CN107055477A - The method and its device of hydrogen fluoride are prepared by fluosilicic acid - Google Patents
The method and its device of hydrogen fluoride are prepared by fluosilicic acid Download PDFInfo
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- CN107055477A CN107055477A CN201710280854.3A CN201710280854A CN107055477A CN 107055477 A CN107055477 A CN 107055477A CN 201710280854 A CN201710280854 A CN 201710280854A CN 107055477 A CN107055477 A CN 107055477A
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- ammonia
- fluoride
- hydrogen fluoride
- fluosilicic acid
- ammonium
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/193—Preparation from silicon tetrafluoride, fluosilicic acid or fluosilicates
Abstract
The present invention proposes a kind of method and its device that hydrogen fluoride is prepared by fluosilicic acid, and preparation includes fluosilicic acid with ammonia by two-stage aminating reaction, ammonium fluoride solution and silica solid are obtained after separation；Ammonium fluoride solution is concentrated, crystallized, separated, and obtains ammonium hydrogen fluoride solid and mother liquor；Ammonium hydrogen fluoride solid is reacted with fluoride, obtains hydrogen fluoride thing solid and ammonia；Hydrogen fluoride thing solid is heated, and is allowed to decompose, is obtained hydrogen fluoride gas and potassium fluoride.Device includes, one-level aminating reaction kettle, secondary amine reactor, the first separator, condensing crystallizing kettle, ammonia destilling tower, heat energy supply equipment, the second separator, reactor and decomposer.The present invention utilizes the hydrogen fluoride of byproduct fluosilicic acid industrialized production, and purity can reach more than 99.96%, and other impurities meet national standard technical grade index request, and low production cost.
Description
Technical field
Prepared the invention belongs to hydrogen fluoride and its device field, more particularly to a kind of side that hydrogen fluoride is prepared by fluosilicic acid
Method and its device.
Background technology
Hydrogen fluoride (Hydrogen Fluoride), chemical molecular formula is HF, molecular weight 20.01, soluble in water, ethanol.Nothing
It is colourless transparent liquid, 19.4 DEG C of boiling point, -83.37 DEG C of fusing point, density under water hydrogen fluoride (abbreviation AHF) low temperature or pressure
1.008g/cm3 (water=1).In room temperature and highly volatile under normal temperature into white smoke.Its chemical property is extremely active, can with alkali,
Metal, oxide and silicate etc. react.Hydrogen fluoride is the basis of modern fluorination work, is to produce element fluorine, various fluorine refrigeration
The most basic raw material of agent, fluorine-containing new material, inorganic fluorine salt dissolving, various organic fluorides etc..Hydrofluoric acid is mainly used in semiconductor row
Industry and glass etching agent because under the chemical property torpescence of silicon, normal temperature not with water, air, acid reaction, with highly basic react.
It can be reacted under conditions of 200~400 DEG C with HF：Si+4HF==SiF4+2H2 ↑ reaction rate is quite fast and complete.It is additionally operable to system
Make the organic or inorganic fluoride such as fluorocarbons, sodium fluoride, aluminum fluoride, hex and ice crystal；Hydrofluoric acid is used as fluorination
Fluorine refrigerant, fluoropolymer, fluorine-containing medicines can be produced by learning the important source material of industry, the aluminum fluoride and ice crystal produced with it
It is the essential auxiliary agent of aluminum smelting industry；Or the alkylation catalyst of oil plant, steel industry uses it as surface derusting agent, stone
Change industry is using it as catalyst, cleaning service industry corrodes cleaning agent or outside Wall Cleaning agent using it as dirt；Other hydrofluoric acid life
The fluoride salt of production is widely used in food protection, special smelting, leather and textile processing, Saving specimen and nuclear industry
Deng.
In recent years, with the development of China's fluorination work, the series of products development such as fluoride salt, fluorinated aromatic hydrocarbon, fluorine resin
Rapidly, the demand to anhydrous hydrogen fluoride increases very fast.In addition, with the continuous appearance of fluoro-containing pesticide, fluorine-containing medicines intermediate,
The application of electron level fluorine product, the demand to anhydrous hydrogen fluoride is also constantly increasing；In addition external many businessmans come to China to adopt one after another
Hydrogen fluoride and fluoride salt etc. are purchased, flourishing for China's hydrogen fluoride production industry is promoted.
