CN115010091B - Impurity removal method for hydrogen fluoride, purification method for hydrogen fluoride and purification device for hydrogen fluoride - Google Patents
Impurity removal method for hydrogen fluoride, purification method for hydrogen fluoride and purification device for hydrogen fluoride Download PDFInfo
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 281
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 279
- 239000012535 impurity Substances 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000000746 purification Methods 0.000 title claims description 28
- 238000005406 washing Methods 0.000 claims abstract description 171
- 239000007789 gas Substances 0.000 claims abstract description 160
- 239000007788 liquid Substances 0.000 claims abstract description 156
- -1 ammonium ions Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 29
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- 238000004062 sedimentation Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical group 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 49
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000002253 acid Substances 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000010436 fluorite Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 238000005276 aerator Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005201 scrubbing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004176 ammonification Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101150096839 Fcmr gene Proteins 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to a method for removing impurities from hydrogen fluoride, a method for purifying hydrogen fluoride and a device for purifying hydrogen fluoride,belonging to the technical field of inorganic chemical product production. The impurity removal method of hydrogen fluoride comprises the following steps: washing the crude hydrogen fluoride gas by adopting a washing liquid; the washing liquid mainly consists of H 2 O-HF azeotrope composition; the mass fraction of ammonium ions in the washing liquid is less than 10%. The impurity removing method of hydrogen fluoride of the invention adopts the method mainly comprising H 2 The washing liquid composed of the O-HF azeotrope washes the crude hydrogen fluoride gas, avoids introducing foreign impurities such as sulfate radical and the like, and simultaneously can efficiently remove NH in the crude hydrogen fluoride raw material 4 + 、PO 4 3‑ 、SO 4 2‑ And the like, has the advantages of simple operation and lower cost.
Description
Technical Field
The invention relates to a method for removing impurities from hydrogen fluoride, a method for purifying hydrogen fluoride and a device for purifying hydrogen fluoride, and belongs to the technical field of inorganic chemical product production.
Background
Hydrogen Fluoride (HF) is the basis of modern fluorine chemical industry, and is the most basic raw material for preparing elemental fluorine, various fluorine refrigerants, new fluorine-containing materials, inorganic fluoride salts, various organic fluorides and the like. In recent years, the fluorine chemical industry in China is rapidly developed, the annual hydrogen fluoride yield in China can reach more than 200 ten thousand tons at present, and the fluorite method is mostly adopted for production. The fluorite method is to prepare hydrogen fluoride gas by utilizing fluorite and sulfuric acid to react, but is limited to exploitation of national strategy resource fluorite, the price of the national fluorite is gradually increased, and searching for a new fluorine source becomes a focus of industry attention.The raw material hydrogen fluoride gas prepared by fluorite method contains SO 4 2- 、PO 4 3- 、H 2 O、SO 2 、As 3+ And the like.
Fluorine is used as one of the elements associated with phosphate ore as the raw material of phosphorus chemical industry, and the content of fluorine is about 3-4% and is 10-20 times of fluorite reserves. A large amount of silicon tetrafluoride gas is produced in the production process of the phosphate fertilizer and is converted into fluosilicic acid after being absorbed by water. Therefore, the byproduct fluosilicic acid in the phosphate fertilizer industry is rich in resources and low in cost. In recent years, a great deal of research is being carried out on the high-efficiency and high-value utilization of industry byproduct fluosilicic acid in China, especially the process development of preparing anhydrous hydrogen fluoride by fluosilicic acid, and technologies such as fluosilicic acid ammonification sulfuric acid decomposition method, fluosilicic acid concentrated sulfuric acid method, and hydrogen fluoride (such as sodium hydrogen fluoride) pyrolysis method are developed successively, but NH is contained in hydrogen fluoride gas prepared by fluosilicic acid ammonification sulfuric acid decomposition method or hydrogen fluoride pyrolysis method by taking fluosilicic acid as raw material 4 + 、PO 4 3- 、SO 4 2- 、As 3+ An equal impurity component, which is different from the impurity contained in the hydrogen fluoride prepared by using fluorite as raw material, but the hydrogen fluoride prepared by both methods contains SO 2 、PO 4 3- 、SO 4 2- Water-soluble impurities are