CN102976336B - Method for preparing ammonium fluosilicate solids from fluorosilicone compounds - Google Patents
Method for preparing ammonium fluosilicate solids from fluorosilicone compounds Download PDFInfo
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- CN102976336B CN102976336B CN201210565016.8A CN201210565016A CN102976336B CN 102976336 B CN102976336 B CN 102976336B CN 201210565016 A CN201210565016 A CN 201210565016A CN 102976336 B CN102976336 B CN 102976336B
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- ammonium silicofluoride
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Abstract
The invention relates to a method for preparing ammonium fluosilicate solids from fluorosilicone compounds. The method comprises the following steps of: mixing a fluorosilicone compound solution with the fluosilicic acid radical SiF6<2-> content of 3-40% and ammonia water or liquid ammonia or ammonium carbonate for reaction in a reaction tank, wherein the end point of reaction control is that the pH value of the reaction liquid ranges from 0.5 to 3; feeding the reaction liquid into an evaporation and concentration system, simultaneously adding hydrofluoric acid or an ammonium fluoride solution or ammonium fluoride solids into the reaction liquid, and concentrating the reaction liquid at a vacuum degree of 50-79 kPa and at the temperature of 50-65 DEG C; processing condensed vapor in a sewage treatment workshop; naturally settling ammonium fluosilicate crystals generated by concentration into a liquid seal slot, and feeding ammonium fluosilicate slurry to be dehydrated by a centrifugal machine through a slurry pump, thus obtaining the ammonium fluosilicate crystals and filtrate which can be recycled; and drying the ammonium fluosilicate crystals to obtain the ammonium fluosilicate solids. The method can be used for producing the ammonium fluosilicate solids economically and effectively, solving the problem of fluorine pollution of phosphate fertilizer enterprises, and simultaneously laying a foundation for development of fluorine chemical industry of the phosphate fertilizer enterprises.
Description
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 silicofluoric acid or silicofluoric acid and ammonium silicon fluoride mixture of utilizing to prepare the technological method of solid ammonium silicofluoride.
background technology:after in traditional industries, ammonium silicofluoride mainly contains fluorite and quartz mixing acidolysis, further ammonification and obtaining again after water absorbs; Ammonium silicofluoride is mainly used as the sterilizing agent in Brewing industry, and glass etching agent, fabric mothproofing agent, wood preservative, metal solder fusing assistant, also for electroplating industry and for the preparation of cryolith etc.Along with going deep into further of phosphorus ore association fluorine silicon resource comprehensive utilization technique, utilize phosphatic fertilizer company by-product fluosilicic acid to produce Neutral ammonium fluoride, anhydrous hydrogen fluoride technology to be mature on the whole, therefore utilize the silicofluoric acid of phosphatic fertilizer company to produce ammonium silicofluoride, ammonium silicofluoride produces the fluorine chemical series product such as solid fluorinated ammonium, solid ammonium hydrogen fluoride, anhydrous hydrogen fluoride more further; Ammonium silicofluoride has become important intermediates of phosphorus ore association fluorine silicon resource comprehensive utilization.Dissolve after silica gel for preventing silica gel blocking system from adding ammonium fluoride solution in the fluorine absorption system of phosphatic fertilizer company Phosphoric Acid Concentration, the mixture that phosphatic fertilizer company by-product will be silicofluoric acid and ammonium silicofluoride.Therefore, while comprehensive utilization phosphatic fertilizer company by-product fluosilicic acid, the utilization of the mixture of silicofluoric acid and ammonium silicofluoride should also be considered.
From fluorosilicone compound solution to fluorine chemical series product such as solid fluorinated ammonium, solid ammonium hydrogen fluoride, anhydrous hydrogen fluorides, a common feature is all the water deviate from silicofluoric acid.Therefore, which operation deviating from water in, is the key of phosphatic fertilizer company by-product fluorosilicone compound comprehensive utilization technique.After fluorine analysis ammonium silicate, Neutral ammonium fluoride, ammonium bifluoride and hydrofluoric physico-chemical property, think prepare the ammonium silicofluoride stage dehydration be easy to most in technique realize.The preparation of solid ammonium silicofluoride, for comprehensive utilization phosphatic fertilizer company fluorosilicone compound development fluorine chemical industry, silicon chemical industry lay the foundation.