China mainly prepares production AHF using fluorite and sulfuric acid reaction, although the hydrogen fluoride production technology of China has been in
The problems of world lead level, but " fluorite-sulfuric acid process " production technology, such as：Energy utilization rate is low, production cost compared with
Height, fluorgypsum processing is difficult, dust pollution is serious etc., still it can not be ignored.Advocate energy-saving, development low-carbon economy in the whole world
Epoch, the new production technology of exploration and technique turn into the common recognition of professional.Along with fluorite is that national requirements is controlled not
Renewable grand strategy resource, in recent years, control of the government to fluorite ore yield is more and more tighter, and policy is also received tighter and tighter,
The fluorine resource price of fluorite must more and more higher.So, how to develop from the fluorine efficient low-consume in by-product fluosilicic acid, environmental protection
Production hydrogen fluoride technology in ground increasingly draws attention.
The content of the invention
The present invention proposes a kind of method and its device that hydrogen fluoride is prepared by fluosilicic acid, solves by-product fluorine in the prior art
Silicic acid is superfluous, and the environmental pollution problem that may thus bring.
The problem of cost is high, and existing hydrogen fluoride Preparation equipment configuration requirement height are prepared this invention also solves hydrogen fluoride
The problem of.
A kind of method that hydrogen fluoride is prepared by fluosilicic acid, including,
1) fluosilicic acid obtains ammonium fluoride solution and silica solid with ammonia by two-stage aminating reaction after separation；
2) by step 1) obtained ammonium fluoride solution concentrated, crystallized, separated, and obtains ammonium hydrogen fluoride solid and mother liquor；
3) by step 2) obtained ammonium hydrogen fluoride solid and fluoride reacted, and obtains hydrogen fluoride thing solid and ammonia；
Ammonia is back to use step 1)；The fluoride is potassium fluoride or sodium fluoride；The hydrogen fluoride thing is potassium hydrogen fluoride or sodium bifluoride；
4) by step 3) heating of obtained hydrogen fluoride thing solid, it is allowed to decompose, obtains hydrogen fluoride gas and fluoride；Fluorination
Thing is back to use step 3)；
Wherein, step 1) in first set reaction add ammonia be outsourcing liquefied ammonia；Step 3) in first set reaction add fluorine
Compound is outsourcing fluoride；Step 2) in mother liquor continue and step 1) obtained ammonium fluoride solution mixes, and repeats step
2) operation.
Be used as preferred technical scheme, the step 1) in fluosilicic acid and liquefied ammonia mol ratio be 1：6~6.02；Reaction temperature
Spend for 75~95 DEG C；Two-stage aminating reaction is continuous, and it is also continuously to be directly separated that silica is separated after reaction；Obtain
Silica purity is more than or equal to 99.5%.
As preferred technical scheme, the one-level aminating reaction in the two-stage aminating reaction is generated by fluosilicic acid and liquefied ammonia
Ammonium fluosilicate；Secondary amineization reaction generates ammonium fluoride by ammonium fluosilicate and liquefied ammonia.
Be used as preferred technical scheme, the step 2) in ammonium fluoride concentration temperature be 65~180 DEG C, pressure for-
0.07~0.2Mpa.
Be used as preferred technical scheme, the step 3) in reaction temperature be 115~225 DEG C.
Be used as preferred technical scheme, the step 4) in decomposition temperature be 150~420 DEG C, pressure be -0.05~
0.15Mpa。
Be used as preferred technical scheme, the step 4) in sodium bifluoride decomposition temperature be 160~210 DEG C.
Be used as preferred technical scheme, the step 4) in potassium hydrogen fluoride decomposition temperature be 360~380 DEG C.As excellent
The technical scheme of choosing, in addition to by step 4) obtain hydrogen fluoride anhydrous hydrogen fluoride is made by condensation；Or it has been absorbed as water with water
Hydrofluoric acid.
As preferred technical scheme, in addition to by step 4) hydrogen fluoride is obtained, first cleaned with the concentrated sulfuric acid, then condense or use
Water absorbs.
