CN105417556A - Preparation method of ammonium bifluoride - Google Patents
Preparation method of ammonium bifluoride Download PDFInfo
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- CN105417556A CN105417556A CN201510943013.7A CN201510943013A CN105417556A CN 105417556 A CN105417556 A CN 105417556A CN 201510943013 A CN201510943013 A CN 201510943013A CN 105417556 A CN105417556 A CN 105417556A
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- ammonium bifluoride
- ammonium
- fluorine
- filter
- filtrate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/162—Ammonium fluoride
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- Silicon Compounds (AREA)
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Abstract
The invention discloses a preparation method of ammonium bifluoride. The method comprises steps as follows: a, dilute ammonia water and ammonium bifluoride mother liquor are mixed to adsorb gas containing fluorine and silicon, and a mixed solution is obtained; b, the mixed solution and filter-press residues obtained in Step d are mixed for slurry making and filter-press separation, and a filtrate and a silica by-product are obtained; c, ammonia is introduced into the filtrate; d, slurry is subjected to filter-press separation, and an ammonium fluoride filtrate and filter-press residues are obtained; e, the ammonium fluoride filtrate is subjected to vacuum concentration; f, concentrated slurry is dissolved, the pH value of the solution is adjusted with hydrogen fluoride, and cooling crystallization is performed; g, ammonium bifluoride crystals are filtered, separated and dried, and the ammonium bifluoride product is obtained. With the adoption of the method, the utilization rate of fluorine and ammonia is increased, the gas containing fluorine and silicon is changed into the ammonium bifluoride product with the high economic value in the phosphoric acid production process, the production cost is low, the economic benefit is significant, meanwhile, the purity and other indexes of the product meet the requirement for superior products, and the method is suitable to be popularized and applied in the field.
Description
Technical field
The present invention relates to the technology of preparing of fluorine chemical industry inorganic fluoride salt, be specifically related to a kind ofly utilize fluorine-containing absorption liquid to prepare the method for ammonium bifluoride.
Background technology
Ammonium bifluoride is white or water white transparency rhomboidal crystal, and easily deliquescence easily lumps in atmosphere, soluble in water.The aqueous solution is strongly-acid, has hydrofluoric tart flavour; Be slightly soluble in alcohol, decompose in the hot water, distil under high temperature.
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 ceramic and aluminum magnesium alloy, organic synthesis fluorizating agent, electroplate liquid, the solvent of extraction rare elements, the acidification agent of oil field sandstone.
Ammonium bifluoride preparation technology can be divided into liquid phase method and gas phase method.Wherein, vapor phase process utilizes ammonia and pure hydrogen fluoride gas to react in handtailor container, vapor phase process made ammonium bifluoride water content is low, purity is high, good stability, but to equipment material require high, investment is large, preparation cost is high, if without particular requirement, ammonium bifluoride uses producer generally to there is no need to use vapor phase process product.
Liquid phase method is different according to raw material, can be divided into: hydrogen fluoride-liquid ammonia process for caustic soda purification, silicofluoric acid-liquid ammonia process for caustic soda purification and fluorine-containing waste liquid-liquid ammonia process for caustic soda purification etc.Current ammonium bifluoride main raw material hydrofluoric acid derives from fluorite, although China is fluorite resource big country, considers from strategic height, has taked to limit exploitation and the behave exported.Therefore, the fluoro-gas produced in Appropriate application phosphoric acid by wet process and phosphate fertilizer preparation process is to prepare fluorine-containing goods, both can solve fluoride pollution problem preferably, can open up again a new fluoride salt and prepare approach, the Sustainable development for fluorine chemical and phosphorous chemical industry will produce great effect.
