CN106241740A - A kind of method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor - Google Patents
A kind of method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor Download PDFInfo
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- CN106241740A CN106241740A CN201610778760.4A CN201610778760A CN106241740A CN 106241740 A CN106241740 A CN 106241740A CN 201610778760 A CN201610778760 A CN 201610778760A CN 106241740 A CN106241740 A CN 106241740A
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- mixed liquor
- acidolysis
- fluoride
- anhydrous hydrogen
- sulphuric acid
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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
- C01B7/194—Preparation from 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
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
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- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to fluorochemical, particularly relate to a kind of method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor, including: 1) concentrated sulphuric acid is heated to 170 220 DEG C, and keep circulation；2) it is sprayed to ammonium fluoride acidolysis mixed liquor circulate concentrated sulphuric acid surface, collects gas, cooled, obtain the thick finished product of fluohydric acid gas；3) by thick for fluohydric acid gas finished product through rectification, degassing, obtain anhydrous hydrogen fluoride product, utilize the inventive method can obtain the content anhydrous hydrogen fluoride product more than 99.9%, and the response rate of fluohydric acid gas is more than 92%, the inventive method has that technique is simple, energy consumption is low, operate safe and reliable feature, the corrosion resistant problem of the equipment that also solves, improves utilization rate of equipment and installations.
Description
Technical field
The present invention relates to fluorochemical, particularly relate to a kind of produce anhydrous hydrogen fluoride from the ammonium fluoride acidolysis mixed liquor
Method.
Background technology
In recent years, along with technological progress and the growth of demand, the application of fluorine product has infiltrated into building, electronics, the energy, ring
The new industry such as guarantor, information, biological medicine, the product such as fluororesin, fluorubber, fluoro coatings, fluoride-containing PMMA, inorganic fluoride
Demand growth rapid, but the high speed development of China's fluorine chemical industry, fluorite resource is the most exhausted, recycles in phosphorus ore rich
Rich fluorine resource not only contributes to administer fluoride pollution, also helps the pressure alleviating fluorite resource.
It is by the concentrated sulphuric acid of solid ammonium fluosilicate Yu 92%-99% that traditional hexafluosilicic acid produces in the method for anhydrous hydrogen fluoride
Carry out acidolysis reaction, produce SiF4Mixed gas with HF；Wherein sulphuric acid is with H2SO4It is calculated as the 100%-of theoretical amount
150%；Resolve the SiF that volatilizees under vacuum4And HF, vacuum degree control at 55kPa-85kPa, temperature control 120 DEG C-
140℃；The SiF that volatilizees is carried out at ambient pressure when resolving4During with HF, temperature controls at 140 DEG C-175 DEG C；Mixed gas is scrubbed,
Anhydrous hydrogen fluoride, SiF is obtained after purification, condensation4For preparing ammonium fluosilicate, such as Patent No. 201210565361.1, " one
The method that the fluorine-containing waste liquid of phosphatic fertilizer company or hexafluosilicic acid prepare anhydrous hydrogen fluoride ", disclose waste gas containing fluoride absorbing liquid or hexafluosilicic acid
In water get rid of by concentrating ammonium fluosilicate, then can prepare, with the concentrated sulphuric acid acidolysis solid ammonium fluosilicate stage, the fluorine that water content is the lowest
Change hydrogen and Silicon fluoride. mixed gas；But in such scheme, the yield of fluohydric acid gas is the most not fully up to expectations.
At present, though there being the production method of a lot of anhydrous hydrogen fluoride, but the yield that mostly there is fluohydric acid gas is the highest, produces equipment
The problem of seriously corroded.
Summary of the invention
For solving above-mentioned technical problem, the invention provides a kind of production anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor
Method.
The present invention is achieved by the following technical programs.
A kind of method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor, comprises the following steps:
1) it is the concentrated sulphuric acid of 94-98% by ammonium fluoride crystal and volumetric concentration, carries out acidolysis reaction, acidolysis reaction equation
As follows: NH4F+H2SO4=HF ↑+NH4HSO4；Wherein, the addition of concentrated sulphuric acid is to generate concentrated sulphuric acid amount needed for ammonium hydrogen sulfate
1.2-1.5 again；
2) 20-25% of thick for acidolysis reaction gained hydrogen fluoride gas total amount sending into refining system, residue is slightly fluorinated hydrogen
Body is dissolved in the liquid after acidolysis reaction, obtains ammonium fluoride acidolysis mixed liquor；
3) temperature of ammonium fluoride acidolysis mixed liquor is controlled at 90-130 DEG C, be at once sprayed in concentrated sulphuric acid circulation fluid, its
In, concentrated sulphuric acid circulation fluid is to use microwave heating to be 170-220 DEG C to concentrated sulphuric acid temperature, and the consumption of concentrated sulphuric acid circulation fluid is acidolysis
The 20-50% of the required concentrated sulphuric acid amount of reaction, collects the gas on circulation fluid surface, and the residual liquid of gained is after cooling, raw for phosphate fertilizer
Produce；
4) by step 3) gas collected, cooled, rectification, degassing process, and obtain anhydrous hydrogen fluoride product.
