CN102976356B - Method for preparing high-quality ammonium hydrogen fluoride from fluorine and silicon compound - Google Patents

Method for preparing high-quality ammonium hydrogen fluoride from fluorine and silicon compound Download PDF

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CN102976356B
CN102976356B CN201210545438.9A CN201210545438A CN102976356B CN 102976356 B CN102976356 B CN 102976356B CN 201210545438 A CN201210545438 A CN 201210545438A CN 102976356 B CN102976356 B CN 102976356B
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ammonium
solution
fluoride
fluorine
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CN102976356A (en
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田娟
陈文兴
张筑南
周昌平
蒋仁波
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GUIZHOU PROVINCIAL INST OF CHEMICAL TECHNOLOGY
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Abstract

The invention provides a method for preparing high-quality ammonium hydrogen fluoride from a fluorine and silicon compound, and relates to a preparation technology of inorganic fluorine salt in fluorine chemical industry in the chemical field. The method provided by the invention comprises the following steps: adding solid fluosilicic acid or silicon tetrafluoride gas into a saturated ammonium fluoride solution, and simultaneously introducing excessive ammonia to perform ammonolysis reaction, thus respectively obtaining ammonium fluoride crystal paste and silicon dioxide suspension after the reaction is finished; and sequentially treating according to six steps stated in the specification, thus finally obtaining the high-quality ammonium hydrogen fluoride product, wherein the reaction solution returns to the system for recycling. According to the process technology provided by the invention, impurities carried by the raw materials are mainly left in silicon dioxide, thereby ensuring that the high-quality ammonium hydrogen fluoride product can be produced more easily. Meanwhile, the method solves the fluorine pollution problem in phosphate fertilizer enterprise production and ensures that fluorine resources can be recycled; and the recycling operation of the system can not cause the increase of three wastes.

Description

A kind of fluorosilicone compound prepares the method for high-quality ammonium bifluoride
Technical field
The present invention relates to the technology of preparing of fluorine chemical industry inorganic fluoride salt in chemical field, relate in particular to a kind of fluorine-containing discarded absorption liquid or silicofluoric acid of utilizing to prepare the technological method of ammonium bifluoride.
background technology:ammonium bifluoride is mainly used as glass etching agent, sanitas, the solvent of beryllium oxide metallic beryllium, chemical reagent, the clean-out system of boiler feed water system and steam generating system, fermentation industry sterilizing agent and silicon element surface of steel plate treatment agent, the oxygenant manufacturing pottery and aluminum magnesium alloy, organic synthesis fluorizating agent, electroplate liquid, the solvent of extraction rare elements, the acidification agent of oil field sandstone, the etching reagent the etc. when surface treatment agent of the plain steel plate of silicon and aluminium shape surface process.Ammonium bifluoride with high purity also can be used for electronics, reagent and pharmaceutical industries.In recent years along with aluminium surface decoration tech brings into use ammonium bifluoride to make etching reagent, its market requirement continues to increase.
At present, the raw materials for production of ammonium bifluoride are hydrofluoric acid (or anhydrous hydrogen fluoride) and ammoniacal liquor (or liquefied ammonia), and its technique comprises direct method and indirect method two kinds, and directly sending out is that high-purity hydrogen fluoride and high-purity ammon direct reaction are produced ammonium bifluoride, quality product is very high, and external form is the flap after melting.Indirect method (liquid phase method) adopts hydrogen fluoride and ammonia to generate ammonium bifluoride in aqueous, then produces ammonium bifluoride by crystallization, separation, dry method.
