CN102976356A - 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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CN102976356A
CN102976356A CN2012105454389A CN201210545438A CN102976356A CN 102976356 A CN102976356 A CN 102976356A CN 2012105454389 A CN2012105454389 A CN 2012105454389A CN 201210545438 A CN201210545438 A CN 201210545438A CN 102976356 A CN102976356 A CN 102976356A
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reaction solution
ammonium
solution
fluoride
ammonium bifluoride
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CN102976356B (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 the chemical field, relate in particular to a kind of technological method that utilizes fluorine-containing discarded absorption liquid or silicofluoric acid to prepare ammonium bifluoride.
Background technology:Ammonium bifluoride mainly is used as clean-out system, fermentation industry sterilizing agent and the silicon element surface of steel plate treatment agent of solvent, chemical reagent, boiler feed water system and the steam generating system of glass etching agent, sanitas, beryllium oxide metallic beryllium processed, the oxygenant of making 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 when surface treatment agent of silicon element steel plate and aluminium shape surface are processed etc.Ammonium bifluoride with high purity also can be used for electronics, reagent and pharmaceutical industries.In recent years bring into use ammonium bifluoride and make etching reagent along with the aluminium surface decoration tech, 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 two kinds of direct method and indirect methods, and directly sending out is with high-purity hydrogen fluoride and high-purity ammon direct reaction production ammonium bifluoride, quality product is very high, and external form is the flap after the melting.Indirect method (liquid phase method) adopts hydrogen fluoride and ammonia to generate ammonium bifluoride in the aqueous solution, then produces ammonium bifluoride by crystallization, separation, dry method.
In domestic hydrofluoric acid (anhydrous hydrogen fluoride) production technique, at present only urn good fortune in Guizhou has one take the production line of silicofluoric acid as raw material production hydrofluoric acid, and other are all take Fluorspar Powder and sulfuric acid as raw material production.And fluorite is a kind of non-renewable strategic resources, though once there was abundant storage in China, but also be 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 quota exports relevant policies such as (export quotas are also reducing year by year).Along with the minimizing of fluorite resource, the Fluorspar Powder supply is becoming tight day, and the price of Fluorspar Powder is also high with one the tunnel, and this will make Fluorspar Powder-Production By Sulfuric Acid Process hydrofluoric acid or anhydrous hydrogen fluoride be subject to greatly restriction even stop production.Therefore, utilize expensive, hard-won hydrogen fluoride to remove to produce ammonium bifluoride fully, just seem economical not.Producing the 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.
It is more at present to produce the technology of ammonium bifluoride with the silicofluoric acid of phosphatic fertilizer company by-product, but all be to adopt variety of way to concentrate ammonium fluoride solution in the ammonium bifluoride production process, obtain the ammonium bifluoride product, will produce a large amount of fluorine-containing weak ammonias at the concentrated initial stage like this, later stage decomposes because Neutral ammonium fluoride is a large amount of and volatilizes concentration systems, Crystallization Plugging pipeline again in exhaust system." a kind of production method of ammonium bifluoride with high purity " mentioned in patent CN101898769A number of Duo-fluoride Chemicals Co., Ltd. application in the Neutral ammonium fluoride reaction solution, and logical anhydrous hydrogen fluoride prepares ammonium bifluoride, and its raw material Neutral ammonium fluoride is made through the ammonia solution by the silicofluoric acid of phosphate fertilizer industry by-product; In fact be to be not easy directly to obtain the Neutral ammonium fluoride reaction solution by silicofluoric acid ammonia solution, and the water that brings in the silicofluoric acid raw material how to leave aborning system also undeclared; If obtain the Neutral ammonium fluoride reaction solution after concentrated with the ammonium fluoride solution after the ammonia solution, just have a large amount of fluorine-containing ammonium water of condensation, and silicofluoric acid with various impurity all enter in the ammonium bifluoride product." a kind of reclaim the method that the fluorine resource is produced ammonium bifluoride in the fluorine-containing white residue " mentions in patent CN102491370A number of Wengfu Group Co., Ltd. application passes into anhydrous hydrogen