The fluorosilicone compound of phosphatic fertilizer company by-product is utilized " to utilize fluorinated tail gas in production of phosphate fertilizer to prepare the method for ammonium silicofluoride " and the patent CN102701214A " a kind of method preparing high-purity ammonium fluosilicate " of Guizhou Kailin Group Co., Ltd.'s application to the patent CN101850978A that the patented technology of producing ammonium silicofluoride and having applied for only has comrade Cheng Jianfang to apply at present." to utilize fluorinated tail gas in production of phosphate fertilizer to prepare the method for ammonium silicofluoride " to be with ammonium silicofluoride crystalline mother solution as washings for absorbing phosphate fertilizer fluorinated tail gas, obtain the fluorine-containing rich solution of high density, again with ammonia neutralization, filter, filtrate is cooled and separates out ammonium silicofluoride crystallization; There are the following problems for this technique: relating in technique can lot of energy by high-temperature material crystallisation by cooling, and low temperature filtrate returns that use need heat up also will lot of energy; A large amount of silica gel can be produced in Phosphoric Acid Concentration system, make that the ammonium silicofluoride that obtains is impure even not easily to be filtered and dry." a kind of method preparing high-purity ammonium fluosilicate " should be mentioned that to adopt and is not less than the liquefied ammonia that 10% silicofluoric acid and ammonia purity is greater than 99.9% and reacts, when pH value of reaction system reaches 3 ~ 5, obtain ammonium silicofluoride by concentrated under the condition of reaction solution vacuum tightness 80kPa and temperature 70 C in low-flash concentration systems; There are the following problems for this technique: higher to liquefied ammonia quality requirements in technique; Reacting liquid pH value more than 3 silicofluoric acid starts to decompose, particularly pH value more than 4 produce a large amount of silicon-dioxide, affect the concentration process of ammonium silicofluoride, ammonium silicofluoride solid filtering and reduce the main content of product.
summary of the invention:
The object of this invention is to provide a kind of method that phosphatic fertilizer company by-product fluorosilicone compound prepares solid ammonium silicofluoride, for comprehensive utilization phosphatic fertilizer company fluorosilicone compound produces the fluorine chemical series product such as solid fluorinated ammonium, solid ammonium hydrogen fluoride, anhydrous hydrogen fluoride, development fluorine chemical industry, silicon chemical industry lay the foundation.
A kind of fluorosilicone compound of the present invention prepares the method for solid ammonium silicofluoride, and the solid silicofluoric acid amine of output can be my No. CN18840773B, unit patent applied for " a kind of ammonia solution of fluorosilicone compound and the separation method of fluorine element silicon " and supplies raw materials or directly put on market.The method of the invention is characterized in that following these steps to successively carry out:
(1) by silicofluoric acid root
content is that fluorosilicone compound solution and the ammoniacal liquor of 3% ~ 40%w/w or liquefied ammonia or volatile salt fully mix and react in reactive tank, and reacting liquid pH value 0.5 ~ 3 is reaction controlling terminal;
(2) reaction solution above-mentioned steps (1) obtained sends into evaporation concentration system, to add concentration be 20% ~ 50%w/w hydrofluoric acid or concentration be simultaneously 15% ~ 45%w/w ammonium fluoride solution also or solid fluorinated ammonium, the consumption of hydrofluoric acid or Neutral ammonium fluoride with fluorine count fluorosilicone compound raw material fluorine-containing 0.1% ~ 10%; Vacuum tightness be 50kPa ~ 79kPa, temperature is concentrated under being the condition of 50 DEG C ~ 65 DEG C; The water vapour that concentration systems is discharged is after circulating water condensing, and water of condensation is delivered to sewage treatment plant and processed;
(3) the ammonium silicofluoride natural crystal sedimentation that above-mentioned steps (2) produces enters liquid seal trough, by slush pump, the ammonium silicofluoride magma bottom liquid seal trough is sent into centrifuge dewatering, obtain ammonium silicofluoride crystal and filtrate, filtrate returns step (2) and continues repetitive operation;
(4) above-mentioned steps (3) obtains ammonium silicofluoride crystal and can obtain solid ammonium silicofluoride product after drying, and ammonium silicofluoride content is greater than 98%.