Duo-fluoride Chemicals Co., Ltd., cloud South 3rd Ring Road and Wengfu phosphorous chemical industry use phosphoric acid by-product fluosilicic acid to carry out ammonium bifluoride technical study, and existing patent documentation is delivered.Wherein application number is mention in the patented method of 200610017486.5: silicofluoric acid or ammonium silicofluoride are raw material, neutralized by logical ammonia, filter, the operating unit such as concentrated and thermal degradation produces ammonium bifluoride, utilize the method can improve the strainability of reaction slurry, but the decomposition temperature of the Neutral ammonium fluoride concentrated solution mentioned in patent is 130 ~ 180 DEG C.The ammonium bifluoride energy consumption using the method to prepare is high, and product purity is low.Application number is mention the fluoro-gas utilizing Neutral ammonium fluoride filtered liquid to absorb production process of phosphoric acid in the patent documentation of 200310104114.2, absorption liquid through in dephosphorization and ammonia and after, concentrated ammonium bifluoride processed, process adopts normal pressure to concentrate, Neutral ammonium fluoride decomposes not exclusively, can not obtain the ammonium bifluoride product that purity is higher.Application number is mention the fluoro-gas using Neutral ammonium fluoride filtered liquid to absorb production process of phosphoric acid in the patent documentation of 201310010638.9, absorption liquid leads to ammonia neutralization, concentrated after using hydrofluoric acid adjustment neutralizer pH value, concentrated solution crystallisation by cooling ammonium bifluoride, crystalline mother solution returns concentration systems, and the method uses Neutral ammonium fluoride to absorb fluoro-gas, and the weak ammonia that concentration process obtains can not obtain Appropriate application, cause production cost higher, product purity difficulty reaches premium grads requirement.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of purity and the better ammonium bifluoride of other indexs.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of ammonium bifluoride, comprises the steps:
A, by weak ammonia and the mixing of ammonium bifluoride mother liquor, for adsorbing fluorine-containing and gas that is silicon after mixing, or the gas of direct and silicon fluorine-containing with weak ammonia absorption, obtain H
2siF
6(NH
4)
2siF
6mixing solutions;
B, the filter-press residues mixed pulp that step a gained mixing solutions and steps d are obtained, then press filtration is separated, and obtains filtrate and silicon-dioxide byproduct;
Pass into ammonia neutralization in c, the filtrate that obtains to step b, control slip endpoint pH 9 ~ 11;
D, the slip press filtration obtained by step c are separated, and obtain Neutral ammonium fluoride filtrate and filter-press residues, filter-press residues returns step b slurrying;
E, Neutral ammonium fluoride filter vacuum steps d obtained are concentrated into the concentrated thick slurry that proportion is 1.05 ~ 1.35g/ml, pH value is 5 ~ 8;
F, the concentrated thick slurry obtained by step e dissolve, and with hydrogen fluoride adjustment solution ph to 3 ~ 3.5, then crystallisation by cooling obtains ammonium bifluoride crystallization; Cooling terminal temperature is 10 ~ 30 DEG C;
G, the ammonium bifluoride crystallization filtering separation obtained by step f, oven dry obtain ammonium bifluoride product; The mother liquor that (when being used for adsorbing the gas of fluorine-containing and silicon after by weak ammonia and the mixing of ammonium bifluoride mother liquor, mixing) filtering separation obtains returns step a and uses.
Wherein, in aforesaid method step a, the mass concentration 2 ~ 15% of described weak ammonia, the mass content 10 ~ 25% of fluorine in described ammonium bifluoride mother liquor.
Wherein, in aforesaid method steps d, the mass content 8 ~ 30% of fluorine in Neutral ammonium fluoride filtrate, NH in filter-press residues
3mass content 2 ~ 5%.
Wherein, in aforesaid method step e, during vacuum concentration, can weak ammonia be produced, return step a and use.
Wherein, the mother liquor that aforesaid method step g obtains returns step f simultaneously, for dissolving concentrated thick slurry.
Wherein, in aforesaid method step a, described gas that is fluorine-containing and silicon contains HF, SiF
4, derive from production process of phosphoric acid or fluorine-containing Raw material processing process.
