CN106698475A - Method used for preparing high quality ammonium bifluoride from fluorine silicon compound - Google Patents
Method used for preparing high quality ammonium bifluoride from fluorine silicon compound Download PDFInfo
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- CN106698475A CN106698475A CN201510789399.0A CN201510789399A CN106698475A CN 106698475 A CN106698475 A CN 106698475A CN 201510789399 A CN201510789399 A CN 201510789399A CN 106698475 A CN106698475 A CN 106698475A
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Abstract
The invention discloses a method used for preparing high quality ammonium bifluoride from a fluorine silicon compound, and belongs to the field of inorganic fluoride salt preparation in fluorine chemical industry. According to the method, solid fluosilicic acid or silicon tetrafluoride gas are added into a saturated ammonium fluoride solution, and excess ammonia is introduced at the same time for ammonolysis reaction; after reaction, an ammonium fluoride crystal slurry and a silicon dioxide suspension are obtained respectively; and six steps of treatment disclosed in the invention are carried out successively so as to obtain a high quality ammonium bifluoride product, and a reaction liquid is recycled back to a system circulation for recycling. Impurities introduced by the raw materials are mainly retained in silicon dioxide, so that the high quality ammonium bifluoride product can be produced easily. The method is capable of solving a fluorine pollution problem in phosphate fertilizer enterprise production, and realizing recycling of fluorine resource; and no three wastes is generated in system recycling operation.
Description
Technical field
The present invention relates to the technology of preparing of fluorine chemical industry inorganic fluoride salt in chemical field, a kind of technical method that ammonium acid fluoride is prepared using fluorine-containing discarded absorbing liquid or fluosilicic acid is related in particular to.
Background technology
Ammonium acid fluoride is mainly used as cleaning agent, the oxidant of fermentation industry disinfectant and silicon element surface of steel plate inorganic agent, manufacture ceramics and almag, organic synthesis fluorization agent, electroplate liquid, the acidification agent of the solvent, oil field sandstone of extraction rare element of glass etching agent, preservative, the solvent of beryllium oxide metallic beryllium, chemical reagent, the feed water system of boiler and steam generating system, the corrosive agent when surface conditioning agent and aluminium shape surface of silicon element steel plate are processed etc..Ammonium bifluoride with high purity can be additionally used in electronics, reagent and pharmaceuticals industry.In recent years as aluminium surface decoration technology begins to use ammonium acid fluoride to make corrosive agent, its market demand continues to increase.
At present, the raw materials for production of ammonium acid fluoride are hydrofluoric acid (or anhydrous hydrogen fluoride) and ammoniacal liquor (or liquefied ammonia), its technique includes two kinds of direct method and indirect method, directly hair is that high-purity hydrogen fluoride and high-purity ammon direct reaction are produced into ammonium acid fluoride, product quality is very high, and external form is the tablet after melting.Indirect method (liquid phase method) generates ammonium acid fluoride in aqueous using hydrogen fluoride and ammonia, then produces ammonium acid fluoride by crystallization, separation, dry method.
In domestic hydrofluoric acid (anhydrous hydrogen fluoride) production technology, only Guizhou Wengfu has a production line for producing hydrofluoric acid as raw material with fluosilicic acid at present, and other are raw material production with Fluorspar Powder and sulfuric acid.And fluorite is a kind of non-renewable strategic resources, though once there was abundant storage in China, but the situation (particularly single rawore is produced) of exhaustion is also faced with present, for this, country has had been carried out no longer providing new fluorite production licence, and carries out the relevant policies such as quota outlet (export quotas are also being reduced year by year).With the reduction of fluorite resource, day, be becoming tight by Fluorspar Powder supply, and the price of Fluorspar Powder also will be high all the way, and this will make Fluorspar Powder-Production By Sulfuric Acid Process hydrofluoric acid or anhydrous hydrogen fluoride be extremely limited even stopping production.Therefore, go to produce ammonium acid fluoride using expensive, hard-won hydrogen fluoride completely, just seem not economical enough.Ammonium acid fluoride product is produced from the waste gas containing fluoride absorbing liquid of phosphatic fertilizer company, is the trend of comprehensive utilization of resources and fluorine development of chemical industry.