In domestic hydrofluoric acid (anhydrous hydrogen fluoride) production technique, only Guizhou Wengfu has one to take silicofluoric acid as the production line of raw material production hydrofluoric acid at present, other all with Fluorspar Powder and sulfuric acid for raw material production.And fluorite is a kind of non-renewable strategic resources, though once there was abundant storage in China, but be also faced with exhausted situation (particularly single rawore produces) at present, for this reason, country has carried out and has no longer provided new fluorite production licence, and carries out the relevant policies such as quota outlet (export quotas are also reducing year by year).Along with the minimizing of fluorite resource, day is becoming tight by Fluorspar Powder supply, and price Ye Jiang mono-tunnel of Fluorspar Powder is high, and this will make Fluorspar Powder-Production By Sulfuric Acid Process hydrofluoric acid or anhydrous hydrogen fluoride be subject to great restriction even to stop production.Therefore, utilize expensive, hard-won hydrogen fluoride to go to produce ammonium bifluoride completely, just seem economical not.Producing ammonium bifluoride product from the waste gas containing fluoride absorption liquid of phosphatic fertilizer company, is the trend of comprehensive utilization of resources and fluorine chemical development.
The technology that the silicofluoric acid of current use phosphatic fertilizer company by-product produces ammonium bifluoride is more, but be all in ammonium bifluoride production process ammonium fluoride solution adopted to concentrate in various manners, obtain ammonium bifluoride product, a large amount of fluorine-containing weak ammonias will be produced like this at the concentrated initial stage, later stage volatilizes concentration systems because Neutral ammonium fluoride decomposes in a large number, Crystallization Plugging pipeline again in exhaust system.The logical anhydrous hydrogen fluoride in Neutral ammonium fluoride reaction solution that in No. CN101898769A, the patent of Duo-fluoride Chemicals Co., Ltd.'s application, " a kind of production method of ammonium bifluoride with high purity " is mentioned prepares ammonium bifluoride, and its raw material fluorinated ammonium is obtained through ammonia solution by the silicofluoric acid of phosphate fertilizer industry by-product; In fact be not easy directly to obtain Neutral ammonium fluoride reaction solution by silicofluoric acid ammonia solution, and the water brought in silicofluoric acid raw material how to leave system aborning also undeclared; If obtain Neutral ammonium fluoride reaction solution after concentrated with the ammonium fluoride solution after ammonia solution, just there is a large amount of fluorine-containing ammonium water of condensation, and silicofluoric acid with various impurity all enter in ammonium bifluoride product.What in No. CN102491370A, the patent of Wengfu Group Co., Ltd.'s application, " a kind of method reclaiming fluorine resource production ammonium bifluoride in fluorine-containing white residue " was mentioned passes into anhydrous hydrogen fluoride in ammonium fluoride solution, and anhydrous hydrogen fluoride is mixed with ammonium fluoride solution, abundant reaction, until solution PH reaches 2 ~ 4, obtain the ammonium hydrogen fluoride solution that mass concentration is 21 ~ 37%; Mix with the ammonium bifluoride mother liquor after crystallization, carry out three-effect evaporation and condensation, until it is 60 ~ 80% that the concentration of ammonium bifluoride reaches mass concentration; Deliver in crystallizer, crystallisation by cooling 3h ~ 7h, obtain ammonium bifluoride solidliquid mixture; Separation obtains ammonium bifluoride product and ammonium bifluoride mother liquor.Because ammonium bifluoride easily decomposes in the hot water, therefore during concentrated ammonium hydrogen fluoride solution, ammonium bifluoride generation decomposition reaction, a large amount of hydrogen fluoride, ammonia with water vapour volatilization thus produce a large amount of fluorine ammonium water of condensation, and silicofluoric acid with various impurity all enter in ammonium bifluoride product.The ammonium fluoride solution obtained after the ammonium silicofluoride ammonia solution that in No. CN1554586A, the patent of Yunnan Prov Sanhuan Chemical Co., Ltd and Tianjin Chemical Research & Desing Inst co-applications, " a kind of preparation method of ammonium bifluoride " mentions, through concentrated, dry, namely obtains required ammonium bifluoride product; There are the following problems for this technique, and one is because Neutral ammonium fluoride very easily decomposes in the hot water, and a large amount of hydrogen fluoride, ammonia volatilize with water vapour thus produces a large amount of fluorine ammonium water of condensation; Two be Neutral ammonium fluoride directly concentrated obtaining be the mixture of Neutral ammonium fluoride and ammonium bifluoride, three are silicofluoric acid with the various impurity entered in ammonium fluoride solution all enter in ammonium bifluoride product.