As preferred technical scheme, the step 2) in contain 1-40%'s in evaporation water of ammonium fluoride solution when concentrating
Ammonia, ammonia therein is reclaimed by ammonia destilling tower, and it can be that ammonia can also be ammoniacal liquor to reclaim ammonia, is reclaimed ammonia and is returned to the 1st grade of ammonia
Change reaction and the 2nd grade of aminating reaction.Water after recovery ammonia can be discharged directly.
A kind of device that hydrogen fluoride is prepared for fluosilicic acid, including,
One-level aminating reaction kettle, secondary amine reactor, the first separator, condensing crystallizing kettle, ammonia destilling tower, heat energy supply
Equipment, the second separator, reactor and decomposer；The one-level aminating reaction kettle, secondary amine reactor, the first separation
Device, condensing crystallizing kettle, the second separator, reactor and decomposer are sequentially communicated；
The one-level aminating reaction kettle has fluosilicic acid charging aperture；
The one-level aminating reaction kettle, secondary amine reactor respectively there is ammonia to feed the mouth of pipe；
The charging aperture of the ammonia destilling tower is connected with the evaporation vapor outlet of condensing crystallizing kettle, and the ammonia of the ammonia destilling tower goes out
The ammonia feed mouth of pipe of the mouth respectively with the one-level aminating reaction kettle, secondary amine reactor is connected, to realize the circulation of ammonia
Utilize；
The ammonia destilling tower is additionally provided with discharge of wastewater mouth；
The reactor also include supplement fluoride charging aperture and ammonia outlet, the ammonia outlet respectively with it is described
One-level aminating reaction kettle, the ammonia feed mouth of pipe of secondary amine reactor are connected, to realize recycling for ammonia；
The heat energy supply equipment is connected with the condensing crystallizing kettle, ammonia destilling tower, reactor and decomposer respectively, to carry
Heat supply energy.
As preferred technical scheme, in addition to condenser, it is connected with the decomposer.
As preferred technical scheme, the mother liquor outlet of second separator is connected by pipeline and the condensing crystallizing kettle
It is logical.
Chemical equation of the present invention：
H2SiF6+2NH3→(NH4)2SiF6………………………………(1)
(NH4)2SiF6+4NH3→6NH4F………………………………(2)
2NH4F→NH4HF2+NH3………………………………(3)
NH4HF2+2KF→2KHF2+NH3………………………………(4)
NH4HF2+2NaF→2NaHF2+NH3………………………………(5)
KHF2→HF+KF………………………………(6)
NaHF2→HF+NaF………………………………(7)
Beneficial effect
(1) present invention is using fluosilicic acid and the two-stage aminating reaction of ammonia, and so operation has 5 advantages：A. ammonia can be saved
Injected volume, ammonia do not need excess it is a lot；B. precipitation of silica is quickly；C. silica separation is easy to；D. in ammonium fluoride
Dioxide-containing silica it is very low；E. good effect of heat exchange.
(2) present invention carries out solid phase reaction using ammonium hydrogen fluoride solid with fluoride, obtains ammonia；Compared in ammonium fluoride
Solution is compared with fluoride reacts the liquid phase reactor for producing potassium hydrogen fluoride solution, and ammonia is recovered more easily；Escapable cost, is conducive to
Environmental protection, realizes green production.
(3) present invention utilizes the hydrogen fluoride of byproduct fluosilicic acid industrialized production, and purity can reach more than 99.96%,
Other impurities meet national standard technical grade index request, and low production cost.
(4) present invention selection contains 2- after 160~380 DEG C of temperature ranges are decomposed in potassium fluoride (or sodium fluoride) product
5% potassium hydrogen fluoride (or sodium bifluoride) is undecomposed, and mixture reuse has no influence into step 3 on reaction, but can effectively save
Energy.
(5) equipment of the invention realizes recycling for raw material, and the water of technique discharge is realized without being handled again
Resource circulation utilization and the combination of environmental protection.Rationally, floor space is small for device layout, is adapted to industrial application.
(6) one-level aminating reaction kettle, secondary amine reactor, the first separator, condensing crystallizing kettle, the ammonia of present device
Between destilling tower, heat energy supply equipment, the second separator, reactor, decomposer and condenser, connected by pipeline closed,
Each reuse material is also to constitute closed reuse pipeline, therefore equipment easily realizes sealing；Process operation is in computer program control
Under system, according to the technological parameter automatic running of setting.