The invention has the beneficial effects as follows: the filter-press residues mixed pulp that step a gained mixing solutions and steps d obtain by the present invention, is in order to the fluorine in recycling step d filter-press residues and ammonia, improves the rate of recovery of fluorine and ammonia, reduces production cost.Step c of the present invention controls slip endpoint pH 9 ~ 11, although increase ammonia consumption, ammonia of the present invention can fully reclaim, and overcomes this defect, can increase SiO again simultaneously
2remove the degree of depth, improve later crystallization product purity.Vacuum concentration is applied to ammonium bifluoride preparation by the present invention, with Neutral ammonium fluoride filtrate normal temperature concentration ratio comparatively, the Neutral ammonium fluoride rate of decomposition of enriching slurry reduces, and the Neutral ammonium fluoride amount namely directly entering product increases, the reduction of thickening temperature, has very large promoter action to energy efficient simultaneously.The present invention utilizes ammonium bifluoride mother liquor to carry out recrystallization to concentrated thick slurry, and through pH value adjustment and recrystallization, be easy to make ammonium bifluoride premium grads, conforming product rate is greater than 95%.Weak ammonia and mother liquor are returned the production for silicofluoric acid by the present invention, improve the utilization ratio of fluorine and reduce further ammonia consumption and production cost.Invention increases the utilization ratio of fluorine and ammonia, fluorine-containing and the silicon gas transition in production process of phosphoric acid or fluorine-containing Raw material processing process is made to be the ammonium bifluoride product that economic worth is high, low production cost, there is significant economic benefit, product purity and other indexs are all higher than the product that existing liquid phase method is produced simultaneously, all meet the requirement of premium grads, be suitable for applying in this area.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention's wherein a kind of embodiment.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
As shown in Figure 1, the preparation method of ammonium bifluoride of the present invention, comprises the steps:
A, by weak ammonia and the mixing of ammonium bifluoride mother liquor, for adsorbing fluorine-containing and gas that is silicon after mixing, or the gas of direct and silicon fluorine-containing with weak ammonia absorption, obtain H
2siF
6(NH
4)
2siF
6mixing solutions;
B, the filter-press residues mixed pulp that step a gained mixing solutions and steps d are obtained, then press filtration is separated, and obtains filtrate and silicon-dioxide byproduct;
Pass into ammonia neutralization in c, the filtrate that obtains to step b, control slip endpoint pH 9 ~ 11;
D, the slip press filtration obtained by step c are separated, and obtain Neutral ammonium fluoride filtrate and filter-press residues, filter-press residues returns step b slurrying;
E, Neutral ammonium fluoride filter vacuum steps d obtained are concentrated into the concentrated thick slurry that proportion is 1.05 ~ 1.35g/ml, pH value is 5 ~ 8;
F, the concentrated thick slurry obtained by step e dissolve, and with hydrogen fluoride adjustment solution ph to 3 ~ 3.5, then crystallisation by cooling obtains ammonium bifluoride crystallization; Cooling terminal temperature is 10 ~ 30 DEG C;
G, the ammonium bifluoride crystallization filtering separation obtained by step f, oven dry obtain ammonium bifluoride product; The mother liquor that (when weak ammonia and ammonium bifluoride mother liquor being mixed, time after mixing for adsorbing the fluorine-containing gas with silicon) filtering separation obtains returns step a and uses.
Preferably, for the ease of present invention process control and obtain the product of high-quality, in aforesaid method step a, the mass concentration 2 ~ 15% of described weak ammonia, the mass content 10 ~ 25% of fluorine in described ammonium bifluoride mother liquor.
Preferably, in aforesaid method steps d, the mass content 8 ~ 30% of fluorine in Neutral ammonium fluoride filtrate, NH in filter-press residues
3mass content 2 ~ 5%.
Preferably, in order to improve ammonia recovery, in aforesaid method step e, during vacuum concentration, can weak ammonia be produced, returning step a and using.
Preferably, the mother liquor that aforesaid method step g obtains returns step f simultaneously, for dissolving concentrated thick slurry.
Wherein, in aforesaid method step a, described gas that is fluorine-containing and silicon contains HF, SiF
4, derive from production process of phosphoric acid.
Below by embodiment, the inventive method is described further, but therefore scope is not limited in one embodiment.
Embodiment one weak ammonia absorbs phosphoric acid fluorine silicon tail gas and prepares ammonium bifluoride
NH
3the weak ammonia of concentration 3.5% is for absorbing phosphoric acid fluorine silicon gas, and the absorption liquid F concentration obtained is 13.52%.Use fluorine absorption liquid with containing ammonia silicon-dioxide slurrying (i.e. steps d of the present invention obtain filter-press residues), weight ratio 1:2, press filtration slurry after slurrying, reclaims F and NH contained in ammonia silicon-dioxide
3.Filtered liquid passes into ammonia and neutralizes, and the endpoint pH of neutralization reaction slip is 11.5, press filtration neutralization reaction slip, obtain F concentration be the Neutral ammonium fluoride filtrate of 15.39% for vacuum concentration ammonium bifluoride, residual NH
3content be 4.28% return slurry process again containing ammonia silicon-dioxide.Vacuum concentration fluorinated ammonium filtered liquid, vacuum tightness is 0.045mpa, and corresponding thickening temperature is 75 DEG C.Concentrated gas after condensation weak ammonia for absorbing fluorine in phosphoric acid system tail gas and silicon.Vacuum Concentrating Process, Neutral ammonium fluoride decomposes, the concentrated thick slurry that to obtain proportion be 1.24g/ml, F concentration is 33.43%, pH value is 6.74.The reactive tank that concentrated thick slurry is put in fluorinated hydrogen crystalline ammonium mother liquor dissolves, solvent temperature 92 DEG C, and use hydrogen fluoride adjustment solution ph to 3.2, cooling terminal temperature 15 DEG C, the crystallization of centrifugation ammonium bifluoride, the centrifugal material drying of ammonium bifluoride is product; Centrate mother liquor is for absorbing fluoro-gas and dissolving concentrated thick slurry.
