CN108439365A - A kind of method that sylvite circular treatment fluosilicic acid prepares ammonium acid fluoride - Google Patents
A kind of method that sylvite circular treatment fluosilicic acid prepares ammonium acid fluoride Download PDFInfo
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- CN108439365A CN108439365A CN201810441726.7A CN201810441726A CN108439365A CN 108439365 A CN108439365 A CN 108439365A CN 201810441726 A CN201810441726 A CN 201810441726A CN 108439365 A CN108439365 A CN 108439365A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention discloses a kind of methods that sylvite circular treatment fluosilicic acid prepares ammonium acid fluoride, belong to technical field of phosphorous chemical industry.This method includes：Potassium fluosilicate is reacted with ammonium hydroxide, is separated by solid-liquid separation after the completion of reaction and obtains potassium fluoride ammonium fluoride solution and silica filter cake, silica filter cake is used to prepare white carbon；Potassium fluoride ammonium fluoride solution is reacted with fluosilicic acid, is separated by solid-liquid separation after the completion of reaction and obtains ammonium acid fluoride ammonium fluoride solution and potassium fluosilicate, potassium fluosilicate return to step (1) is used as raw material；It is passed through hydrogen fluoride into ammonium acid fluoride ammonium fluoride solution ammonium fluoride is made to be fully converted to ammonium acid fluoride and obtains ammonium hydrogen fluoride solution, ammonium acid fluoride is obtained after concentrated, dry.The economic value of the present invention is that the ammonium acid fluoride and white carbon of high value can be obtained simultaneously, has accomplished to utilize the comprehensive high-efficiency of fluorine silicon resource.
Description
Technical field
The invention belongs to technical field of phosphorous chemical industry, more particularly to a kind of sylvite circular treatment fluosilicic acid prepares ammonium acid fluoride
Method.
Background technology
Largely dilute fluosilicic acid, the substance have certain toxicity and corrosion to meeting by-product during Wet-process Phosphoric Acid Production
Property, direct emission can cause serious pollution to environment.If can be utilized effectively, pollution can be not only reduced, moreover it is possible to by institute
Fluorine-containing cycling of elements is the higher fluorine product of economic value, so that the fluosilicic acid of enterprise is utilized and reaches a new high, and increases
Add the output value and profit.The selection of target fluorine product determines the processing technology routine that fluosilicic acid utilizes.Ammonium acid fluoride be wherein compared with
Good one of target product.
Ammonium acid fluoride is a kind of important industrial chemicals, be mainly used as glass etching agent, chemical reagent, boilercompound,
Fermentation industry disinfectant and steel plate and aluminium shape surface inorganic agent etc..Ammonium acid fluoride dosage in glass processing is very big, common saturating
The medicament that bright glass can be prepared easily with a kind of ammonium acid fluoride is allowed to frosted glass.The formula and concentration of transformation medicament are again
Television picture tube can be made to generate low specular reflectivity.Textile processing in, ammonium acid fluoride can be used to remove alkali cleaning after it is residual
Stay basic species on the fabric.Ammonium acid fluoride is widely used in metallurgical industry, it can be with many metal oxygens in higher temperature
Compound or carbonate form double salt.Decomposable asymmetric choice net generates pure metal fluoride again for double salt heating, and releases NH3And HF, to
A kind of unique process route is formed in terms of rare metal smelting.In oil recovery, silica and silicon can be dissolved using ammonium acid fluoride
The characteristic of hydrochlorate, 15% hydrochloric acid solution containing 2% ammonium acid fluoride is used to be acidified the silicalite layer of oil well can restore to be on the verge of to discard
The oil recovery ability of oil well.High-purity electron level ammonium acid fluoride can be used for semi-conductor industry.In recent years with ground glass container, dress
The fast development of the industries such as lamps and lanterns, aluminium section bar is adornd, market gradually increases the demand of ammonium acid fluoride.