fluoride in ammonium fluoride solution, and anhydrous hydrogen fluoride and ammonium fluoride solution are mixed, fully reaction, until solution PH reaches 2～4, obtain mass concentration and be 21～37% ammonium hydrogen fluoride solution; Mixing with the ammonium bifluoride mother liquor after the crystallization, carry out three-effect evaporation and condensation, is 60～80% until the concentration of ammonium bifluoride reaches mass concentration; Deliver in the crystallizer, crystallisation by cooling 3h～7h obtains the ammonium bifluoride solidliquid mixture; Separate and obtain ammonium bifluoride product and ammonium bifluoride mother liquor.Because ammonium bifluoride easily decomposes in hot water, during therefore concentrated ammonium hydrogen fluoride solution, ammonium bifluoride generation decomposition reaction, thus a large amount of hydrogen fluoride, ammonia produce a large amount of fluorine ammonium water of condensation with the water vapour volatilization, and silicofluoric acid with various impurity all enter in the ammonium bifluoride product.The ammonium fluoride solution that obtains after the ammonium silicofluoride ammonia solution that " a kind of preparation method of ammonium bifluoride " mentions in the patent CN1554586A of Yunnan Prov Sanhuan Chemical Co., Ltd and Tianjin Chemical Research ﹠ Desing Inst co-applications number namely obtains required ammonium bifluoride product through concentrated, dry; There are the following problems for this technique, and the one, because Neutral ammonium fluoride very easily decomposition in hot water, thereby hydrogen fluoride, ammonia produce a large amount of fluorine ammonium water of condensation with the water vapour volatilization in a large number; The 2nd, Neutral ammonium fluoride directly concentrated obtaining is the mixture of Neutral ammonium fluoride and ammonium bifluoride, the 3rd, silicofluoric acid with the various impurity that enter in the ammonium fluoride solution all entered in the ammonium bifluoride product.
Use at present fluorine-containing discarded absorption liquid or silicofluoric acid to produce the technology of ammonium bifluoride, all be it to be carried out a step ammonia solution become Neutral ammonium fluoride and silicon-dioxide, obtain ammonium fluoride solution after removing by filter silicon-dioxide, obtain after ammonium fluoride solution heating is concentrated ammonium bifluoride or concentrated after add again hydrogen fluoride obtain ammonium bifluoride or add first the hydrogen fluoride production ammonium bifluoride after reconcentration, because Neutral ammonium fluoride is unstable in hot water, can produce a large amount of fluorine-containing ammonium waste water during evaporation concentration.Ammonium fluoride solution directly is concentrated into crystallization, namely after the silicofluoric acid ammonia solution in ammonium fluoride solution still soluble material all can enter the ammonium bifluoride product, mainly comprise phosphorus, silicon, iron etc.
Fluorine-containing discarded absorption liquid or silicofluoric acid mainly come from phosphatic fertilizer company at present.The technology of producing ammonium bifluoride with silicofluoric acid is more, but all be that fluorine-containing discarded absorption liquid or the silicofluoric acid that concentration is rarer obtains 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 the ammonium bifluoride product.Therefore the contained large water gaging of rare Neutral ammonium fluoride needs evaporation concentration, derives two kinds of techniques, one of be that the Neutral ammonium fluoride dilute solution concentrates afterwards first and neutralizes, two be that the Neutral ammonium fluoride dilute solution neutralizes first and concentrates afterwards.The main drawback of these existing Technologies: the one, in rare Neutral ammonium fluoride or rare ammonium bifluoride evaporating concentration process, decomposition reaction can occur, thereby a large amount of hydrogen fluoride, ammonia produce the fluorine ammonium water of condensation of a large amount of fluorinated ammoniums, ammonium hydroxide or ammonium bifluoride composition with the water vapour volatilization.And if control in the concentrated later stage and badly may cause a large amount of distillations of Neutral ammonium fluoride or ammonium bifluoride and to stop up the gas phase pipeline.Neutral ammonium fluoride in the fluorine ammonium water of condensation that prior art produces and ammonium hydroxide or ammonium bifluoride composition are not easy to be recycled, and all higher as investment and the working cost of wastewater treatment; The 2nd, fluorine-containing discarded absorption liquid or silicofluoric acid with various impurity all enter in the ammonium bifluoride product, reduced product quality.Technical problem to be solved by this invention namely is to eliminate the generation of fluorine ammonium water of condensation and produce high-quality ammonium bifluoride product.