The fluorine-containing discarded absorption liquid of current use or silicofluoric acid produce the technology of ammonium bifluoride, carried out a step ammonia solution to become Neutral ammonium fluoride and silicon-dioxide, cross after filtering silicon-dioxide and obtain ammonium fluoride solution, by obtain ammonium bifluoride after concentrated for ammonium fluoride solution heating or concentrated after add again hydrogen fluoride obtain ammonium bifluoride or first add hydrogen fluoride production ammonium bifluoride after reconcentration, because Neutral ammonium fluoride is unstable in the hot water, a large amount of fluorine-containing ammonium waste water during evaporation concentration, can be produced.Ammonium fluoride solution is directly concentrated into crystallization, and namely still solvable in ammonium fluoride solution after silicofluoric acid ammonia solution material all can enter ammonium bifluoride product, mainly comprises phosphorus, silicon, iron etc.
Current fluorine-containing discarded absorption liquid or silicofluoric acid mainly come from phosphatic fertilizer company.The technology that use silicofluoric acid produces ammonium bifluoride is more, but be all that fluorine-containing discarded absorption liquid rarer for concentration or silicofluoric acid are obtained rare ammonium fluoride solution by ammonolysis reaction, then carry out neutralization reaction with rare ammonium fluoride solution and hydrofluoric acid or hydrogen fluoride and produce ammonium bifluoride product.Large water gaging contained by rare Neutral ammonium fluoride needs evaporation concentration, therefore derives two kinds of techniques, one of be that Neutral ammonium fluoride dilute solution first concentrates and neutralizes afterwards, two be that Neutral ammonium fluoride dilute solution first neutralizes and concentrates afterwards.The main drawback of these existing Technologies: one is decomposition reaction can occur in rare Neutral ammonium fluoride or rare ammonium bifluoride evaporating concentration process, a large amount of hydrogen fluoride, ammonia volatilize with water vapour thus produce the fluorine ammonium water of condensation of a large amount of fluorinated ammoniums, ammonium hydroxide or ammonium bifluoride composition.And if the phase controls bad Neutral ammonium fluoride or the ammonium bifluoride of may causing and distils in a large number and block gas phase pipeline after concentration.Neutral ammonium fluoride in the fluorine ammonium water of condensation that prior art produces and ammonium hydroxide or ammonium bifluoride composition not easy to be recycled, and as the investment of wastewater treatment and working cost all higher; Two be fluorine-containing discarded absorption liquid or silicofluoric acid with various impurity all enter in ammonium bifluoride product, reduce product quality.Namely technical problem to be solved by this invention is eliminate the generation of fluorine ammonium water of condensation and production high-quality ammonium bifluoride product.
summary of the invention:
The object of this invention is to provide a kind of fluorine-containing discarded absorption liquid or silicofluoric acid of utilizing to prepare the technological method of high-quality ammonium bifluoride, use anhydrous hydrogen fluoride and Neutral ammonium fluoride solid reaction, prepare high-quality ammonium bifluoride.