Brief description of the drawings
, below will be to embodiment in order to illustrate more clearly of embodiment of the present invention or technical scheme of the prior art
Or the accompanying drawing used required in description of the prior art is briefly described, it should be apparent that, drawings in the following description are only
It is some embodiments of the present invention, for those of ordinary skill in the art, is not paying the premise of creative labor
Under, other accompanying drawings can also be obtained according to these accompanying drawings.
The structural representation of the device that hydrogen fluoride is prepared for fluosilicic acid of Fig. 1 embodiments 1.
Fig. 2 is prepared the process chart of the method for hydrogen fluoride by fluosilicic acid.
Wherein,
One-level aminating reaction kettle 11, secondary amine reactor 12, the first separator 13, condensing crystallizing kettle 14, ammonia destilling tower
15th, heat energy supply equipment 16, the second separator 17, reactor 18, decomposer 19, condenser 20.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
Embodiment 1
It is shown in Figure 1, it is a kind of to prepare the device of hydrogen fluoride for fluosilicic acid, including, one-level aminating reaction kettle 11, two grades
Aminating reaction kettle 12, the first separator 13, condensing crystallizing kettle 14, ammonia destilling tower 15, heat energy supply equipment 16, the second separator
17th, reactor 18 and decomposer 19.Wherein one-level aminating reaction kettle 11, secondary amine reactor 12, the first separator 13, dense
Contracting crystallization kettle 14, the second separator 17, reactor 18 and decomposer 19 are sequentially communicated by pipeline and valve.One-level ammonification is anti-
Answer kettle 11 that there is fluosilicic acid charging aperture, one-level aminating reaction kettle 11 and secondary amine reactor 12 have ammonia feeding pipe respectively.
The charging aperture of ammonia destilling tower 15 is connected with the evaporation moisture outlet of condensing crystallizing kettle 14, is given birth to during for condensing crystallizing kettle 14 to be concentrated
Into be passed through containing ammonia vapor in ammonia destilling tower 15.The ammonia outlet of ammonia destilling tower 15 respectively with one-level aminating reaction kettle 11, two
The ammonia feeding pipe of level aminating reaction kettle 12 is connected, to realize recycling for ammonia.Ammonia destilling tower 15 is additionally provided with waste water row
Mouth is put, unnecessary water can be expelled directly out after ammonia still process.Reactor 18 also includes the charging aperture and ammonia outlet of supplement fluoride,
Ammonia feed pipeline of the ammonia outlet respectively with one-level aminating reaction kettle 11, secondary amine reactor 12 is connected, to realize ammonia
Gas is recycled.Heat energy supply equipment 16 connects with condensing crystallizing kettle 14, ammonia destilling tower 15, reactor 18 and decomposer 19 respectively
Connect, to provide heat energy.In order to which by obtained fluorination hydrogen retrieval, condenser 20 is also provided with this implementation row, itself and decomposer 19
Connection.In order to utilize raw material to greatest extent, the discharge of waste is reduced, the second separator 17 is connected with condensing crystallizing kettle 14,
Mother liquor in separator is back to recycling in condensing crystallizing kettle 14 by pipeline.The one-level aminating reaction kettle of the equipment,
Secondary amine reactor, the first separator, condensing crystallizing kettle, ammonia destilling tower, heat energy supply equipment, the second separator, reactor,
Between decomposer and condenser, connected by pipeline closed, each reuse material is also to constitute closed reuse pipeline, therefore is set
It is standby easily to realize sealing；Process operation is under computer program control, according to the technological parameter automatic running of setting.
Embodiment 2
Hydrogen fluoride is prepared using the equipment in embodiment 1.
Raw material：30% fluosilicic acid is 1000kg, liquefied ammonia 20kg, potassium fluoride 75kg.
Specific steps：
(1) fluosilicic acid and liquefied ammonia are added in one-level aminating reaction kettle 11, reaction condition is controlled at 80 DEG C, reaction is complete
Afterwards, secondary amine reactor 12 is passed through, continues to react, obtains silica and ammonium fluoride solution.By 13 points of the first separator
Separate out silica and ammonium fluoride solution.Wherein dioxide-containing silica is 99.6%, and dioxide-containing silica is low in ammonium fluoride solution
In 0.3%.