The mixed solution of embodiment two weak ammonia and ammonium bifluoride crystalline mother solution absorbs phosphoric acid fluorine silicon tail gas and prepares ammonium bifluoride
NH
3the mixed solution of the weak ammonia of concentration 3.5% and the ammonium bifluoride mother liquor of F concentration 21.75% is for absorbing phosphoric acid fluoro-gas, and obtaining F concentration is 19.67%.Use fluorine absorption liquid with containing ammonia waste residue (i.e. steps d of the present invention obtain filter-press residues) slurrying, weight ratio 1.5:2, then press filtration slurry after slurry, reclaim F and NH contained in ammonia waste residue
3.Filtered liquid passes into ammonia and neutralizes, and the endpoint pH of neutralization reaction slip is 11.2, press filtration neutralization reaction slip, obtain F concentration be the Neutral ammonium fluoride filtrate of 21.36% for vacuum concentration ammonium bifluoride, residual NH
3content be 3.97% filter-press residues return slurry process again.Vacuum concentration fluorinated ammonium filtered liquid, vacuum tightness is 0.055mpa, and corresponding thickening temperature is 68 DEG C.Concentrated gas after condensation weak ammonia for absorbing fluorine in phosphoric acid system tail gas and silicon.Vacuum Concentrating Process, Neutral ammonium fluoride decomposes, the concentrated thick slurry that to obtain proportion be 1.25g/ml, F concentration is 34.69%, pH value is 6.68.The reactive tank that concentrated thick slurry is put in fluorinated hydrogen crystalline ammonium mother liquor dissolves, solvent temperature 93 DEG C, and use hydrogen fluoride adjustment solution ph to 2.7, cooling terminal temperature 15 DEG C, the crystallization of centrifugation ammonium bifluoride, the centrifugal material drying of ammonium bifluoride is product; Centrate mother liquor is for absorbing fluoro-gas and dissolving concentrated thick slurry.
Comparative example one Neutral ammonium fluoride absorbs phosphoric acid fluorinated tail gas and prepares ammonium bifluoride
The Neutral ammonium fluoride filtered liquid of Neutral ammonium fluoride concentration 13.7%, for absorbing the fluorine silicon gas in phosphoric acid tail gas, to pass in ammonia and Funing tablet is the absorption liquid of 20.67%, and terminal pH is 9.2, in filtration and slip, in the Neutral ammonium fluoride filtrate obtained siliceous 3.75%.Concentrating filter liquor, to proportion 1.15g/ml, uses hydrogen fluoride adjustment pH to 3.1, through cooling to 18 DEG C.Gained crystalline product can not detect ammonium bifluoride content.
In comparative example one, the Neutral ammonium fluoride filtered liquid of working concentration 13.7% absorbs the fluorine silicon gas in phosphoric acid tail gas, obtains the absorption liquid of concentration 20.67%, can reduce the concentration and evaporation amount of rear operation.Absorption liquid leads in ammonia inadequate with the removal of impurities degree of depth, silicon content 3.75% in Neutral ammonium fluoride filtrate, when using hydrofluoric acid that the pH value of Neutral ammonium fluoride concentrated solution is reduced to 3.1 from 9.2, and F, NH4 meeting in solution and SiO
2in conjunction with, can ammonium silicofluoride be generated in pH value 2 ~ 5 scope, reduce the turnout of ammonium bifluoride, therefore, adopt comparative example one can not obtain ammonium bifluoride product or content little.
Comparative example fluoram filtrate condensing crystal prepares ammonium bifluoride
The silicofluoric acid of F concentration 14.52% is led to ammonia and is neutralized to pH value 10.9, the Neutral ammonium fluoride filtrate that filtering separation obtains for concentrated, vacuum tightness 0.05Mpa, thickening temperature 60 ~ 70 DEG C.Enriching slurry proportion 1.15g/ml, clear liquid pH value depreciation 6.5 after concentrated, use hydrogen fluoride adjustment solution ph to 3.1, cooling terminal temperature 15 DEG C, the crystallization of centrifugation ammonium bifluoride, the centrifugal material drying of ammonium bifluoride is product; Centrate mother liquor returns enrichment process.