A kind of fluorosilicone compound of the present invention prepares the method for high-quality ammonium bifluoride, comprise described in my No. CN18840773B, unit patent applied for " a kind of ammonia solution of fluorosilicone compound and the separation method of fluorine element silicon " by solid silicofluoric acid or silicon tetrafluoride gas, be added in saturated ammonium fluoride solution, pass into excess of ammonia simultaneously and carry out ammonolysis reaction, after question response is complete, obtain Neutral ammonium fluoride magma and silicon-dioxide suspension liquid respectively, it is characterized in that following these steps to successively carry out: (1) allows Neutral ammonium fluoride magma and silicon-dioxide suspension liquid material natural subsidence in subsider, the Neutral ammonium fluoride crystal on subsider upper strata is taken out, centrifuge dehydration obtains solid fluorinated ammonium, be used as to produce ammonium bifluoride NH 4hF 2raw material, (2) in the closed reactor of inner lining fluoroplastics, the NH of pH=1 ~ 5 is added 4f-NH 4hF 2reaction solution or NH 4hF 2reaction solution, (3) by solid fluorinated ammonium NH 4f raw material joins in the reaction solution of above-mentioned steps (2), NH 4f solid add that weight is reaction solution 5% ~ 50%, (4) under agitation add hydrogen fluoride HF, make reaction solution pH=1 ~ 5, in reactor, separate out NH 4hF 2crystal, (5) question response liquid temp releases the material in reactor after being down to envrionment temperature, filters and obtains ammonium bifluoride NH 4hF 2crystal and NH 4f-NH 4hF 2solution or NH 4hF 2solution, ammonium bifluoride NH 4hF 2crystal can obtain high-quality ammonium bifluoride product after drying, (6) by step (5) gained NH 4f-NH 4hF 2solution or NH 4hF 2solution returns step (2), and causes NH in replenish step (5) operation 4f-NH 4hF 2reaction solution or NH 4hF 2the loss amount of reaction solution.
The NH caused in described replenish step (5) operation 4f-NH 4hF 2reaction solution or NH 4hF 2the method of reaction solution loss amount is at NH 4f-NH 4hF 2reaction solution or NH 4hF 2add pure water in reaction solution, its volume adds to and step (2) NH 4f-NH 4hF 2reaction solution or NH 4hF 2reaction solution volume is equal, passes into hydrogen fluoride simultaneously, makes NH 4f-NH 4hF 2reaction solution or NH 4hF 2reaction solution pH=1 ~ 5.
Because liquid-fluorination hydrogen price is more expensive, in order to reduce the consumption of liquid-fluorination hydrogen in step (4), pure water can be replaced with the aqueous solution of fluorinated hydrogen, making NH 4f-NH 4hF 2reaction solution or NH 4hF 2the volume of reaction solution is equal with step (2), passes into HF simultaneously, makes NH 4f-NH 4hF 2reaction solution or NH 4hF 2reaction solution pH=1 ~ 5.
The hydrogen fluoride HF that step (4) passes into passes in the form of a gas or liquid.
Optimum condition is step (3) NH 4f solid add that weight is reaction solution 10% ~ 30%; Step (4) pH=2 ~ 4.
The technology of the present invention combines with No. CN18840773B, last the patent of our unit " a kind of ammonia solution of fluorosilicone compound and the separation method of fluorine element silicon ", produces one of fluorine chemical series product.Its advantage be water in fluorine-containing discarded absorption liquid or silicofluoric acid in the removing of ammonium silicofluoride preparatory phase, because ammonium silicofluoride stability is in the hot water better than Neutral ammonium fluoride, be only a small amount of fluorine cpd that liquid foam is taken out of in the waste water evaporated.Do not need to concentrate at ammonium bifluoride preparatory phase, fluorine-containing weak ammonia can not be produced.The Neutral ammonium fluoride raw material used is the Neutral ammonium fluoride crystal taking from ammonolysis reaction system upper strata, and the impurity in ammonolysis reaction system is mainly stayed in silicon-dioxide and reaction solution, and the foreign matter content in Neutral ammonium fluoride crystal is very low, more easily produces the ammonium bifluoride product of high-quality.
The invention solves the fluoride pollution problem in the production of production of phosphate fertilizer enterprise, make fluorine resource be recycled utilization; Cyclical operation of the present invention, the not newly-increased three wastes; The present invention uses aqueous hydrogen fluoride solution to replace part anhydrous hydrogen fluoride, reduces costs.