Dilute fluosilicic acid using other product --- silica can be in the form of white carbon as product.White carbon has
There is the characteristics of good small grain size, large specific surface area, polymolecularity, chemical stability, high temperature resistant and good insulating, is widely used in rubber
The numerous areas such as glue, plastics, coating, ink, papermaking, agriculture medicine and daily-use chemical industry, are a kind of important chemical products.With
The progress and development of China's economy, the demand of the industries of many field of fine chemical to white carbon are increasing.
Due to ammonium acid fluoride and the extensive purposes of white carbon and huge dimensions of market, it is fluorinated so being prepared using dilute fluosilicic acid
Hydrogen ammonium and white carbon can meet the requirement that phosphoric acid by wet process and phosphatic fertilizer company handle the dilute fluosilicic acid of by-product, meet country to dilute
The encouragement policy that fluosilicic acid utilizes, and can be that this kind of enterprise creates the new output value.
It is domestic and international at present to report there are mainly two types of the process routes for directly preparing ammonium acid fluoride using fluosilicic acid.The first work
Skill route approximately as：Ammonia or ammonium hydroxide reaction are passed through in dilute fluosilicic acid, it is molten through silica and ammonium fluoride is obtained by filtration
Liquid；It is passed directly into anhydrous hydrofluoric acid in ammonium fluoride solution, controls certain pH value, the slurry after filtering reaction, filter cake is through low
Temperature vacuum drying is to get ammonium acid fluoride product.Such as a kind of " fluorosilicone compound preparation high-quality fluorination of Guizhou Provincial Inst. of Chemical Technology
The method of hydrogen ammonium "（CN 102976356 A）Deng.Second of process route is that the ammonium fluoride for preparing the first process route is molten
Liquid is concentrated, crystallization obtains ammonium hydrogen fluoride solid.Such as opening plum, " fluosilicic acid legal system ammonium acid fluoride co-production of high-quality white carbon black technique is ground
Study carefully "（Inorganic chemicals industry, 2010,42 (1) 55-56）, bang rosy clouds etc. " fluosilicic acid produces ammonium acid fluoride co-producing white carbon black new process "
（Inorganic chemicals industry, 2008,40 (10) 41-42）, Duo-fluoride Chemicals Co., Ltd. " a kind of production ammonium acid fluoride coproduction is white
The method of carbon black "（Application number 200610017486.5）.The shortcomings that analyzing above two process route is：（1）The first work
Skill route needs to use the hydrogen fluoride of a large amount of costlinesses, and the dosage of hydrogen fluoride accounts for the 35% of ammonium acid fluoride gross mass；（2）Second of work
Skill route uses decomposition technique, needs 130-180 DEG C of decomposition temperature, and energy consumption is very high, and equipment requirement and investment are high, and hydrogen fluoride
The disposable yield of ammonium is low.These technological deficiencies greatly restrict the application of above-mentioned process route in the industrial production.
Therefore, it is very necessary research and invent it is a kind of using dilute fluosilicic acid prepare the new process of ammonium acid fluoride and white carbon with
The shortcomings that overcoming above two technique, to be industrially used widely.
Invention content
It is an object of the invention to overcome the existing technological deficiency for preparing ammonium acid fluoride using dilute fluosilicic acid, one kind is provided more
For the cost-effective method for preparing ammonium acid fluoride using sylvite circular treatment fluosilicic acid.The scheme is as follows：
This method includes：
(1) potassium fluosilicate is reacted with ammonium hydroxide, is separated by solid-liquid separation after the completion of reaction and obtains potassium fluoride-ammonium fluoride solution and dioxy
SiClx filter cake, silica filter cake are washed（Washing lotion can be incorporated into potassium fluoride-ammonium fluoride solution）, drying be used to prepare hard charcoal
It is black.