equal. For example, in the case of preparing anhydrous hydrogen fluoride by pyrolysis of hydrogen fluoride, ammonium fluoride and/or ammonium bifluoride is first converted into alkali metal hydrogen fluoride, and then the hydrogen fluoride is subjected to pyrolysis. When anhydrous hydrogen fluoride is prepared by fluosilicic acid ammoniation sulfuric acid decomposition method, fluosilicic acid is firstly mixed with liquid ammonia or ammonia water and then enters an ammonolysis reactor to form ammonium fluoride solution and silicon dioxide precipitate, and NH is obtained after filtration 4 The F filtrate is subjected to evaporation concentration, pre-reaction and premixing to form ammonia hydrogen fluoride reaction liquid, the ammonia hydrogen fluoride reaction liquid enters a reaction furnace to react with sulfuric acid to generate ammonium sulfate and raw material HF gas, the raw material HF gas is condensed to obtain crude HF liquid, and the crude HF liquid enters a rectification process to be refined, so that light component SiF with low boiling point is removed 4 、SO 2 、CO 2 Equal impurities and high boiling point heavy component H 2 SO 4 、H 2 O, and other impurities. But due toSO 2 And NH 4 + Is mutually soluble with water, is easy to mix with heavy component impurities such as sulfuric acid, water and the like, aggravates the limitation of rectification phase balance, and further is difficult to realize the deep impurity removal of HF through rectification. Chinese patent application CN112744788A discloses a method for separating and purifying FTrPSA by deep dehydration and impurity removal for producing anhydrous HF refined by fluosilicic acid method, comprising the following steps: the raw material HF gas is subjected to cold and heat exchange to 60-80 ℃ and normal pressure or micro-positive pressure, enters a medium temperature pressure swing adsorption process consisting of two sections of Pressure Swing Adsorption (PSA), each section of pressure swing adsorption consists of at least 2 adsorption towers, at least 1 adsorption tower is in an adsorption step, the rest adsorption towers are in desorption steps comprising different stages of depressurization reverse discharge or vacuumizing, pressurizing or final filling, and the raw material HF gas subjected to medium temperature pressure swing adsorption is subjected to rectification for further purification and impurity removal to obtain hydrogen fluoride. Pressure swing adsorption has problems of complicated operation and high cost.
Disclosure of Invention
The invention aims to provide a method for removing impurities from hydrogen fluoride, which is simple to operate and low in cost.
The second object of the present invention is to provide a method for purifying hydrogen fluoride.
A third object of the present invention is to provide a purification apparatus for hydrogen fluoride.
In order to achieve the above purpose, the impurity removal method for hydrogen fluoride of the present invention adopts the following technical scheme:
a method for removing impurities from hydrogen fluoride, comprising the steps of: washing the crude hydrogen fluoride gas by adopting a washing liquid; the washing liquid mainly consists of H 2 O-HF azeotrope composition; the mass fraction of ammonium ions in the washing liquid is less than 10%.
The impurity removing method of hydrogen fluoride of the invention adopts the method mainly comprising H 2 The washing liquid composed of the O-HF azeotrope washes the crude hydrogen fluoride gas, avoids introducing foreign impurities such as sulfate radical and the like, and simultaneously can efficiently remove NH in the crude hydrogen fluoride raw material 4 + 、PO 4 3- 、SO 4 2- And the like, has the advantages of simple operation and lower cost.
Preferably, the H 2 The mass fraction of HF in the O-HF azeotrope is 35-40%. For example, the H 2 The mass fraction of HF in the O-HF azeotrope is 35-38%. When H is 2 When the mass fraction of HF in the O-HF azeotrope is 35-40%, the mixture is mainly composed of H 2 The washing liquid composed of the O-HF azeotrope washes the crude hydrogen fluoride gas, so that the use of strong-corrosiveness concentrated sulfuric acid raw materials can be avoided, on one hand, the introduction of new impurities is stopped, on the other hand, the production cost of the raw materials is reduced, and the method has the advantages of high impurity removal efficiency and good product quality.
It is understood that the main component in the washing liquid is H 2 The O-HF azeotrope, the washing liquid also contains a small amount of impurities, and the impurities are mainly dissolved in H in the crude hydrogen fluoride gas 2 Substances of the O-HF azeotrope, e.g. NH 4 + 、PO 4 3- 、SO 4 2- Etc.
To avoid H 2 The O-HF azeotrope forms a gas, preferably the temperature of the scrubbing liquid is 50-90 ℃. When the temperature of the washing liquid is 50-90 ℃, the crude hydrogen fluoride gas and the washing liquid are washed in countercurrent, the hydrogen fluoride gas is easy to overflow from the washing liquid, and water and NH 4 + 、PO 4 3- SO and SO 4 2- And the solubility of the soluble impurities in the washing liquid is large, so that high-efficiency washing separation is realized.