Embodiment
Embodiment 1
The NH that pH value is 2 ~ 4 is added in the closed reactor of inner lining fluoroplastics 4f-NH 4hF 2reaction solution 350g, add NH 4f massfraction is the Neutral ammonium fluoride solid 60g of 95%, the rotating speed arranging agitator is more than 500r/min, add hydrogen fluoride 31g, pure water 9g, in reinforced process, temperature of charge gives free rein to raise and reduce, and after hydrogen to be fluorinated adds, reaction mass is cooled to residing envrionment temperature, filtration obtains ammonium bifluoride crystal, obtains ammonium bifluoride product after drying.Filtrate to be pH value be 1 ~ 5 NH 4f-NH 4hF 2reaction solution, filtrate cycle use.Experiment obtains ammonium bifluoride filter cake and is about 100g, and filtrate is about 350g.After Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4hF 2content is the ammonium bifluoride product 90.5g of 97%.
Embodiment 2
The NH that pH value is 1 ~ 5 is added in the closed reactor of inner lining fluoroplastics 4f-NH 4hF 2reaction solution 350g, add NH 4f massfraction is the Neutral ammonium fluoride solid 60g of 95%, the rotating speed arranging agitator is more than 500r/min, add hydrogen fluoride 22g, HF content is the hydrofluoric acid 18g of 50%, in reinforced process, temperature of charge gives free rein to raise and reduce, and after hydrogen to be fluorinated adds, reaction mass is cooled to residing envrionment temperature, filtration obtains ammonium bifluoride crystal, obtains ammonium bifluoride product after drying.Filtrate to be pH value be 1 ~ 5 NH 4f-NH 4hF 2reaction solution, filtrate cycle use.Experiment obtains ammonium bifluoride filter cake and is about 98g, and filtrate is about 352g.After Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4hF 2content is the ammonium bifluoride product 90g of 97%.
Embodiment 3
The NH that pH value is 2 ~ 4 is added in the closed reactor of inner lining fluoroplastics 4f-NH 4hF 2reaction solution 350g, add NH 4f massfraction is the Neutral ammonium fluoride solid 60g of 95%, the rotating speed arranging agitator is more than 500r/min, add hydrogen fluoride 26g, HF content is the hydrofluoric acid 14g of 35%, in reinforced process, temperature of charge gives free rein to raise and reduce, and after hydrogen to be fluorinated adds, reaction mass is cooled to residing envrionment temperature, filtration obtains ammonium bifluoride crystal, obtains ammonium bifluoride product after drying.Filtrate to be pH value be 1 ~ 5 NH 4f-NH 4hF 2reaction solution, filtrate cycle use.Experiment obtains ammonium bifluoride filter cake and is about 100g, and filtrate is about 350g.After Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4hF 2content is the ammonium bifluoride product 90.5g of 97%.
Embodiment 4
The NH that pH value is 2 ~ 4 is added in the closed reactor of inner lining fluoroplastics 4f-NH 4hF 2reaction solution 350g, add NH 4f massfraction is the Neutral ammonium fluoride solid 60g of 95%, the rotating speed arranging agitator is more than 500r/min, add hydrogen fluoride 27g, HF content is the hydrofluoric acid 18g of 50%, in reinforced process, temperature of charge gives free rein to raise and reduce, and after hydrogen to be fluorinated adds, reaction mass is cooled to residing envrionment temperature, filtration obtains ammonium bifluoride crystal, obtains ammonium bifluoride product after drying.Filtrate to be pH value be 4 NH 4f-NH 4hF 2reaction solution, filtrate cycle use.Experiment obtains ammonium bifluoride filter cake and is about 118g, and filtrate is about 337g.After Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4hF 2content is the ammonium bifluoride product 107g of 97%.
Embodiment 5
The NH that pH value is 1 ~ 5 is added in the closed reactor of inner lining fluoroplastics 4f-NH 4hF 2reaction solution 350g, add NH 4f massfraction is the Neutral ammonium fluoride solid 60g of 95%, the rotating speed arranging agitator is more than 500r/min, add hydrogen fluoride 17g, HF content is the hydrofluoric acid 18g of 50%, in reinforced process, temperature of charge gives free rein to raise and reduce, and after hydrogen to be fluorinated adds, reaction mass is cooled to residing envrionment temperature, filtration obtains ammonium bifluoride crystal, obtains ammonium bifluoride product after drying.Filtrate to be pH value be 1 ~ 5 NH 4f-NH 4hF 2reaction solution, filtrate cycle use.Experiment obtains ammonium bifluoride filter cake and is about 78g, and filtrate is about 367g.After Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4hF 2content is the ammonium bifluoride product 70.5g of 97%.