(2) ammonium fluoride solution that step (1) is isolated is passed through in condensing crystallizing kettle 14, and reaction condition is controlled at 95 DEG C, instead
Ammonium acid fluoride and mother liquor are isolated after answering completely through the second separator 17 again.Wherein mother liquor is returned continues to make in condensing crystallizing kettle 14
With.Ammonia destilling tower 15 is passed through containing ammonia vapor, the ammonia after purification is passed through one-level aminating reaction kettle 11 and secondary amine reactor
In 12.In the present embodiment, the ammonia being recycled back into for the last time is absorbed as ammoniacal liquor, obtains 6% ammoniacal liquor 300kg；With this
Conversion, the ammonia consumption that the present invention prepares hydrogen fluoride per ton only has 8.1kg.
(3) by isolated ammonium hydrogen fluoride solid and potassium fluoride in reactor 18 hybrid reaction, reaction condition control
At 170 DEG C, potassium hydrogen fluoride solid and ammonia are obtained.Ammonia is back to use step (1).
(4) potassium hydrogen fluoride solid is sent into decomposition reactor 18, temperature control is decomposed 1 hour at 420 DEG C, reaction life
Into hydrogen fluoride and potassium fluoride.Hydrogen fluoride obtains anhydrous liquid hydrogen fluoride 246.6kg after -5 DEG C of condenser condensation.It is made
Fluorination hydrogen purity be more than 99.96%.
Remaining potassium fluoride weight is 74.5kg；Converted with this, the present invention prepares the potassium fluoride consumption of hydrogen fluoride per ton only
There is 2kg.
Embodiment 3
Hydrogen fluoride is prepared using the equipment in embodiment 1.
The method that hydrogen fluoride is prepared by fluosilicic acid, including,
1) fluosilicic acid and liquefied ammonia are according to mol ratio 1:1.8 are passed through in first order reaction kettle, and temperature control is 75 DEG C, and reaction is complete
After obtain ammonium fluosilicate, be passed through in second order reaction kettle, the mol ratio of ammonium fluosilicate and liquefied ammonia is 1：4.22, continue to react, obtain
Silica and ammonium fluoride solution.Silica and ammonium fluoride solution are isolated by the first separator 13.Obtained titanium dioxide
Silicon purity is more than 99.5%.
2) by step 1) obtained ammonium fluoride solution is passed through in condensing crystallizing kettle 14, reaction condition control in 65 DEG C of temperature,
Pressure -0.07Mpa, ammonium acid fluoride and mother liquor are isolated after reaction completely through the second separator 17 again.Wherein mother liquor returns to concentration
It is continuing with crystallization kettle 14.The ammonia and vapor escaped during concentration is passed through ammonia destilling tower 15, and the ammonia after purification is passed through one
In level aminating reaction kettle 11 and secondary amine reactor 12.The direct qualified discharge of water after ammonia still process.In the present embodiment, last
The secondary ammonia being recycled back into is absorbed as ammoniacal liquor, obtains 6% ammoniacal liquor 300kg；Converted with this, the present invention prepares hydrogen fluoride per ton
Ammonia consumption there was only 8.1kg.
3) by isolated ammonium hydrogen fluoride solid and sodium fluoride in reactor 18 hybrid reaction, reaction condition control exist
125 DEG C, obtain sodium bifluoride solid and ammonia.Ammonia is back to use step 1).
4) sodium bifluoride solid is sent into decomposition reactor 18, temperature control is decomposed 1.5 hours at 150 DEG C, reaction life
Into hydrogen fluoride and sodium fluoride.Hydrogen fluoride is passed through in condenser 20, using -5 DEG C of brine-cooleds, obtains anhydrous liquid hydrogen fluoride.System
The fluorination hydrogen purity obtained is more than 99.96%.
Embodiment 4
Hydrogen fluoride is prepared using the equipment in embodiment 1.