Summary of the invention:
The purpose of this invention is to provide a kind of technological method that utilizes fluorine-containing discarded absorption liquid or silicofluoric acid to prepare 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, the patent applied for CN18840773B of unit number " a kind of ammonia solution of fluorosilicone compound and the separation method of fluorine element silicon " is described with solid silicofluoric acid or silicon tetrafluoride gas to comprise me, be added in the saturated ammonium fluoride solution, pass into simultaneously excess of ammonia and carry out ammonolysis reaction, after question response is complete, obtain respectively Neutral ammonium fluoride magma and silicon-dioxide suspension liquid, 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 gets the solid Neutral ammonium fluoride, as producing ammonium bifluoride NH 4HF 2Raw material; (2) in the closed reactor of inner lining fluoroplastics, add the NH of pH=1～5 4F-NH 4HF 2Reaction solution or NH 4HF 2Reaction solution; (3) with solid Neutral ammonium fluoride NH 4The F raw material joins in the reaction solution of above-mentioned steps (2); NH 4It is 5%～50% of reaction solution that the F solid adds weight; (4) under agitation add hydrogen fluoride HF, make reaction solution pH=1～5, separate out NH in the reactor 4HF 2Crystal; (5) the question response liquid temp is down to the material of emitting after the envrionment temperature in the reactor, filters to obtain 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) with 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 that causes 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 the reaction solution, its volume adds to and step (2) NH 4F-NH 4HF 2Reaction solution or NH 4HF 2The reaction solution volume equates, passes into simultaneously hydrogen fluoride, 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, can replace pure water with the aqueous solution of fluorinated hydrogen in the step (4), make NH 4F-NH 4HF 2Reaction solution or NH 4HF 2The volume of reaction solution equates with step (2), passes into simultaneously HF, makes NH 4F-NH 4HF 2Reaction solution or NH 4HF 2Reaction solution pH=1～5.
The hydrogen fluoride HF that step (4) passes into is that the form with gas or liquid passes into.
Optimum condition is step (3) NH 4It is 10%～30% of reaction solution that the F solid adds weight; Step (4) pH=2～4.
The technology of the present invention is to combine with last patent CN18840773B number " a kind of ammonia solution of fluorosilicone compound and the separation method of fluorine element silicon " of our unit, produces one of fluorine chemical series product.Its advantage is that the water in fluorine-containing discarded absorption liquid or the silicofluoric acid is removed at the ammonium silicofluoride preparatory phase, because the stability of ammonium silicofluoride in hot water is better than Neutral ammonium fluoride, only is a small amount of fluorine cpd that the liquid foam is taken out of in the waste water that evaporates.Do not need to concentrate at the ammonium bifluoride preparatory phase, can not produce fluorine-containing weak ammonia.The Neutral ammonium fluoride raw material that uses is the Neutral ammonium fluoride crystal of taking from ammonolysis reaction system upper strata, and the impurity in the ammonolysis reaction system is mainly stayed in silicon-dioxide and the reaction solution, and the foreign matter content in the Neutral ammonium fluoride crystal is very low, produces high-quality ammonium bifluoride product easilier.