The ammonium bifluoride product content obtained in comparative example two is lower than the ammonium bifluoride product content obtained in embodiment one and embodiment two.Reason is: in Neutral ammonium fluoride filtrate reconcentration process, decompose not exclusively, for the mixture of Neutral ammonium fluoride and ammonium bifluoride, if do not adopt method shown in comparative example one or comparative example two: the ammonium bifluoride utilizing ammonium bifluoride crystalline mother solution to produce concentration process, the mixture of Neutral ammonium fluoride carry out recrystallization, and the crystalline product obtained is the mixture of ammonium bifluoride and Neutral ammonium fluoride.Therefore the ammonium bifluoride comparision contents in comparative example two is poor, can not obtain excellent ammonium bifluoride product.
The product index measured value obtained in table 1 embodiment and comparative example
Claims (6)
1. a preparation method for ammonium bifluoride, is characterized in that comprising the steps:
A, by weak ammonia and the mixing of ammonium bifluoride mother liquor, for adsorbing fluorine-containing and gas that is silicon after mixing, or the gas of direct and silicon fluorine-containing with weak ammonia absorption, obtain H
2siF
6(NH
4)
2siF
6mixing solutions;
B, the filter-press residues mixed pulp that step a gained mixing solutions and steps d are obtained, then press filtration is separated, and obtains filtrate and silicon-dioxide byproduct;
Pass into ammonia neutralization in c, the filtrate that obtains to step b, control slip endpoint pH 9 ~ 11;
D, the slip press filtration obtained by step c are separated, and obtain Neutral ammonium fluoride filtrate and filter-press residues, filter-press residues returns step b slurrying;
E, Neutral ammonium fluoride filter vacuum steps d obtained are concentrated into the concentrated thick slurry that proportion is 1.05 ~ 1.35g/ml, pH value is 5 ~ 8;
F, the concentrated thick slurry obtained by step e dissolve, and with hydrogen fluoride adjustment solution ph to 3 ~ 3.5, then crystallisation by cooling obtains ammonium bifluoride crystallization; Cooling terminal temperature is 10 ~ 30 DEG C;
G, the ammonium bifluoride crystallization filtering separation obtained by step f, oven dry obtain ammonium bifluoride product; The mother liquor that filtering separation obtains returns step a and uses.
2. the preparation method of ammonium bifluoride according to claim 1, is characterized in that: in step a, the mass concentration 2 ~ 15% of described weak ammonia, the mass content 10 ~ 25% of fluorine in described ammonium bifluoride mother liquor.
3. the preparation method of ammonium bifluoride according to claim 1, is characterized in that: in steps d, the mass content 8 ~ 30% of fluorine in Neutral ammonium fluoride filtrate, NH in filter-press residues
3mass content 2 ~ 5%.
4. the preparation method of ammonium bifluoride according to claim 1, is characterized in that: in step e, can produce weak ammonia during vacuum concentration, returns step a and uses.
5. the preparation method of ammonium bifluoride according to claim 1, is characterized in that: the mother liquor that step g obtains returns step f simultaneously, for dissolving concentrated thick slurry.
6. the preparation method of ammonium bifluoride according to claim 1, is characterized in that: in step a, and described gas that is fluorine-containing and silicon contains HF, SiF
4, derive from production process of phosphoric acid or fluorine-containing Raw material processing process.
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Cited By (3)
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| CN106673015A (en) * | 2017-01-24 | 2017-05-17 | 浙江大洋生物科技集团股份有限公司 | Method for producing high-purity ammonium fluoride by utilizing sodium hydride waste residues |
| CN113023749A (en) * | 2021-03-15 | 2021-06-25 | 盛隆资源再生（无锡）有限公司 | Method for resource utilization of etching process waste |
| CN115676851A (en) * | 2022-11-23 | 2023-02-03 | 贵州省化工研究院 | Method and device for preparing ammonium bifluoride from solid ammonium fluoride |
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| CN115676851B (en) * | 2022-11-23 | 2024-05-21 | 贵州省化工研究院 | Method and device for preparing ammonium bifluoride from solid ammonium fluoride |
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