The method that hydrogen fluoride is prepared by fluosilicic acid, including,
1) fluosilicic acid and liquefied ammonia are according to mol ratio 1:2.2 are passed through in first order reaction kettle, and temperature control is 95 DEG C, and reaction is complete
After obtain ammonium fluosilicate, be passed through in second order reaction kettle, the mol ratio of ammonium fluosilicate and liquefied ammonia is 1：3.8, continue to react, obtain two
Silica and ammonium fluoride solution.Silica and ammonium fluoride solution are isolated by the first separator 13.Obtained silica
Purity is more than 99.5%.
2) by step 1) obtained ammonium fluoride solution is passed through in condensing crystallizing kettle 14, reaction condition control in 180 DEG C of temperature,
Pressure 0.2Mpa, ammonium acid fluoride and mother liquor are isolated after reaction completely through the second separator 17 again.Wherein mother liquor returns to concentration knot
It is continuing with brilliant kettle 14.The ammonia and vapor escaped during concentration is passed through ammonia destilling tower 15, and the ammonia after purification is passed through one-level
In aminating reaction kettle 11 and secondary amine reactor 12.The direct qualified discharge of water after ammonia still process.
3) by isolated ammonium hydrogen fluoride solid and sodium fluoride in reactor 18 hybrid reaction, reaction condition control exist
115 DEG C, obtain sodium bifluoride solid and ammonia.Ammonia is back to use step 1).
4) sodium bifluoride solid is sent into decomposition reactor 18, temperature control is at 210 DEG C, and pressure 0.15Mpa is decomposed
1.0 hours, reaction generated hydrogen fluoride and sodium fluoride.Hydrogen fluoride is first cleaned with the concentrated sulfuric acid, is then absorbed as hydrofluoric acid with water.Wherein
After 160~210 DEG C of temperature ranges are decomposed, the sodium bifluoride containing 2-5% is undecomposed in sodium fluoride product, and mixture reuse is extremely
Influence is had no on reaction in step 3, but can effectively be saved.
Embodiment 5
Hydrogen fluoride is prepared using the equipment in embodiment 1.
1) fluosilicic acid and liquefied ammonia are according to mol ratio 1:2 are passed through in first order reaction kettle, and temperature control is 90 DEG C, after reaction completely
Ammonium fluosilicate is obtained, is passed through in second order reaction kettle, the mol ratio of ammonium fluosilicate and liquefied ammonia is 1：4, continue to react, obtain titanium dioxide
Silicon and ammonium fluoride solution.Silica and ammonium fluoride solution are isolated by the first separator 13.Obtained silica purity
More than 99.5%.
2) by step 1) obtained ammonium fluoride solution is passed through in condensing crystallizing kettle 14, reaction condition control in 100 DEG C of temperature,
Pressure 0.1Mpa, ammonium acid fluoride and mother liquor are isolated after reaction completely through the second separator 17 again.Wherein mother liquor returns to concentration knot
It is continuing with brilliant kettle 14.Ammonia is passed through ammonia destilling tower 15, and the ammonia after purification is passed through one-level aminating reaction kettle 11 and secondary amine
Change in reactor 12.Waste liquid is directly discharged.
3) by isolated ammonium hydrogen fluoride solid and potassium fluoride in reactor 18 hybrid reaction, reaction condition control exist
150 DEG C, obtain potassium hydrogen fluoride solid and ammonia.Ammonia is back to use step 1).
4) potassium hydrogen fluoride solid is sent into decomposition reactor 18, temperature control is in 360 DEG C, pressure -0.05Mpa, reaction
1.5 hours, reaction generated hydrogen fluoride and potassium fluoride.Hydrogen fluoride is first cleaned with the concentrated sulfuric acid, is then passed in condenser 20, is used -5
DEG C brine-cooled, obtains anhydrous liquid hydrogen fluoride；Obtained fluorination hydrogen purity is more than 99.96%.Wherein temperature 360~
380 DEG C of temperature ranges are decomposed, and the potassium hydrogen fluoride containing 2-5% is undecomposed in potassium fluoride product, and mixture reuse is right into step 3
Reaction has no influence, but can effectively save.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of method that hydrogen fluoride is prepared by fluosilicic acid, it is characterised in that including,
1) fluosilicic acid obtains ammonium fluoride solution and silica solid with ammonia by two-stage aminating reaction after separation；
2) by step 1) obtained ammonium fluoride solution concentrated, crystallized, separated, and obtains ammonium hydrogen fluoride solid and mother liquor；
3) by step 2) obtained ammonium hydrogen fluoride solid and fluoride reacted, and obtains hydrogen fluoride thing solid and ammonia；Ammonia
It is back to use step 1)；The fluoride is potassium fluoride or sodium fluoride；The hydrogen fluoride thing is potassium hydrogen fluoride or sodium bifluoride；
4) by step 3) heating of obtained hydrogen fluoride thing solid, it is allowed to decompose, obtains hydrogen fluoride gas and fluoride；Fluoride is returned
Use step 3)；
Wherein, step 1) in first set reaction add ammonia be outsourcing liquefied ammonia；Step 3) in first set reaction add fluoride
For outsourcing fluoride；Step 2) in mother liquor continue and step 1) obtained ammonium fluoride solution mixes, and repeats step 2)
Operation.
