuric acid mixes be gaseous state or liquid or solid-state; Content with fluorine ionometer in the described inorganic fluoride composition is 0.5%～95%; Its concentration of described sulfuric acid is with H
2SO
4Count 50%～104.5%, and available its acid anhydrides---sulphur trioxide is replaced; Described inorganic fluoride and vitriolic acidic mixture be by sulfuric acid with obtain simple mixing of inorganic fluoride, or the intermediate material thorough mixing by sulfuric acid and fluorinated hydrogen, through washing or absorb or extraction and obtaining, or form by the useless vitriolic of fluorinated hydrogen that produces in the control fluorine chemical industry technological process and to obtain, or obtain by sulfuric acid and silicofluoric acid or silicofluoride thorough mixing, decomposition, conversion.
3 as the described method in one of claim 1 or 2, it is characterized in that for inorganic fluoride be Neutral ammonium fluoride, or Sodium Fluoride, or Potassium monofluoride, or during magnesium fluoride, described inorganic fluoride and vitriolic acidic mixture are that the sulfuric acid with the liquid material of fluoride or solid materials and finite concentration and weight mixes and obtains, and the mol ratio of controlling this acidic mixture main component is a fluorochemical: sulfuric acid: water=1: 1～10: 0～10, described acidic mixture is reacted volatilization, or fractionation by distillation, or rectifying separation operation, and controlling its operating procedure condition is: 80 ℃～180 ℃ of temperature of charge, the gas phase absolute pressure less than 0.08MPa or vacuum tightness be-0.02～-0.1MPa, residence time of material 2～120min.
4 as the described method in one of claim 1 or 2, when it is characterized in that being hydrogen fluoride for inorganic fluoride, described inorganic fluoride and vitriolic acidic mixture are the gas material of fluorinated hydrogen or liquid material are mixed with the sulfuric acid of finite concentration and weight and to obtain, and this acidic mixture is uniform liquid state or the gas material of fluorinated hydrogen and the heterogeneous admixture of sulphuric acid soln in gas-liquid mass transfer (contact) equipment; And control that the mol ratio of sulfuric acid and water is a sulfuric acid in this acidic mixture: water=1: 0.1～8, described acidic mixture is carried out fractionation by distillation or rectifying separation operation, and controlling its operating procedure condition is: 40～180 ℃ of temperature of charge, the gas phase absolute pressure less than 0.08MPa or vacuum tightness be-0.02～-0.1MPa, residence time of material 2～120min.
5 as the described method in one of claim 1 or 2, it is characterized in that the Separation and Recovery for useless vitriolic Separation and Recovery of the fluorinated hydrogen in the fluorine chemical industry technological process and fluorinated hydrogen intermediate material, described inorganic fluoride and vitriolic acidic mixture are respectively that to make its mol ratio that meets sulfuric acid and water by the useless vitriolic composition of fluorinated hydrogen in the control fluorine chemical industry technological process be sulfuric acid: water=1: 0.1～8 obtain; Or by carrying out thorough mixing with the sulfuric acid of finite concentration and weight and the intermediate material of fluorinated hydrogen, wash or absorb or extract with intermediate material fluorinated hydrogen, make hydrogen fluoride enter sulphuric acid soln and obtain, and control that the mol ratio of sulfuric acid and water is a sulfuric acid in this acidic mixture: water=1: 0.1～8.Described acidic mixture is carried out the operation of fractionation by distillation or rectifying separation, and controls its operating procedure condition and be: 40～180 ℃ of temperature of charge, the gas phase absolute pressure less than 0.08MPa or vacuum tightness be-0.02～-0.1MPa, residence time of material 2～120min.
6 as the described method in one of claim 1 or 2, it is characterized in that reclaiming silicofluoric acid or silicofluoride system hydrogen fluoride for fluorine chemical industry or phosphorous chemical industry industry, described inorganic fluoride and vitriolic acidic mixture are with finite concentration and the sulfuric acid of weight and the liquid material or the solid materials thorough mixing of fluorine-containing silicic acid or silicofluoride, decompose, transform and get, and control this mixing, decompose, the mol ratio of sulfuric acid and water is a sulfuric acid in the acidic mixture that transforms and get: water=1: 0.1～8, described acidic mixture is carried out fractionation by distillation or rectifying separation operation, and controlling its operating procedure condition is: 40～180 ℃ of temperature of charge, the gas phase absolute pressure less than 0.08MPa or vacuum tightness be-0.02～-0.1MPa, residence time of material 2～120min.
7 the method for claim 1, it is characterized in that described volatilization or fractionation by distillation or the rectifying separation apparatus operating space of reacting adopt and can satisfy working pressure and provide less than the reactor of the conventional structure of 40～180 ℃ of 0.08MPa, service temperature or vaporizer or evaporator room or various tower, the equipment material that contacts with material comprises a kind of in graphite, fluoroplastics, resol, the nickelalloy.