(2) potassium fluoride-ammonium fluoride solution is reacted with fluosilicic acid, is separated by solid-liquid separation after the completion of reaction and obtains ammonium acid fluoride-fluorine
Change ammonium salt solution and potassium fluosilicate, potassium fluosilicate return to step (1) can realize that potassium fluosilicate constantly recycles as raw material（Base
This is without being supplemented potassium fluosilicate, it is only necessary to which supplement is on a small quantity to make up loss of material）.
(3) it is passed through hydrogen fluoride into ammonium acid fluoride-ammonium fluoride solution ammonium fluoride is made to be fully converted to ammonium acid fluoride and obtain fluorine
Change hydrogen ammonium salt solution, ammonium acid fluoride is obtained after concentrated, dry.
Wherein, the source of potassium fluosilicate can be by phosphoric acid industry in step (1)（Wet method）Fluosilicic acid as byproduct and sulphur
Sour nak response obtains, and is supplemented as starting material and sequential loss.
Wherein, in step (1), reaction temperature is 20-70 DEG C, reaction time 30-60min, potassium fluosilicate and ammonia
Molar ratio is 1:The mass concentration of 4.0-4.5, ammonium hydroxide are 10%-30%.
Wherein, in step (2), reaction temperature is 20-50 DEG C, reaction time 10-30min, fluosilicic acid and potassium fluoride
Molar ratio be 1:2.
Wherein, fluosilicic acid is phosphoric acid industry by-product（Containing a small amount of or not hydrofluoric acid containing, but on this patent without influence）,
Mass concentration is 8%-18%.Preparation method i.e. provided by the invention is to rely on Wet Processes of Phosphoric Acid, passes through its by-product fluorine silicon
Acid（Concentration is diluter）Maximumlly fluorine is utilized to produce ammonium acid fluoride.
Wherein, in step (3), reaction temperature is 20-50 DEG C, and being passed through hydrogen fluoride makes ammonium acid fluoride-ammonium fluoride solution
PH value makes ammonium fluoride just be fully converted to ammonium acid fluoride for 3.
Wherein, in step (3), condensed water that concentration process generates, which is sent, to be washed process to phosphoric acid tail and obtains fluosilicic acid, is used for
Realize the recycling of water resource.
Wherein, in step (3), concentration and dry absolute pressure are 35-80KPa, and drying temperature is 80-100 DEG C.
Specifically, method provided by the invention includes：
(1) by phosphoric acid industry fluosilicic acid as byproduct and potassium sulfate be obtained by the reaction potassium fluosilicate as the starting material of step (2) and
Supplement loss of material.
(2) by step (1)（Starting material）And/or step (3)（Mainly, after starting）Obtained potassium fluosilicate and ammonium hydroxide
It is reacted, reaction temperature is 20-70 DEG C, and the molar ratio of potassium fluosilicate and ammonia is 1:4.0-4.5 is separated by solid-liquid separation after the completion of reaction
Potassium fluoride-ammonium fluoride solution and silica filter cake are obtained, silica filter cake is used to prepare white carbon, the mass concentration of ammonium hydroxide
For 10%-30%.
(3) potassium fluoride-ammonium fluoride solution that step (2) obtains is reacted with phosphoric acid industry fluosilicic acid as byproduct, reaction temperature
Degree is 20-50 DEG C, and the molar ratio of fluosilicic acid and potassium fluoride is 1:2, it is separated by solid-liquid separation after the completion of reaction and obtains ammonium acid fluoride-ammonium fluoride
Solution and potassium fluosilicate, the potassium fluosilicate return to step (2) are used as raw material.
(4) hydrogen fluoride is passed through in the ammonium acid fluoride-ammonium fluoride solution obtained to step (3) makes pH value be 3, and reaction temperature is
20-50 DEG C, after the completion of reaction, ammonium acid fluoride is obtained after concentrated, dry, the condensed water that concentration process generates, which is sent to phosphoric acid tail, to be washed
Process obtains fluosilicic acid.
Wherein, in step (1) and (2), the mass concentration of phosphoric acid industry fluosilicic acid as byproduct is 8%-18%.