2. a kind of method that hydrogen fluoride is prepared by fluosilicic acid according to claim 1, it is characterised in that the step 1) in
The mol ratio of fluosilicic acid and liquefied ammonia is 1：6~6.02；Reaction temperature is 75~95 DEG C；Two-stage aminating reaction is continuous, reaction
Separation silica is also continuously to be directly separated afterwards；Obtained silica purity is more than or equal to 99.5%.
3. a kind of method that hydrogen fluoride is prepared by fluosilicic acid according to claim 2, it is characterised in that
One-level aminating reaction in the two-stage aminating reaction generates ammonium fluosilicate by fluosilicic acid and liquefied ammonia；Secondary amineization reaction by
Ammonium fluosilicate generates ammonium fluoride with liquefied ammonia.
4. a kind of method that hydrogen fluoride is prepared by fluosilicic acid according to claim 1, it is characterised in that the step 2) in
Ammonium fluoride concentration temperature be 65~180 DEG C, pressure be -0.07~0.2Mpa；The step 3) in reaction temperature be 115
~225 DEG C；The step 4) in decomposition temperature be 150~420 DEG C, pressure be -0.05~0.15Mpa.
5. a kind of method that hydrogen fluoride is prepared by fluosilicic acid according to claim 1, it is characterised in that also including by step
4) obtain hydrogen fluoride and anhydrous hydrogen fluoride is made by condensation；Or water hydrofluoric acid has been absorbed as with water；The step 4) in fluorination
The decomposition temperature of hydrogen sodium is 160~210 DEG C；The step 4) in potassium hydrogen fluoride decomposition temperature be 360~380 DEG C.
6. a kind of method that hydrogen fluoride is prepared by fluosilicic acid according to claim 1, it is characterised in that also including by step
4) hydrogen fluoride is obtained, is first cleaned with the concentrated sulfuric acid, then condenses or is absorbed with water.
7. a kind of method that hydrogen fluoride is prepared by fluosilicic acid according to claim 1, it is characterised in that the step 2) in
Ammonia containing 1-40% in evaporation water when ammonium fluoride solution is concentrated, ammonia therein is reclaimed by ammonia destilling tower, is reclaimed ammonia and is returned
Into two-stage aminating reaction；Water after recovery ammonia is directly discharged.
8. a kind of device that hydrogen fluoride is prepared for fluosilicic acid, it is characterised in that including,
One-level aminating reaction kettle, secondary amine reactor, the first separator, condensing crystallizing kettle, ammonia destilling tower, heat energy supply are set
Standby, the second separator, reactor and decomposer；The one-level aminating reaction kettle, secondary amine reactor, the first separator,
Condensing crystallizing kettle, the second separator, reactor and decomposer are sequentially communicated；
There is the one-level aminating reaction kettle fluosilicic acid to feed the mouth of pipe；The one-level aminating reaction kettle, secondary amine reactor point
Ju You not ammonia feeding pipe；
The charging aperture of the ammonia destilling tower is connected with the steam (vapor) outlet of condensing crystallizing kettle, the ammonia outlet difference of the ammonia destilling tower
It is connected with the ammonia feed pipeline of the one-level aminating reaction kettle, secondary amine reactor, to realize recycling for ammonia；
The ammonia destilling tower is additionally provided with discharge of wastewater mouth；
The reactor also include supplement fluoride charging aperture and ammonia outlet, the ammonia outlet respectively with the one-level
Aminating reaction kettle, the ammonia feed pipeline of secondary amine reactor are connected, to realize recycling for ammonia；
The heat energy supply equipment is connected with the condensing crystallizing kettle, ammonia destilling tower, reactor and decomposer respectively, to provide heat
Energy.