The technology for producing ammonium acid fluoride using the fluosilicic acid of phosphatic fertilizer company by-product at present is more, but all it is to adopt ammonium fluoride solution in ammonium acid fluoride production process to be concentrated in various manners, obtain ammonium acid fluoride product, substantial amounts of fluorine-containing weak aqua ammonia thus can be produced at the concentration initial stage, later stage volatilizes concentration systems because ammonium fluoride is largely decomposed, and blocking pipeline is recrystallized in exhaust system.What " a kind of production method of ammonium bifluoride with high purity " was mentioned in the patent CN101898769A of Duo-fluoride Chemicals Co., Ltd.'s application prepares ammonium acid fluoride to logical anhydrous hydrogen fluoride in ammonium fluoride reaction solution, and its raw material fluorinated ammonium is obtained by the fluosilicic acid of phosphate fertilizer industry by-product through ammonolysis；In fact it is to be not easy to directly obtain the water brought in ammonium fluoride reaction solution, and fluosilicic acid raw material how to leave system aborning and also do not specify by fluosilicic acid ammonolysis；If obtaining ammonium fluoride reaction solution after being concentrated with the ammonium fluoride solution after ammonolysis, substantial amounts of fluorine-containing ammonium condensed water is there is, and the various impurity of fluosilicic acid institute band fully enter ammonium acid fluoride product.What " a kind of method for reclaiming fluorine resource production ammonium acid fluoride in fluorine-containing white residue " was mentioned in the patent CN102491370A of Wengfu Group Co., Ltd.'s application is passed through anhydrous hydrogen fluoride in ammonium fluoride solution, and anhydrous hydrogen fluoride is well mixed with ammonium fluoride solution, fully reaction, until solution PH reaches 2~4, the ammonium hydrogen fluoride solution that mass concentration is 21~37% is obtained；Mix with the ammonium acid fluoride mother liquor after crystallization, carry out three-effect evaporation and condensation, be 60~80% until the concentration of ammonium acid fluoride reaches mass concentration；Deliver in crystallizer, crystallisation by cooling 3h~7h obtains ammonium acid fluoride solidliquid mixture；Isolated ammonium acid fluoride product and ammonium acid fluoride mother liquor.Because ammonium acid fluoride is easily decomposed in the hot water, therefore during concentration ammonium hydrogen fluoride solution, ammonium acid fluoride is decomposed reaction, and a large amount of hydrogen fluoride, ammonia volatilize so as to produce substantial amounts of fluorine ammonium cold water with vapor, and the various impurity of fluosilicic acid institute band fully enter ammonium acid fluoride product.The ammonium fluoride solution obtained after the ammonium fluosilicate ammonolysis that " a kind of preparation method of ammonium acid fluoride " is mentioned in the patent CN1554586A of Yunnan Prov Sanhuan Chemical Co., Ltd and Tianjin Chemical Research ＆ Desing Inst joint application is concentrated, dry, that is, obtain required ammonium acid fluoride product；There are the following problems for the technique, and one is that, because ammonium fluoride is extremely easy in decomposition in the hot water, a large amount of hydrogen fluoride, ammonia volatilize so as to produce substantial amounts of fluorine ammonium condensed water with vapor；Two be ammonium fluoride directly concentration obtain be ammonium fluoride and ammonium acid fluoride mixture, three is during various impurity in the entrance ammonium fluoride solution of fluosilicic acid institute band enter ammonium acid fluoride product.
The technology of ammonium acid fluoride is produced using fluorine-containing discarded absorbing liquid or fluosilicic acid at present, it is to be carried out a step ammonolysis into ammonium fluoride and silica, ammonium fluoride solution is obtained after being filtered to remove silica, hydrogen fluoride is added after ammonium acid fluoride or concentration will be obtained after ammonium fluoride solution heating concentration to obtain ammonium acid fluoride or concentrated again after first adding hydrogen fluoride production ammonium acid fluoride, a large amount of fluorine-containing ammonium waste water can be produced because ammonium fluoride is unstable in the hot water, during evaporation and concentration.Ammonium fluoride solution is directly thickened to crystallization, that is, material still solvable in ammonium fluoride solution after fluosilicic acid ammonolysis can enter ammonium acid fluoride product, mainly including phosphorus, silicon, iron etc..