The present invention produces ammonium acid fluoride using the dilute fluosilicic acid of phosphoric acid by-product and commodity ammonia, hydrogen fluoride with used at present as raw material
It is compared with the technique of white carbon, compared to having the following advantages that：
(1) and the first process route ratio, the usage amount of the hydrogen fluoride of ammonium acid fluoride per ton reduce 50%.
(2) and 1. energy consumption is greatly reduced in second of process route ratio, no pyrolysis process；2. pair setting
Standby, public work（Such as heat steam grade）Deng requirement it is low, reduce investment；Yield is up to 95% or more.
To sum up, production cost can be greatly reduced compared with existing technique in this method, be a kind of more economical, efficient
The method that dilute fluosilicic acid is prepared ammonium acid fluoride co-producing white carbon black, not only technological process is simple, and operating flexibility is big, can be by continuous
Method or batch process are realized, industrialized production is relatively suitble to；Meanwhile potassium fluosilicate and water are Ke Xunhuanliyong.The economic valence of the present invention
Value is that the ammonium acid fluoride and white carbon of high value can be obtained simultaneously, has accomplished to utilize the comprehensive high-efficiency of fluorine silicon resource.
Description of the drawings
The present invention is described in conjunction with attached drawing embodiment in detail below, to that will become detailed in the description of embodiment and understand this
Invent above-mentioned or additional aspect and advantage.
Fig. 1 is the process flow chart of the present invention.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
The method that a kind of sylvite circular treatment fluosilicic acid of the present invention prepares ammonium acid fluoride, in advance using potassium sulfate and
Fluosilicic acid carries out pre-reaction and prepares potassium fluosilicate, and processing step thereafter is：
a）Potassium fluosilicate is added in ammonium hydroxide, after being stirred, is separated by filtration to obtain potassium fluoride-ammonium fluoride solution and titanium dioxide
Silicon filter cake；
b）By silica filter cake by washing, drying, white carbon is obtained；
c）Fluosilicic acid is added into potassium fluoride-ammonium fluoride solution, after being stirred and being separated by filtration, obtains ammonium acid fluoride-fluorination
Ammonium salt solution and potassium fluosilicate, potassium fluosilicate return to step a；
d）It is passed through anhydrous hydrogen fluoride into ammonium acid fluoride-ammonium fluoride solution, it is 3 to adjust the pH of solution, obtains ammonium hydrogen fluoride solution；
e）Ammonium hydrogen fluoride solution is concentrated, is dried, ammonium acid fluoride product is obtained.
Pre-reaction
290 g potassium sulfates are added to the fluosilicic acid that mass concentration is 12%（2000g）In, reaction temperature is 40 DEG C, stirring
After 30min, 10min is stood, is filtered, it is dry, obtain potassium fluosilicate product 366g.
Embodiment 1
220g potassium fluosilicates are added to the ammonium hydroxide that mass concentration is 20%（347g）In, it is stirred to react 40min at 40 DEG C, stands
Silica filter cake and potassium fluoride-ammonium fluoride solution are obtained by filtration after 10min, silica filter cake is washed, is obtained after dry
White carbon black product.Washing filtrate merges with potassium fluoride-ammonium fluoride solution, and the fluosilicic acid that mass concentration is 12% is added
（1200g）, it is stirred to react 20min at 40 DEG C, potassium fluosilicate and ammonium acid fluoride-ammonium fluoride solution is obtained by filtration after standing 10min.
It is passed through hydrogen fluoride into ammonium acid fluoride-ammonium fluoride solution at 30 DEG C, the pH value for adjusting solution is 3, obtains ammonium hydrogen fluoride solution, should
Solution concentrates at absolute pressure 35kPa, is dry（Drying temperature is 80 DEG C）, obtain ammonium acid fluoride product.