The fluorosilicone compound that above-mentioned steps (1) refers to can be silicofluoric acid, also can be the mixture of silicofluoric acid and ammonium silicofluoride.
Above-mentioned steps (1) if in the massfraction of phosphoric acid when being greater than 0.5%, fluorosilicone compound solution enter step (1) front first by solution except phosphoric acid, ironic hydroxide solid is added in fluorosilicone compound solution, add-on is the theoretical amount of phosphoric acid in precipitation solution, and after filtering, filtrate is undertaken by step (1) operation again.
The optimal conditions of above-mentioned steps (2) is 40% ~ 50%w/w for adding hydrofluoric acid concentration, and ammonium fluoride solution concentration is 35% ~ 45%w/w or solid fluorinated ammonium, and the consumption of hydrofluoric acid or Neutral ammonium fluoride counts 0.5% fluorine-containing ~ 5%w/w of fluorosilicone compound raw material with fluorine.
The liquid seal trough of above-mentioned steps (3) and the mode of connection of vacuum concentration system are that the straight tube extended bottom evaporator room inserts below the liquid level of liquid seal trough, utilize pressure reduction between normal atmosphere and system vacuum to set up liquid level in concentrating unit.
The ammonium silicofluoride crystal after centrifuge dewatering of above-mentioned steps (3), can directly be used as without drying the raw material producing Neutral ammonium fluoride, ammonium bifluoride, hydrofluoric acid, anhydrous hydrogen fluoride.
Above-mentioned optimum condition is step (1) reacting liquid pH value 1.5 ~ 2.5 is reaction controlling terminal.
Compared with prior art, tool of the present invention has the following advantages: 1, reacting liquid pH value 1.5 ~ 2.5 is reaction controlling terminal, and reaction process does not separate out silica gel; 2, concentration process adds hydrofluoric acid or ammonium fluoride solution, dissolves the silica gel brought in raw material, also suppresses to be hydrolyzed in silicofluoric acid radical ion concentration process simultaneously, and production of high purity solid ammonium silicofluoride of making a living provides safeguard; 3, atmospheric pressure device liquid seal trough is adopted to be connected with the evaporator room of vacuum concentration system, can ensure that concentration process carries out under vacuum, the ammonium silicofluoride crystal of generation can be deposited to liquid seal trough in time again, realize in vacuum concentration production process, ammonium silicofluoride crystal being taken out in atmospheric pressure device, liquid seal trough has very large solid ammonium silicofluoride storage capacity simultaneously, can not affect the normal operation of concentration systems because solid ammonium silicofluoride does not take out in time; If the solid ammonium silicofluoride produced in concentration systems evaporator room does not enter liquid seal trough and directly sends into whizzer, when whizzer fault stops or stopping without plan, the solid of failing to take out in time will block concentration systems.
Industrial test of the present invention proves produce solid ammonium silicofluoride cost-effectively; Solid ammonium silicofluoride is used as the raw material producing Neutral ammonium fluoride, ammonium bifluoride, hydrofluoric acid, anhydrous hydrogen fluoride, also can come into the market to sell as end product after drying; For comprehensive utilization phosphatic fertilizer company fluorosilicone compound development fluorine chemical industry, silicon chemical industry lay the foundation.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the inventive method.In figure: I is reactive tank, II is evaporator room, and III is steam condenser, and IV is liquid seal trough, and V is whizzer, and VI is filtrate cycle groove, and VII is graphite heat exchanger, and VIII is propeller pump, and Ⅸ is magma pump, and Ⅹ is filtrate cycle pump.The straight tube that wherein extends bottom evaporator room II inserts below the liquid level of liquid seal trough IV, utilizes pressure reduction between normal atmosphere and system vacuum to set up liquid level in concentrating unit; Liquid seal trough normal pressure, all materials when volume is large enough to hold the operation of concentration systems; The ammonium silicofluoride crystal that evaporator room concentrates generation is deposited to liquid seal trough in time, and ammonium silicofluoride crystal takes out in atmospheric conditions.