The content of the invention
It is an object of the invention to provide a kind of technical method that high-quality ammonium acid fluoride is prepared using fluorine-containing discarded absorbing liquid or fluosilicic acid, high-quality ammonium acid fluoride is prepared using anhydrous hydrogen fluoride and ammonium fluoride solid reaction.
The method that a kind of fluorosilicone compound of the present invention prepares high-quality ammonium acid fluoride, by solid fluosilicic acid or silicon tetrafluoride gas, it is added in saturation ammonium fluoride solution, being passed through excess of ammonia carries out ammonolysis reaction simultaneously, after question response is complete, respectively obtain ammonium fluoride magma and silica suspension, it is characterized in that following these steps to carry out (1) successively allows ammonium fluoride magma and silica suspension material natural subsidence in subsider, the ammonium fluoride crystal on subsider upper strata is taken out, centrifugal dehydration obtains solid fluorinated ammonium, as production ammonium acid fluoride NH4HF2Raw material (2) in the closed reactor of inner lining fluoroplastics, add pH=1~5 NH4F-NH4HF2Reaction solution or NH4HF2Be added to solid fluorinated ammonium NH4F raw materials in the reaction solution of above-mentioned steps (2) by reaction solution (3)；NH4F solids add 5%~50% (4) that weight is reaction solution to add hydrogen fluoride HF under agitation, make reaction solution pH=1~5, and NH is separated out in reactor4HF2Crystal (5) question response liquid temperature degree is down to the material released in reactor after environment temperature, is filtrated to get ammonium acid fluoride NH4HF2 crystal and NH4F-NH4HF2 solution or NH4HF2 solution, ammonium acid fluoride NH4HF2Crystal can obtain high-quality ammonium acid fluoride product after drying；(6) by step (5) gained NH4F-NH4HF2Solution or NH4HF2Solution return to step (2), and supplement step (5) operation in cause NH4F-NH4HF2 reaction solutions or NH4HF2The loss amount of reaction solution.
The NH4F-NH caused in supplement step (5) operation4HF2Reaction solution or NH4HF2The method of reaction solution loss amount is in NH4F-NH4HF2Reaction solution or NH4HF2Pure water is added in reaction solution, its volume is added to and step (2) NH4F-NH4HF2Reaction solution or NH4HF2Reaction solution volume is equal, while being passed through hydrogen fluoride, makes NH4F-NH4HF2Reaction solution or NH4HF2Reaction solution pH=1~5.
Because liquid-fluorination hydrogen is expensive, in order to reduce the consumption of liquid-fluorination hydrogen in step (4), pure water can be replaced with the aqueous solution containing hydrogen fluoride, make NH4F-NH4HF2Reaction solution or NH4HF2The volume of reaction solution is equal with step (2), while being passed through HF, makes NH4F-NH4HF2Reaction solution or NH4HF2Reaction solution pH=1~5.
The hydrogen fluoride HF that step (4) is passed through is to be passed through in the form of a gas or liquid.
Optimum condition is that step (3) NH4F solids addition weight is the 10%~30% of reaction solution；Step (4) pH=2~4.
The technology of the present invention advantage is that water in fluorine-containing discarded absorbing liquid or fluosilicic acid is removed in ammonium fluosilicate preparatory phase, is only a small amount of fluorine compounds that liquid foam is taken out of in the waste water for evaporating because ammonium fluosilicate stability in the hot water is better than ammonium fluoride.Need not be concentrated in ammonium acid fluoride preparatory phase, fluorine-containing weak aqua ammonia will not be produced.The ammonium fluoride raw material for using is taken from the ammonium fluoride crystal on ammonolysis reaction system upper strata, and the impurity in ammonolysis reaction system is remained predominantly in silica and reaction solution, and the impurity content in ammonium fluoride crystal is very low, it is easier to produce the ammonium acid fluoride product of high-quality.
The present invention solves the problems, such as the fluoride pollution in the production of production of phosphate fertilizer enterprise, fluorine resource is recycled utilization；Circulate operation of the present invention, does not increase the three wastes newly；The present invention replaces part anhydrous hydrogen fluoride, reduces cost using aqueous hydrogen fluoride solution.