White carbon 59.5g is obtained in this process, and yield is more than 99%, and purity is more than 98%, specific surface area 170m2/g；
Obtain ammonium acid fluoride 220g, yield 96.5%, purity 98.2%.
Embodiment 2
220g potassium fluosilicates are added to the ammonium hydroxide that mass concentration is 15%（463g）In, it is stirred to react 30min at 30 DEG C, stands
Silica filter cake and potassium fluoride-ammonium fluoride solution are obtained by filtration after 10min, silica filter cake is washed, is obtained after dry
White carbon black product.Washing filtrate merges with potassium fluoride-ammonium fluoride solution, and the fluosilicic acid that mass concentration is 14% is added
（1030g）, it is stirred to react 15min at 40 DEG C, potassium fluosilicate and ammonium acid fluoride-ammonium fluoride solution is obtained by filtration after standing 10min.
It is passed through hydrogen fluoride into ammonium acid fluoride-ammonium fluoride solution at 50 DEG C, the pH value for adjusting solution is 3, obtains ammonium hydrogen fluoride solution, should
Solution concentrates at absolute pressure 80kPa, is dry（Drying temperature is 100 DEG C）, obtain ammonium acid fluoride product.
White carbon 59.6g is obtained in this process, and yield is more than 99%, and purity is more than 98%, specific surface area 174m2/g；
Obtain ammonium acid fluoride 218g, yield 95.5%, purity 97.8%.
Embodiment 3
220g potassium fluosilicates are added to the ammonium hydroxide that mass concentration is 10%（694g）In, it is stirred to react 30min at 70 DEG C, stands
Silica filter cake and potassium fluoride-ammonium fluoride solution are obtained by filtration after 10min, silica filter cake is washed, is obtained after dry
White carbon black product.Washing filtrate merges with potassium fluoride-ammonium fluoride solution, and the fluosilicic acid that mass concentration is 18% is added（800g）,
It is stirred to react 30min at 50 DEG C, potassium fluosilicate and ammonium acid fluoride-ammonium fluoride solution is obtained by filtration after standing 10min.At 30 DEG C to
It is passed through hydrogen fluoride in ammonium acid fluoride-ammonium fluoride solution, the pH value for adjusting solution is 3, obtains ammonium hydrogen fluoride solution, the solution is exhausted
To concentration, drying under pressure 50kPa（Drying temperature is 90 DEG C）, obtain ammonium acid fluoride product.
White carbon 59.7g is obtained in this process, and yield is more than 99%, and purity is more than 98%, specific surface area 178m2/g；
Obtain 215.4 g of ammonium acid fluoride, yield 94.5%, purity 98.1%.
Embodiment 4
220 g potassium fluosilicates are added to the ammonium hydroxide that mass concentration is 30%（232g）In, it is stirred to react 60min at 70 DEG C, stands
Silica filter cake and potassium fluoride-ammonium fluoride solution are obtained by filtration after 10min, silica filter cake is washed, is obtained after dry
White carbon black product.Washing filtrate merges with potassium fluoride-ammonium fluoride solution, and the fluosilicic acid that mass concentration is 8% is added（1800g）,
It is stirred to react 30min at 40 DEG C, potassium fluosilicate and ammonium acid fluoride-ammonium fluoride solution is obtained by filtration after standing 10min.At 30 DEG C to
It is passed through hydrogen fluoride in ammonium acid fluoride-ammonium fluoride solution, the pH value for adjusting solution is 3, obtains ammonium hydrogen fluoride solution, the solution is exhausted
To concentration, drying under pressure 35kPa（Drying temperature is 80 DEG C）, obtain ammonium acid fluoride product.
White carbon 59g, yield 98.3% are obtained in this process, and purity is more than 98%, specific surface area 174m2/g；
To 221.2 g of ammonium acid fluoride, yield 97%, purity 97.5%.