8 the method for claim 1, it is characterized in that described in the device space temperature condition keep or control method is respectively one of following method: 1. adopt interchanger that raw material or acidic mixture are carried out heat exchange to keep reaction volatilization or fractionation by distillation or rectifying separation temperature condition; The material that contacts with material in the interchanger comprises a kind of in graphite, fluoroplastics, resol, the nickelalloy; 2. do not join interchanger in addition, and utilize the heat of high temperature raw material or hot mixture self and the heat of gasification of hydrogen fluoride and moisture to volatilize or fractionation by distillation or rectifying separation temperature condition to keep reaction; 3. utilize high temperature intermediate material and sulfuric acid directly to contact and carry out mass transfer and conduct heat volatilizing or fractionation by distillation or rectifying separation temperature condition to keep reaction.
9 the method for claim 1 is characterized in that the described method of keeping in device space internal pressure is to adopt reciprocating vacuum pump or liquid-ring vacuum pump or liquid-jet vacuum pump or rotary-vane vaccum pump or Roots vaccum pump to keep the pressure condition of reaction volatilization or fractionation by distillation or rectifying separation;
10 the method for claim 1 is characterized in that described technological process adopts the continuous production operation or is interrupted production operation.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100686612A CN101353156A (en) | 2008-03-14 | 2008-03-14 | Method for preparing fluorine hydride from acidic mixture of inorganic fluoride and sulphuric acid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2447013C2 (en) * | 2010-04-19 | 2012-04-10 | Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" | Method of producing anhydrous hydrogen fluoride and hydrofluoric acid |
| CN102424367A (en) * | 2011-09-20 | 2012-04-25 | 六九硅业有限公司 | Fluorine-containing sulfuric acid separation concentration device and separation concentration method |
| 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 |
| CN103696307A (en) * | 2013-12-17 | 2014-04-02 | 西南交通大学 | Process for removing ash content in straw cellulose |
| CN103910333A (en) * | 2013-01-08 | 2014-07-09 | 中核四0四有限公司 | Method for recovering hydrogen fluoride in hydrofluorination process tail gas |
| CN106829867A (en) * | 2017-04-14 | 2017-06-13 | 衢州市鼎盛化工科技有限公司 | The method and apparatus of fluorine-containing mixing spent acid comprehensive reutilization |
| CN110736805A (en) * | 2019-08-28 | 2020-01-31 | 广西银亿高新技术研发有限公司 | method for measuring content of aluminum ions in lithium solution containing fluorine and aluminum |
| RU2793317C1 (en) * | 2022-04-27 | 2023-03-31 | Закрытое акционерное общество "ТЕХНОИНВЕСТ АЛЬЯНС" (ЗАО "ТЕХНОИНВЕСТ АЛЬЯНС") | Method for the concentration of hydrofluoric acid |
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| RU2447013C2 (en) * | 2010-04-19 | 2012-04-10 | Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" | Method of producing anhydrous hydrogen fluoride and hydrofluoric acid |
| CN102424367A (en) * | 2011-09-20 | 2012-04-25 | 六九硅业有限公司 | Fluorine-containing sulfuric acid separation concentration device and separation concentration method |
| 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 |
| CN102951611B (en) * | 2012-12-24 | 2017-03-15 | 贵州省化工研究院 | The method that a kind of fluorine-containing waste liquid of phosphatic fertilizer company or hexafluosilicic acid prepare anhydrous hydrogen fluoride |
| CN103910333A (en) * | 2013-01-08 | 2014-07-09 | 中核四0四有限公司 | Method for recovering hydrogen fluoride in hydrofluorination process tail gas |
| CN103910333B (en) * | 2013-01-08 | 2016-01-27 | 中核四0四有限公司 | A kind of hydrofluoric method in recovery hydrofluorination process tail gas |
| CN103696307A (en) * | 2013-12-17 | 2014-04-02 | 西南交通大学 | Process for removing ash content in straw cellulose |
| CN103696307B (en) * | 2013-12-17 | 2016-05-18 | 西南交通大学 | A kind of stalk cellulose ash content removing process |
| CN106829867A (en) * | 2017-04-14 | 2017-06-13 | 衢州市鼎盛化工科技有限公司 | The method and apparatus of fluorine-containing mixing spent acid comprehensive reutilization |
| CN110736805A (en) * | 2019-08-28 | 2020-01-31 | 广西银亿高新技术研发有限公司 | method for measuring content of aluminum ions in lithium solution containing fluorine and aluminum |
| RU2793317C1 (en) * | 2022-04-27 | 2023-03-31 | Закрытое акционерное общество "ТЕХНОИНВЕСТ АЛЬЯНС" (ЗАО "ТЕХНОИНВЕСТ АЛЬЯНС") | Method for the concentration of hydrofluoric acid |
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Application publication date: 20090128 |