The invention solves the fluoride pollution problem in the production of production of phosphate fertilizer enterprise, make the 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 the part anhydrous hydrogen fluoride, reduces cost.
Embodiment
Embodiment 1
Adding pH value is 2～4 NH in the closed reactor of inner lining fluoroplastics 4F-NH 4HF 2Reaction solution 350g, add NH 4The F massfraction is 95% Neutral ammonium fluoride solid 60g, the rotating speed that agitator is set is more than the 500r/min, add hydrogen fluoride 31g, pure water 9g, temperature of charge gives free rein to raise and reduce in the reinforced process, after hydrogen fluoride adds, reaction mass is cooled to residing envrionment temperature, filtration obtains the ammonium bifluoride crystal, obtains the ammonium bifluoride product after the drying.Filtrate is that the pH value is 1～5 NH 4F-NH 4HF 2Reaction solution, filtrate cycle is used.Experiment obtains the about 100g of ammonium bifluoride filter cake, the about 350g of filtrate.Behind the Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4HF 2Content is 97% ammonium bifluoride product 90.5g.
Embodiment 2
Adding pH value is 1～5 NH in the closed reactor of inner lining fluoroplastics 4F-NH 4HF 2Reaction solution 350g, add NH 4The F massfraction is 95% Neutral ammonium fluoride solid 60g, the rotating speed that agitator is set is more than the 500r/min, add hydrogen fluoride 22g, HF content is 50% hydrofluoric acid 18g, temperature of charge gives free rein to raise and reduce in the reinforced process, after hydrogen fluoride adds, reaction mass is cooled to residing envrionment temperature, filtration obtains the ammonium bifluoride crystal, obtains the ammonium bifluoride product after the drying.Filtrate is that the pH value is 1～5 NH 4F-NH 4HF 2Reaction solution, filtrate cycle is used.Experiment obtains the about 98g of ammonium bifluoride filter cake, the about 352g of filtrate.Behind the Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4HF 2Content is 97% ammonium bifluoride product 90g.
 
Embodiment 3
Adding pH value is 2～4 NH in the closed reactor of inner lining fluoroplastics 4F-NH 4HF 2Reaction solution 350g, add NH 4The F massfraction is 95% Neutral ammonium fluoride solid 60g, the rotating speed that agitator is set is more than the 500r/min, add hydrogen fluoride 26g, HF content is 35% hydrofluoric acid 14g, temperature of charge gives free rein to raise and reduce in the reinforced process, after hydrogen fluoride adds, reaction mass is cooled to residing envrionment temperature, filtration obtains the ammonium bifluoride crystal, obtains the ammonium bifluoride product after the drying.Filtrate is that the pH value is 1～5 NH 4F-NH 4HF 2Reaction solution, filtrate cycle is used.Experiment obtains the about 100g of ammonium bifluoride filter cake, the about 350g of filtrate.Behind the Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4HF 2Content is 97% ammonium bifluoride product 90.5g.
Embodiment 4
Adding pH value is 2～4 NH in the closed reactor of inner lining fluoroplastics 4F-NH 4HF 2Reaction solution 350g, add NH 4The F massfraction is 95% Neutral ammonium fluoride solid 60g, the rotating speed that agitator is set is more than the 500r/min, add hydrogen fluoride 27g, HF content is 50% hydrofluoric acid 18g, temperature of charge gives free rein to raise and reduce in the reinforced process, after hydrogen fluoride adds, reaction mass is cooled to residing envrionment temperature, filtration obtains the ammonium bifluoride crystal, obtains the ammonium bifluoride product after the drying.Filtrate is that the pH value is 4 NH 4F-NH 4HF 2Reaction solution, filtrate cycle is used.Experiment obtains the about 118g of ammonium bifluoride filter cake, the about 337g of filtrate.Behind the Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4HF 2Content is 97% ammonium bifluoride product 107g.