Embodiment 5
220 g potassium fluosilicates are added to the ammonium hydroxide that mass concentration is 18%（387g）In, it is stirred to react 50min at 60 DEG C, stands
Silica filter cake and potassium fluoride-ammonium fluoride solution are obtained by filtration after 10min, silica filter cake is washed, is obtained after dry
White carbon black product.Washing filtrate merges with potassium fluoride-ammonium fluoride solution, and the fluosilicic acid that mass concentration is 10% is added
（1440g）, it is stirred to react 40min at 30 DEG C, potassium fluosilicate and ammonium acid fluoride-ammonium fluoride solution is obtained by filtration after standing 10min.
It is passed through hydrogen fluoride into ammonium acid fluoride-ammonium fluoride solution at 20 DEG C, the pH value for adjusting solution is 3, obtains ammonium hydrogen fluoride solution, should
Solution concentrates at 35 kPa of absolute pressure, is dry（Drying temperature is 80 DEG C）, obtain ammonium acid fluoride product.
White carbon 58.4g, yield 97.3% are obtained in this process, and purity is more than 98%, specific surface area 181m2/g；
Obtain ammonium acid fluoride 221g, yield 96.9%, purity 98.3%.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method that sylvite circular treatment fluosilicic acid prepares ammonium acid fluoride, which is characterized in that the method includes：
(1) potassium fluosilicate is reacted with ammonium hydroxide, is separated by solid-liquid separation after the completion of reaction and obtains potassium fluoride-ammonium fluoride solution and dioxy
SiClx filter cake, the silica filter cake are used to prepare white carbon；
(2) potassium fluoride-ammonium fluoride solution is reacted with fluosilicic acid, is separated by solid-liquid separation after the completion of reaction and obtains ammonium acid fluoride-ammonium fluoride
Solution and potassium fluosilicate, the potassium fluosilicate return to step (1) are used as raw material；
(3) it is passed through hydrogen fluoride into ammonium acid fluoride-ammonium fluoride solution ammonium fluoride is made to be fully converted to ammonium acid fluoride and obtain hydrogen fluoride
Ammonium salt solution obtains ammonium acid fluoride after concentrated, dry.
2. the method that sylvite circular treatment fluosilicic acid according to claim 1 prepares ammonium acid fluoride, which is characterized in that in step
Suddenly the source of potassium fluosilicate can be to be obtained by the reaction with potassium sulfate by phosphoric acid industry fluosilicic acid as byproduct in (1).
3. the method that sylvite circular treatment fluosilicic acid according to claim 1 prepares ammonium acid fluoride, which is characterized in that in step
Suddenly in (1), reaction temperature is 20-70 DEG C, reaction time 30-60min, and the molar ratio of the potassium fluosilicate and ammonia is 1:4.0-
4.5, the mass concentration of the ammonium hydroxide is 10%-30%.
4. the method that sylvite circular treatment fluosilicic acid according to claim 1 prepares ammonium acid fluoride, which is characterized in that in step
Suddenly in (2), reaction temperature is 20-50 DEG C, reaction time 10-30min, and the molar ratio of the fluosilicic acid and potassium fluoride is 1:2.
5. the method that sylvite circular treatment fluosilicic acid according to claim 1 or 2 prepares ammonium acid fluoride, which is characterized in that
The fluosilicic acid is phosphoric acid industry by-product, mass concentration 8%-18%.
6. the method that sylvite circular treatment fluosilicic acid according to claim 1 prepares ammonium acid fluoride, which is characterized in that in step
Suddenly in (3), reaction temperature is 20-50 DEG C, and it is 3 to be passed through hydrogen fluoride adjustment pH value.
7. the method that sylvite circular treatment fluosilicic acid according to claim 1 prepares ammonium acid fluoride, which is characterized in that in step
Suddenly in (3), condensed water that concentration process generates, which is sent, to be washed process to phosphoric acid tail and obtains fluosilicic acid.
8. the method that sylvite circular treatment fluosilicic acid according to claim 1 prepares ammonium acid fluoride, which is characterized in that in step
Suddenly in (3), concentration and dry absolute pressure are 35-80KPa, and drying temperature is 80-100 DEG C.