9. a kind of device that hydrogen fluoride is prepared for fluosilicic acid according to claim 8, it is characterised in that also including condensation
Device, it is connected with the decomposer.
10. a kind of device that hydrogen fluoride is prepared for fluosilicic acid according to claim 8, it is characterised in that described second
The mother liquor outlet of separator is connected by pipeline with the condensing crystallizing kettle.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108163812A (en) * | 2017-12-06 | 2018-06-15 | 多氟多化工股份有限公司 | A kind of preparation method of hydrogen fluoride, the preparation method of hydrofluoric acid |
| CN112119035A (en) * | 2018-05-08 | 2020-12-22 | “新化学产品”有限责任公司 | Method for treating hexafluorosilicic acid to produce hydrogen fluoride |
| CN113800470A (en) * | 2021-10-11 | 2021-12-17 | 苏州金宏气体股份有限公司 | Device and process for preparing hydrogen fluoride by ammoniation method |
| CN113880049A (en) * | 2021-11-01 | 2022-01-04 | 衢州市鼎盛化工科技有限公司 | Method and system for recovering hydrogen fluoride |
| CN114804030A (en) * | 2022-04-28 | 2022-07-29 | 多氟多新材料股份有限公司 | Preparation method and device of anhydrous hydrogen fluoride |
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| CN112119035B (en) * | 2018-05-08 | 2024-01-16 | “新化学产品”有限责任公司 | Method for treating hexafluorosilicic acid to produce hydrogen fluoride |
| CN112119035A (en) * | 2018-05-08 | 2020-12-22 | “新化学产品”有限责任公司 | Method for treating hexafluorosilicic acid to produce hydrogen fluoride |
| KR20210003246A (en) * | 2018-05-08 | 2021-01-11 | 오브쉐스트보 에스 오그라니첸노이 오트베트스트벤노스티유 “노비에 키미체스키에 프로덕티” | Method of treating hexafluorine silicic acid to produce hydrogen fluoride |
| JP2021523081A (en) * | 2018-05-08 | 2021-09-02 | オブシェストヴォ エス オグラニチェノジェ オトヴェトストヴェノストジュ“ノヴィエ クヒミチェスキー プロダクティ” | Method of treating hexafluorosilicic acid to produce hydrogen fluoride |
| JP7162362B2 (en) | 2018-05-08 | 2022-10-28 | オブシェストヴォ エス オグラニチェノジェ オトヴェトストヴェノストジュ“ノヴィエ クヒミチェスキー プロダクティ” | Method for treating hexafluorosilicic acid to produce hydrogen fluoride |
| KR102491311B1 (en) * | 2018-05-08 | 2023-01-27 | 오브쉐스트보 에스 오그라니첸노이 오트베트스트벤노스티 유 “노비에 키미체스키에 프로덕티” | Method for producing hydrogen fluoride by treating hexafluorine silicic acid |
| CN113800470A (en) * | 2021-10-11 | 2021-12-17 | 苏州金宏气体股份有限公司 | Device and process for preparing hydrogen fluoride by ammoniation method |
| CN113880049A (en) * | 2021-11-01 | 2022-01-04 | 衢州市鼎盛化工科技有限公司 | Method and system for recovering hydrogen fluoride |
| CN114804030A (en) * | 2022-04-28 | 2022-07-29 | 多氟多新材料股份有限公司 | Preparation method and device of anhydrous hydrogen fluoride |
| CN114804030B (en) * | 2022-04-28 | 2024-02-02 | 多氟多新材料股份有限公司 | Preparation method and device of anhydrous hydrogen fluoride |
| CN115771901A (en) * | 2022-11-30 | 2023-03-10 | 多氟多新材料股份有限公司 | Synthetic method of sodium hydrogen fluoride |
| CN115744827A (en) * | 2022-11-30 | 2023-03-07 | 福建省龙氟新材料有限公司 | Method and device for preparing hydrogen fluoride from fluosilicic acid |
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