Embodiment
Embodiment 1
1600 tons/year of ammonium silicofluoride pilot plants of my unit construction adopt the inventive method to produce solid ammonium silicofluoride.
From Phosphoric Acid Concentration fluorine absorption system silicofluoric acid root
content is that the fluorosilicone compound solution of 8%w/w fully mixes with liquefied ammonia and reacts in reactive tank, and reacting liquid pH value 2 is reaction controlling terminal; Reaction solution is sent into evaporation concentration system, adds the ammonium fluoride solution that concentration is about 30% simultaneously, adopt 110 ~ 120 DEG C, the water vapour of 0.05 ~ 0.2Mpa heats, and heat-exchange equipment is tubulation graphite heat exchanger; Be about 75kPa in vacuum tightness, temperature is about under the condition of 60 DEG C concentrated; The water vapour that concentration systems is discharged is after circulating water condensing, and water of condensation enters muddy water station, then delivers to sewage treatment plant and process.
The ammonium silicofluoride natural crystal sedimentation that concentration process produces enters liquid seal trough, and ammonium silicofluoride magma sends into centrifuge dewatering by slush pump, and obtain ammonium silicofluoride crystal and filtrate, filtrate returns evaporation concentration system.
Image data select stablize in production charging, control stable condition under material in 1h is recorded, statistics and analysis.Enter the silicofluoric acid root of system
content is 8%, and flow is 2.3m
3/ h, the ammonium silicofluoride magma of system produce is after tripod pendulum type batch centrifugal dehydration, and undried solid ammonium silicofluoride is about 261kg.By analysis, ammonium silicofluoride content is greater than 94% to undried solid ammonium silicofluoride.After the drying of solid ammonium silicofluoride, ammonium silicofluoride content is greater than 98.5%.
After this ammonium silicofluoride pilot plant builds up, run the nearly trimestral time, stable, achieve the experimental data needed for project.
Embodiment 2
In middle control analysis process, find that the massfraction of phosphoric acid in filtrate cycle groove is 0.75%, the solution in filtrate cycle groove is delivered to phosphoric acid precipitates groove, and feeding speed is 2.5m
3/ h, adds ironic hydroxide solid at phosphoric acid precipitates groove, adds speed 27.5kg/h.Filter after stirring lower fully reaction, filtrate is undertaken by the operation of embodiment 1 again.
Claims (3)
1. fluorosilicone compound prepares a method for solid ammonium silicofluoride, it is characterized in that following these steps to successively carry out:
(1) be that fluorosilicone compound solution and the ammoniacal liquor of 3% ~ 40%w/w or liquefied ammonia or volatile salt fully mix and react in reactive tank by silicofluoric acid radical content, reacting liquid pH value 1.5 ~ 2.5 is reaction controlling terminal, and reaction process does not separate out silica gel;
(2) reaction solution above-mentioned steps (1) obtained sends into evaporation concentration system, to add concentration be 40% ~ 50%w/w hydrofluoric acid or concentration is simultaneously 35% ~ 45%w/w ammonium fluoride solution or solid fluorinated ammonium, dissolve the silica gel brought in raw material, also suppress to be hydrolyzed in silicofluoric acid radical ion concentration process, the consumption of hydrofluoric acid or Neutral ammonium fluoride counts 0.5% fluorine-containing ~ 5%w/w of fluorosilicone compound raw material with fluorine simultaneously; Vacuum tightness be 50kPa ~ 79kPa, temperature is concentrated under being the condition of 50 DEG C ~ 65 DEG C; The water vapour that concentration systems is discharged is after circulating water condensing, and water of condensation is delivered to sewage treatment plant and processed;
(3) the ammonium silicofluoride natural crystal sedimentation that above-mentioned steps (2) produces enters liquid seal trough, by slush pump, the ammonium silicofluoride magma bottom liquid seal trough is sent into centrifuge dewatering, obtain ammonium silicofluoride crystal and filtrate, filtrate returns step (2) and continues repetitive operation;
(4) above-mentioned steps (3) obtains ammonium silicofluoride crystal and can obtain solid ammonium silicofluoride product after drying, and ammonium silicofluoride content is greater than 98%;
Described step (1) if in the massfraction of phosphoric acid when being greater than 0.5%, fluorosilicone compound solution enter step (1) front first by solution except phosphoric acid, ironic hydroxide solid is added in fluorosilicone compound solution, add-on is the theoretical amount of phosphoric acid in precipitation solution, and after filtering, filtrate is undertaken by step (1) operation again;
The liquid seal trough of described step (3) and the mode of connection of vacuum concentration system are that the straight tube extended bottom evaporator room inserts below the liquid level of liquid seal trough, utilize pressure reduction between normal atmosphere and system vacuum to set up liquid level in concentrating unit.