The beneficial effects of the present invention is:
After the cooled process of hydrogen fluoride gas utilizing the inventive method to parse, can obtain content is 88%-95%'s
Thick fluohydric acid gas, thick fluohydric acid gas, after rectification, degassing process, can obtain the content anhydrous hydrogen fluoride product more than 99.9%, and fluorine
Change the response rate of hydrogen more than 92%；The present invention is by utilizing the sulfuric acid absorption hydrogen fluoride gas of excess in acidolysis reaction so that mixed
Compound can utilize self heat and fluohydric acid gas liquidation exothermic reaction to meet separated condition, improves the response rate of fluohydric acid gas, logical
Crossing and utilize acidolysis mixed liquor and sulphuric acid to carry out mass transfer and heat transfer, the spray temperature of binding mixture controls so that fluohydric acid gas is able to
Purify, meanwhile, by sulphuric acid is carried out microwave heating treatment, accelerate material reaction speed, improve heat transfer efficiency so that heat
Utilization rate can be improved, meet rectification separation condition, by controlling sulfuric acid concentration and consumption, utilize the water absorption of concentrated sulphuric acid,
Decrease the water content of hydrogen fluoride gas, decrease energy needed for the recovery of anhydrous hydrogen fluoride, in the balance of this converting heat
Under structure so that concentrated sulphuric acid concentration is balanced, and then effectively reduce equipment corrosion problem.
The present invention has that technique is simple, energy consumption is low, operate safe and reliable feature, and the equipment that also solves is corrosion resistant asks
Topic, improves utilization rate of equipment and installations.
Detailed description of the invention
Technical scheme is described further below, but claimed scope is not limited to described.
Embodiment 1
A kind of method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor, comprises the following steps:
1) it is the concentrated sulphuric acid of 96% by ammonium fluoride crystal and volumetric concentration, under tiny structure, carries out acidolysis reaction, wherein, dense
The addition of sulphuric acid is to generate needed for ammonium hydrogen sulfate 1.3 times of concentrated sulphuric acid amount；
2) 20-25% of thick for acidolysis reaction gained hydrogen fluoride gas total amount sending into refining system, residue is slightly fluorinated hydrogen
Body is dissolved in the liquid after acidolysis reaction, obtains ammonium fluoride acidolysis mixed liquor；
3) control the temperature of ammonium fluoride acidolysis mixed liquor, at 100 DEG C, to be at once sprayed in concentrated sulphuric acid circulation fluid, wherein,
Concentrated sulphuric acid circulation fluid be use microwave heating to concentrated sulphuric acid temperature be 200 DEG C, the consumption of concentrated sulphuric acid circulation fluid is acidolysis reaction institute
Need the 40% of concentrated sulphuric acid amount, collect the gas on circulation fluid surface, the residual liquid of gained after cooling, for production of phosphate fertilizer；
4) gas that will collect, sends in refining system after cooling, is sent directly into the thick fluorine of refining system after reaction
Change hydrogen jointly to process through rectification, degassing, obtain anhydrous hydrogen fluoride product.
Embodiment 2
A kind of method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor, comprises the following steps:
1) it is the concentrated sulphuric acid of 94% by ammonium fluoride crystal and volumetric concentration, under tiny structure, carries out acidolysis reaction, wherein, dense
The addition of sulphuric acid is to generate needed for ammonium hydrogen sulfate 1.5 times of concentrated sulphuric acid amount；
2) 20-25% of thick for acidolysis reaction gained hydrogen fluoride gas total amount sending into refining system, residue is slightly fluorinated hydrogen
Body is dissolved in the liquid after acidolysis reaction, obtains ammonium fluoride acidolysis mixed liquor；
3) control the temperature of ammonium fluoride acidolysis mixed liquor, at 90 DEG C, to be at once sprayed in concentrated sulphuric acid circulation fluid, wherein, dense
Sulphuric acid circulation fluid be use microwave heating to concentrated sulphuric acid temperature be 220 DEG C, needed for the consumption of concentrated sulphuric acid circulation fluid is acidolysis reaction
The 20% of concentrated sulphuric acid amount, collect circulation fluid surface gas, the residual liquid of gained after cooling, for production of phosphate fertilizer；
4) gas that will collect, sends in refining system after cooling, is sent directly into the thick fluorine of refining system after reaction
Change hydrogen jointly to process through rectification, degassing, obtain anhydrous hydrogen fluoride product.