Embodiment 5
Adding pH value is 1～5 NH in the closed reactor of inner lining fluoroplastics 4F-NH 4HF 2Reaction solution 350g, add NH 4The F massfraction is 95% Neutral ammonium fluoride solid 60g, the rotating speed that agitator is set is more than the 500r/min, add hydrogen fluoride 17g, HF content is 50% hydrofluoric acid 18g, temperature of charge gives free rein to raise and reduce in the reinforced process, after hydrogen fluoride adds, reaction mass is cooled to residing envrionment temperature, filtration obtains the ammonium bifluoride crystal, obtains the ammonium bifluoride product after the drying.Filtrate is that the pH value is 1～5 NH 4F-NH 4HF 2Reaction solution, filtrate cycle is used.Experiment obtains the about 78g of ammonium bifluoride filter cake, the about 367g of filtrate.Behind the Neutral ammonium fluoride filtration cakes torrefaction, obtain NH 4HF 2Content is 97% ammonium bifluoride product 70.5g.

Claims (5)

1. a fluorosilicone compound prepares the method for high-quality ammonium bifluoride, comprise solid silicofluoric acid or silicon tetrafluoride gas, be added in the saturated ammonium fluoride solution, pass into simultaneously excess of ammonia and carry out ammonolysis reaction, after question response is complete, obtain respectively Neutral ammonium fluoride magma and silicon-dioxide suspension liquid, 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 gets the solid Neutral ammonium fluoride, as producing ammonium bifluoride NH 4HF 2Raw material; (2) in the closed reactor of inner lining fluoroplastics, add the NH of pH=1～5 4F-NH 4HF 2Reaction solution or NH 4HF 2Reaction solution; (3) with solid Neutral ammonium fluoride NH 4The F raw material joins in the reaction solution of above-mentioned steps (2); NH 4It is 5%～50% of reaction solution that the F solid adds weight; (4) under agitation add hydrogen fluoride HF, make reaction solution pH=1～5, separate out NH in the reactor 4HF 2Crystal; (5) the question response liquid temp is down to the material of emitting after the envrionment temperature in the reactor, filters to obtain 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) with 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.
2. a kind of fluorosilicone compound according to claim 1 prepares the method for high-quality ammonium bifluoride, it is characterized in that the NH that causes in 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 the reaction solution, its volume adds to and step (2) NH 4F-NH 4HF 2Reaction solution or NH 4HF 2The reaction solution volume equates, passes into simultaneously hydrogen fluoride, makes NH 4F-NH 4HF 2Reaction solution or NH 4HF 2Reaction solution pH=1～5.
3. a kind of fluorosilicone compound as claimed in claim 2 prepares the method for high-quality ammonium bifluoride, it is characterized in that can replacing pure water with the aqueous solution of fluorinated hydrogen in order to reduce the hydrofluoric consumption of step (4), makes NH 4F-NH 4HF 2Reaction solution or NH 4HF 2The volume of reaction solution equates with step (2), passes into simultaneously HF, makes NH 4F-NH 4HF 2Reaction solution or NH 4HF 2Reaction solution pH=1～5.
4. a kind of fluorosilicone compound as claimed in claim 1 or 2 prepares the method for high-quality ammonium bifluoride, it is characterized in that hydrogen fluoride HF that step (4) passes into is that form with gas or liquid passes into.
5. a kind of fluorosilicone compound as claimed in claim 1 prepares the method for high-quality ammonium bifluoride, it is characterized in that optimum condition is step (3) NH 4It is 10%～30% of reaction solution that the F solid adds weight; Step (4) pH=2～4.
CN201210545438.9A 2012-12-17 2012-12-17 Method for preparing high-quality ammonium hydrogen fluoride from fluorine and silicon compound Active CN102976356B (en)

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CN107934988A (en) * 2017-12-14 2018-04-20 江西渠成氟化学有限公司 A kind of preparation method of ammonium acid fluoride

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