Claims (2)

1. a fluorosilicone compound prepares the method for high-quality ammonium bifluoride, comprise and solid silicofluoric acid is added in saturated ammonium fluoride solution, pass into excess of ammonia simultaneously and carry out ammonolysis reaction, after question response is complete, obtain Neutral ammonium fluoride magma and silicon-dioxide suspension liquid respectively, it is characterized in that following these steps to successively carry out: (1) allows Neutral ammonium fluoride magma and silicon-dioxide suspension liquid material natural subsidence in subsider, the Neutral ammonium fluoride crystal on subsider upper strata is taken out, centrifuge dehydration obtains solid fluorinated ammonium, is used as to produce ammonium bifluoride NH 4f-NH 4hF 2raw material; (2) in the closed reactor of inner lining fluoroplastics, the NH of pH=1 ~ 5 is added 4f-NH 4hF 2reaction solution or NH 4hF 2reaction solution; (3) by solid fluorinated ammonium NH 4f raw material joins in the reaction solution of above-mentioned steps (2); NH 4f solid add that weight is reaction solution 10% ~ 30%; (4) at agitator speed be more than 500r/min agitation condition under add hydrogen fluoride HF, in reinforced process, temperature of charge gives free rein to raise and reduce, and makes reaction solution pH=2 ~ 4, separates out NH in reactor 4hF 2crystal; (5) question response liquid temp releases the material in reactor after being down to envrionment temperature, filters and obtains ammonium bifluoride NH 4hF 2crystal and NH 4f-NH 4hF 2solution or NH 4hF 2solution, ammonium bifluoride NH 4hF 2crystal can obtain high-quality ammonium bifluoride product after drying; (6) by step (5) gained NH 4f-NH 4hF 2solution or NH 4hF 2solution returns step (2), and causes NH in replenish step (5) operation 4f-NH 4hF 2reaction solution or NH 4hF 2the loss amount of reaction solution;
The NH caused in described replenish step (5) operation 4f-NH 4hF 2reaction solution or NH 4hF 2the method of reaction solution loss amount is at NH 4f-NH 4hF 2reaction solution or NH 4hF 2add pure water in reaction solution, its volume adds to and step (2) NH 4f-NH 4hF 2reaction solution or NH 4hF 2reaction solution volume is equal, passes into hydrogen fluoride simultaneously, makes NH 4f-NH 4hF 2reaction solution or NH 4hF 2reaction solution pH=1 ~ 5;
The hydrogen fluoride HF that step (4) passes into passes in the form of a gas or liquid.
2. a kind of fluorosilicone compound as claimed in claim 1 prepares the method for high-quality ammonium bifluoride, it is characterized in that to reduce step (4) hydrofluoric consumption, can replace pure water, make NH with the aqueous solution of fluorinated hydrogen 4f-NH 4hF 2reaction solution or NH 4hF 2the volume of reaction solution is equal with step (2), passes into HF simultaneously, makes NH 4f-NH 4hF 2reaction solution or NH 4hF 2reaction solution pH=1 ~ 5.
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CN105417556B (en) * 2015-12-16 2017-05-10 贵州川恒化工股份有限公司 Preparation method of ammonium bifluoride
CN106517244B (en) * 2016-10-21 2018-06-15 昆明培铭科技有限公司 The method that fluorine containing etchant waste liquid produces ammonium acid fluoride
CN107934988B (en) * 2017-12-14 2021-03-12 江西渠成氟化学有限公司 Preparation method of ammonium bifluoride

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