Embodiment 3
A kind of method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor, comprises the following steps:
1) it is the concentrated sulphuric acid of 98% by ammonium fluoride crystal and volumetric concentration, under tiny structure, carries out acidolysis reaction, wherein, dense
The addition of sulphuric acid is to generate needed for ammonium hydrogen sulfate 1.2 times of concentrated sulphuric acid amount；
2) 20-25% of thick for acidolysis reaction gained hydrogen fluoride gas total amount sending into refining system, residue is slightly fluorinated hydrogen
Body is dissolved in the liquid after acidolysis reaction, obtains ammonium fluoride acidolysis mixed liquor；
3) control the temperature of ammonium fluoride acidolysis mixed liquor, at 130 DEG C, to be at once sprayed in concentrated sulphuric acid circulation fluid, wherein,
Concentrated sulphuric acid circulation fluid be use microwave heating to concentrated sulphuric acid temperature be 170 DEG C, the consumption of concentrated sulphuric acid circulation fluid is acidolysis reaction institute
Need the 50% of concentrated sulphuric acid amount, collect the gas on circulation fluid surface, the residual liquid of gained after cooling, for production of phosphate fertilizer；
4) gas that will collect, sends in refining system after cooling, is sent directly into the thick fluorine of refining system after reaction
Change hydrogen jointly to process through rectification, degassing, obtain anhydrous hydrogen fluoride product.
Claims (6)
1. the method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor, it is characterised in that comprise the following steps:
1) concentrated sulphuric acid is heated to 170-220 DEG C, and keeps circulation；
2) it is sprayed to ammonium fluoride acidolysis mixed liquor circulate concentrated sulphuric acid surface, collects gas, cooled, obtain the thick finished product of fluohydric acid gas；
3) by thick for fluohydric acid gas finished product through rectification, degassing, anhydrous hydrogen fluoride product is obtained.
2. the method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor as claimed in claim 1, it is characterised in that institute
State heating and use microwave heating technique.
3. the method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor as claimed in claim 1, it is characterised in that institute
The volumetric concentration stating concentrated sulphuric acid is 94-98%.
4. the method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor as claimed in claim 1, it is characterised in that institute
Stating ammonium fluoride acidolysis mixed liquor, temperature during its spray is 90-130 DEG C.
5. the method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor as described in claim 1 or 4, its feature exists
It is that ammonium fluoride crystal carries out acidolysis reaction with concentrated sulphuric acid and obtains in, described ammonium fluoride acidolysis mixed liquor.
6. the method producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor as claimed in claim 5, it is characterised in that institute
Stating acidolysis reaction, wherein the addition of sulphuric acid is to produce needed for ammonium hydrogen sulfate 1.2-1.5 times of concentrated sulphuric acid amount.
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| CN201610778760.4A CN106241740B (en) | 2016-08-31 | 2016-08-31 | A method of producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111498809A (en) * | 2020-05-13 | 2020-08-07 | 好科（上海）环保科技有限公司 | From containing H2SiF6Method for recovering hydrofluoric acid from etching waste acid |
| CN113233422A (en) * | 2021-06-02 | 2021-08-10 | 四川大学 | Method and system for separating SiF4 and HF mixed gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914398A (en) * | 1974-12-16 | 1975-10-21 | Du Pont | Process for making anhydrous hydrogen fluoride from fluosilicic acid |
| CN85101146A (en) * | 1985-04-01 | 1987-01-17 | 三菱金属株式会社 | Processing contains the method for ammonium and fluorium ion liquid |
| CN102491370A (en) * | 2011-12-02 | 2012-06-13 | 瓮福（集团）有限责任公司 | Method for producing ammonium bifluoride by recovering fluorine resource from fluorine-containing silicon slag |
| CN102689877A (en) * | 2012-06-28 | 2012-09-26 | 贵州开磷（集团）有限责任公司 | Preparation method of hydrogen fluoride |
-
2016
- 2016-08-31 CN CN201610778760.4A patent/CN106241740B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914398A (en) * | 1974-12-16 | 1975-10-21 | Du Pont | Process for making anhydrous hydrogen fluoride from fluosilicic acid |
| CN85101146A (en) * | 1985-04-01 | 1987-01-17 | 三菱金属株式会社 | Processing contains the method for ammonium and fluorium ion liquid |
| CN102491370A (en) * | 2011-12-02 | 2012-06-13 | 瓮福（集团）有限责任公司 | Method for producing ammonium bifluoride by recovering fluorine resource from fluorine-containing silicon slag |
| CN102689877A (en) * | 2012-06-28 | 2012-09-26 | 贵州开磷（集团）有限责任公司 | Preparation method of hydrogen fluoride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111498809A (en) * | 2020-05-13 | 2020-08-07 | 好科（上海）环保科技有限公司 | From containing H2SiF6Method for recovering hydrofluoric acid from etching waste acid |
| CN111498809B (en) * | 2020-05-13 | 2023-07-25 | 好科（上海）环保科技有限公司 | From H-containing 2 SiF 6 Method for recycling hydrofluoric acid from etching waste acid |
| CN113233422A (en) * | 2021-06-02 | 2021-08-10 | 四川大学 | Method and system for separating SiF4 and HF mixed gas |
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| CN106241740B (en) | 2018-09-25 |
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