9. the method that sylvite circular treatment fluosilicic acid according to claim 1 prepares ammonium acid fluoride, which is characterized in that described
Method includes the following steps：
(1) potassium fluosilicate is obtained by the reaction by phosphoric acid industry fluosilicic acid as byproduct and potassium sulfate；
(2) potassium fluosilicate that step (1) and/or step (3) obtain is reacted with ammonium hydroxide, reaction temperature is 20-70 DEG C, institute
The molar ratio for stating potassium fluosilicate and ammonia is 1:4.0-4.5 is separated by solid-liquid separation after the completion of reaction and obtains potassium fluoride-ammonium fluoride solution and two
Silica filter cake, the silica filter cake are used to prepare white carbon, and the mass concentration of the ammonium hydroxide is 10%-30%；
(3) potassium fluoride-ammonium fluoride solution that step (2) obtains is reacted with phosphoric acid industry fluosilicic acid as byproduct, reaction temperature is
20-50 DEG C, the molar ratio of the fluosilicic acid and potassium fluoride is 1:2, it is separated by solid-liquid separation after the completion of reaction and obtains ammonium acid fluoride-ammonium fluoride
Solution and potassium fluosilicate, the potassium fluosilicate return to step (2) are used as raw material；
(4) hydrogen fluoride is passed through in the ammonium acid fluoride-ammonium fluoride solution obtained to step (3) makes pH value be 3, reaction temperature 20-
50 DEG C, after the completion of reaction, ammonium acid fluoride is obtained after concentrated, dry, the condensed water that concentration process generates, which is sent to phosphoric acid tail, washes work
Sequence obtains fluosilicic acid；
The mass concentration of the phosphoric acid industry fluosilicic acid as byproduct is 8%-18%.
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Cited By (3)
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| CN114436216A (en) * | 2022-03-03 | 2022-05-06 | 盛隆资源再生（无锡）有限公司 | Method for separating and recovering mixed acid of hydrofluoric acid and hydrochloric acid |
| CN114933316A (en) * | 2022-05-09 | 2022-08-23 | 盛隆资源再生（无锡）有限公司 | Resourceful treatment method for fluosilicic acid and hydrofluoric acid mixed acid and product thereof |
| CN115124019A (en) * | 2022-06-15 | 2022-09-30 | 湖北大学 | Method for preparing silicon-carbon material by utilizing fluosilicic acid waste |
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| CN107867701A (en) * | 2016-09-26 | 2018-04-03 | 青岛九洲千和机械有限公司 | A kind of method that fluorosilicone compound prepares high-quality ammonium acid fluoride |
Cited By (4)
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| CN114436216A (en) * | 2022-03-03 | 2022-05-06 | 盛隆资源再生（无锡）有限公司 | Method for separating and recovering mixed acid of hydrofluoric acid and hydrochloric acid |
| CN114933316A (en) * | 2022-05-09 | 2022-08-23 | 盛隆资源再生（无锡）有限公司 | Resourceful treatment method for fluosilicic acid and hydrofluoric acid mixed acid and product thereof |
| CN115124019A (en) * | 2022-06-15 | 2022-09-30 | 湖北大学 | Method for preparing silicon-carbon material by utilizing fluosilicic acid waste |
| CN115124019B (en) * | 2022-06-15 | 2024-05-28 | 湖北大学 | Method for preparing silicon-carbon material by utilizing fluosilicic acid waste |
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Denomination of invention: A Method for Preparing Ammonium Hydrogen Fluoride from Fluorosilicic Acid by Potassium Salt Cyclic Treatment Effective date of registration: 20230731 Granted publication date: 20191112 Pledgee: Bank of China Limited Huanggang branch Pledgor: HUBEI XIANGYUN (Group) CHEMICAL Co.,Ltd. Registration number: Y2023420000318 |