Specific embodiment
Embodiment 1
The NH4F-NH that pH value is 2~4 is added in the closed reactor of inner lining fluoroplastics4HF2Reaction solution 350g, add the ammonium fluoride solid 60g that NH4F mass fractions are 95%, the rotating speed for setting agitator is more than 500r/min, hydrogen fluoride 31g, pure water 9g are added, temperature of charge gives free rein to raise and reduces during charging, after hydrogen to be fluorinated is added, reaction mass is cooled to residing environment temperature, ammonium acid fluoride crystal is filtrated to get, ammonium acid fluoride product is obtained after drying.Filtrate is NH4F-NH that pH value is 1~54HF2Reaction solution, filtrate cycle uses.Experiment obtains ammonium acid fluoride filter cake about 100g, filtrate about 350g.After ammonium fluoride filtration cakes torrefaction, NH is obtained4HF2Content is 97% ammonium acid fluoride product 90.5g.
Embodiment 2
The NH4F-NH that pH value is 1~5 is added in the closed reactor of inner lining fluoroplastics4HF2Reaction solution 350g, add the ammonium fluoride solid 60g that NH4F mass fractions are 95%, the rotating speed for setting agitator is more than 500r/min, the hydrofluoric acid 18g that hydrogen fluoride 22g, HF content is 50% is added, temperature of charge gives free rein to raise and reduces during charging, after hydrogen to be fluorinated is added, reaction mass is cooled to residing environment temperature, ammonium acid fluoride crystal is filtrated to get, ammonium acid fluoride product is obtained after drying.Filtrate is NH4F-NH that pH value is 1~54HF2Reaction solution, filtrate cycle uses.Experiment obtains ammonium acid fluoride filter cake about 98g, filtrate about 352g.After ammonium fluoride filtration cakes torrefaction, NH is obtained4HF2Content is 97% ammonium acid fluoride product 90g.
Embodiment 3
The NH4F-NH that pH value is 2~4 is added in the closed reactor of inner lining fluoroplastics4HF2Reaction solution 350g, add the ammonium fluoride solid 60g that NH4F mass fractions are 95%, the rotating speed for setting agitator is more than 500r/min, the hydrofluoric acid 14g that hydrogen fluoride 26g, HF content is 35% is added, temperature of charge gives free rein to raise and reduces during charging, after hydrogen to be fluorinated is added, reaction mass is cooled to residing environment temperature, ammonium acid fluoride crystal is filtrated to get, ammonium acid fluoride product is obtained after drying.Filtrate is NH4F-NH that pH value is 1~54HF2Reaction solution, filtrate cycle uses.Experiment obtains ammonium acid fluoride filter cake about 100g, filtrate about 350g.After ammonium fluoride filtration cakes torrefaction, NH is obtained4HF2Content is 97% ammonium acid fluoride product 90.5g.
Embodiment 4
The NH4F-NH that pH value is 2~4 is added in the closed reactor of inner lining fluoroplastics4HF2Reaction solution 350g, add the ammonium fluoride solid 60g that NH4F mass fractions are 95%, the rotating speed for setting agitator is more than 500r/min, the hydrofluoric acid 18g that hydrogen fluoride 27g, HF content is 50% is added, temperature of charge gives free rein to raise and reduces during charging, after hydrogen to be fluorinated is added, reaction mass is cooled to residing environment temperature, ammonium acid fluoride crystal is filtrated to get, ammonium acid fluoride product is obtained after drying.Filtrate is NH4F-NH that pH value is 44HF2Reaction solution, filtrate cycle uses.Experiment obtains ammonium acid fluoride filter cake about 118g, filtrate about 337g.After ammonium fluoride filtration cakes torrefaction, NH is obtained4HF2Content is 97% ammonium acid fluoride product 107g.