2. a kind of fluorosilicone compound as claimed in claim 1 prepares the method for solid ammonium silicofluoride, it is characterized in that the fluorosilicone compound that step (1) refers to is silicofluoric acid, or the mixture of silicofluoric acid and ammonium silicofluoride.
3. a kind of fluorosilicone compound as claimed in claim 1 prepares the method for solid ammonium silicofluoride, it is characterized in that the ammonium silicofluoride crystal after centrifuge dewatering of step (3), be directly used as without drying the raw material producing Neutral ammonium fluoride, ammonium bifluoride, hydrofluoric acid, anhydrous hydrogen fluoride.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210565016.8A CN102976336B (en) | 2012-12-24 | 2012-12-24 | Method for preparing ammonium fluosilicate solids from fluorosilicone compounds |
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| CN201210565016.8A CN102976336B (en) | 2012-12-24 | 2012-12-24 | Method for preparing ammonium fluosilicate solids from fluorosilicone compounds |
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| CN102976336B true CN102976336B (en) | 2015-07-15 |
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| CN107522519A (en) * | 2017-07-27 | 2017-12-29 | 宜昌鄂中化工有限公司 | A kind of recycling technique of wet process phosphoric acid by-product fluosilicic acid |
| CN108101069A (en) * | 2017-12-28 | 2018-06-01 | 天津普恒康泰科技有限公司 | A kind of exhaust gas produces ammonium fluosilicate co-producing white carbon black raw material process after recycling |
| CN115259118A (en) * | 2021-04-30 | 2022-11-01 | 中国科学院过程工程研究所 | Method for separating phosphorus from phosphorus-containing fluorine-containing substance |
| CN113860258A (en) * | 2021-11-04 | 2021-12-31 | 多氟多新材料股份有限公司 | Preparation method of hydrogen fluoride |
| CN115072666B (en) * | 2022-06-23 | 2023-08-18 | 中石化南京工程有限公司 | System and method for preparing anhydrous hydrogen fluoride from fluosilicic acid |
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| CN1283548C (en) * | 2003-12-22 | 2006-11-08 | 云南三环化工有限公司 | Method for comprehensively utilizing phosphate fertilizer by-product |
| CN101850978B (en) * | 2010-06-06 | 2012-04-25 | 程建方 | Method for preparing ammonium fluosilicate by utilizing tail gas containing fluorine in phosphatic fertilizer production |
| CN102674367B (en) * | 2012-06-07 | 2014-01-15 | 瓮福（集团）有限责任公司 | Method for preparing ammonium fluorosilicate by utilizing fluorine-containing white slime in anhydrous hydrogen fluoride production |
| CN102701214A (en) * | 2012-06-28 | 2012-10-03 | 贵州开磷（集团）有限责任公司 | Method for preparing high-purity ammonium fluosilicate |
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Effective date of registration: 20170706 Address after: Xifeng County in Guizhou Province, Guiyang city town 551109 Patentee after: Guiyang Kailin Chemical Co. Ltd. Address before: 550002 Guizhou city of Guiyang Province sun Tian Ba Lu No. 1 Patentee before: Guizhou Provincial Inst. of Chemical Technology |