Embodiment 5
The NH4F-NH that pH value is 1~5 is added in the closed reactor of inner lining fluoroplastics4HF2Reaction solution 350g, add the ammonium fluoride solid 60g that NH4F mass fractions are 95%, the rotating speed for setting agitator is more than 500r/min, the hydrofluoric acid 18g that hydrogen fluoride 17g, HF content is 50% is added, temperature of charge gives free rein to raise and reduces during charging, after hydrogen to be fluorinated is added, reaction mass is cooled to residing environment temperature, ammonium acid fluoride crystal is filtrated to get, ammonium acid fluoride product is obtained after drying.Filtrate is NH4F-NH that pH value is 1~54HF2Reaction solution, filtrate cycle uses.Experiment obtains ammonium acid fluoride filter cake about 78g, filtrate about 367g.After ammonium fluoride filtration cakes torrefaction, NH is obtained4HF2Content is 97% ammonium acid fluoride product 70.5g.
Claims (3)
1. a kind of method that fluorosilicone compound prepares high-quality ammonium acid fluoride, including solid fluosilicic acid is added in saturation ammonium fluoride solution, being passed through excess of ammonia carries out ammonolysis reaction simultaneously, after question response is complete, ammonium fluoride magma and silica suspension are respectively obtained, it is characterized in that following these steps to carry out successively：(1) allow ammonium fluoride magma and silica suspension material natural subsidence in subsider, the ammonium fluoride crystal on subsider upper strata is taken out, centrifugal dehydration obtains solid fluorinated ammonium, as production ammonium acid fluoride NH4F-NH4HF2Raw material；(2) in the closed reactor of inner lining fluoroplastics, the NH of pH=1~5 is added4F-NH4HF2Reaction solution or NH4HF2Reaction solution；(3) by solid fluorinated ammonium NH4F raw materials are added in the reaction solution of above-mentioned steps (2)；NH4It is the 10%~30% of reaction solution that F solids add weight；(4) hydrogen fluoride HF is added in the case where agitator speed is for the stirring condition of more than 500r/min, temperature of charge gives free rein to raise and reduces during charging, makes reaction solution pH=2~4, and NH is separated out in reactor4HF2Crystal；(5) question response liquid temperature degree is down to the material released in reactor after environment temperature, is filtrated to get ammonium acid fluoride NH4HF2Crystal and NH4F-NH4HF2Solution or NH4HF2Solution, ammonium acid fluoride NH4HF2Crystal can obtain high-quality ammonium acid fluoride product after drying；(6) by step (5) gained NH4F-NH4HF2Solution or NH4HF2Solution return to step (2), and supplement step (5) operation in cause NH4F-NH4HF2Reaction solution or NH4HF2The loss amount of reaction solution.
2. the method that a kind of fluorosilicone compound as claimed in claim 1 prepares high-quality ammonium acid fluoride, it is characterized in that the NH caused in supplement step (5) operation4F-NH4HF2Reaction solution or NH4HF2The method of reaction solution loss amount is in NH4F-NH4HF2Reaction solution or NH4HF2Pure water is added in reaction solution, its volume is added to and step (2) NH4F-NH4HF2Reaction solution or NH4HF2Reaction solution volume is equal, while being passed through hydrogen fluoride, makes NH4F-NH4HF2Reaction solution or NH4HF2Reaction solution pH=1~5；The hydrogen fluoride HF that step (4) is passed through is to be passed through in the form of a gas or liquid.
3. the method that a kind of fluorosilicone compound as claimed in claim 1 prepares high-quality ammonium acid fluoride, it is characterized in that the consumption in order to reduce step (4) hydrogen fluoride, can replace pure water with the aqueous solution containing hydrogen fluoride, makes NH4F-NH4HF2Reaction solution or NH4HF2The volume of reaction solution is equal with step (2), while being passed through HF, makes NH4F-NH4HF2 reaction solutions or NH4HF2Reaction solution pH=1~5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108439365A (en) * | 2018-05-10 | 2018-08-24 | 湖北祥云(集团)化工股份有限公司 | A kind of method that sylvite circular treatment fluosilicic acid prepares ammonium acid fluoride |
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| CN108439365A (en) * | 2018-05-10 | 2018-08-24 | 湖北祥云(集团)化工股份有限公司 | A kind of method that sylvite circular treatment fluosilicic acid prepares ammonium acid fluoride |
| CN108439365B (en) * | 2018-05-10 | 2019-11-12 | 湖北祥云(集团)化工股份有限公司 | A kind of method that sylvite circular treatment fluosilicic acid prepares ammonium acid fluoride |
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Application publication date: 20170524 |