Preferably, the mass fraction of solid particles in the crude hydrogen fluoride gas is not more than 0.5%. When the mass fraction of the solid particles in the crude hydrogen fluoride gas is more than 0.5%, the crude hydrogen fluoride gas can be subjected to gas-solid separation, and then the crude hydrogen fluoride gas after the gas-solid separation is washed. Preferably, the crude hydrogen fluoride gas is obtained by dedusting raw material hydrogen fluoride gas. Preferably, the dust removal is achieved by sedimentation. The sedimentation technology is adopted to carry out natural sedimentation on the particulate matters in the raw material hydrogen fluoride gas, so that on one hand, the fluoride can be recovered, and on the other hand, the pressure of subsequent purification and impurity removal can be reduced. The raw material hydrogen fluoride gas is unrefined hydrogen fluoride gas obtained by reaction when anhydrous hydrogen fluoride is prepared by adopting a fluorosilicic acid method or a fluorite method. For example, the raw material hydrogen fluoride gas is an unrefined hydrogen fluoride gas produced from fluorosilicic acid as a raw material by fluorosilicic acid ammonification sulfuric acid decomposition and/or hydrogen fluoride pyrolysis. Preferably, the temperature of the raw material hydrogen fluoride gas is 100 to 220 ℃.
In the washing, the washing liquid may be contacted with the crude hydrogen fluoride gas in any manner, for example, the crude hydrogen fluoride gas may be bubbled into the washing liquid to wash the crude hydrogen fluoride gas, or the washing liquid may be contacted with the crude hydrogen fluoride gas in countercurrent to wash the crude hydrogen fluoride gas. Preferably, the washing is by countercurrent contact of the washing liquid with crude hydrogen fluoride gas. For example, the scrubbing may be performed in a scrubbing tower, in which the scrubbing liquid is countercurrently contacted with the crude hydrogen fluoride gas to effect scrubbing of the crude hydrogen fluoride gas. Preferably, the scrubber is a spray scrubber. Preferably, the liquid-gas ratio adopted by the washing tower is 2.2-2.6.
It will be appreciated that when the raw material hydrogen fluoride gas is an unrefined hydrogen fluoride gas produced from fluorosilicic acid as a raw material by the ammonification of sulfuric acid by fluorosilicic acid and/or the thermal decomposition of hydrogen fluoride, the raw material hydrogen fluoride gas contains NH 4 + 、PO4 3- 、SO 4 2- 、As 3+ And the like.
The crude hydrogen fluoride gas is washed by the washing liquid, the washing liquid can be recycled, and the concentration of ammonium ions in the washing liquid is detected, preferably, when the mass fraction of the ammonium ions in the washed washing liquid is more than 10%, the washing liquid is reacted with a proper amount of ammonia gas to prepare the ammonium bifluoride. When the mass fraction of ammonium ions in the washing liquid is more than 10%, the main component in the washing liquid is NH 4 HF 2 、HF、H 2 O, etc., and the washing liquid can be reacted with ammonia gas to prepare byproduct ammonium bifluoride, and the obtained ammonium bifluoride can be sold or returned to a fluosilicic acid preparation anhydrous hydrofluoric acid production line.
The technical scheme adopted by the purification method of hydrogen fluoride is as follows:
a method for purifying hydrogen fluoride comprising the steps of: condensing the crude hydrogen fluoride gas washed in the impurity removal method of the hydrogen fluoride, mixing an impurity removing agent and an oxidant into the liquid hydrogen fluoride obtained by condensation for reaction, carrying out solid-liquid separation, and rectifying the liquid obtained by the solid-liquid separation to obtain the hydrogen fluoride; the impurity removing agent is metal oxide and/or metal fluoride, and metal ions formed by metal elements in the metal oxide and/or the metal fluoride in liquid hydrogen fluoride can form phosphate precipitation with phosphate; the oxidant is ozone.
The method for purifying hydrogen fluoride of the invention adopts the method that H is mainly adopted at first 2 The washing liquid composed of the O-HF azeotrope is used for washing the crude hydrogen fluoride gas, so that most water-soluble impurities can be removed, then the impurity removing agent is used for removing phosphate impurities, and then the trivalent arsenic is oxidized by ozone, so that the use of oxidizing agents such as highly toxic fluorine gas, potassium permanganate and the like can be avoided, the working environment of production personnel is improved, and the safety of the production process is improved; on the other hand, the introduction of foreign ion can be avoided, the subsequent purification difficulty is reduced, and the product quality can be further improved. The purification method of hydrogen fluoride can effectively remove NH in raw material hydrogen fluoride 4 + 、PO4 3- 、SO 4 2- 、As 3+ And the impurities are removed, and the purified hydrogen fluoride has the advantages of high purity and low impurity content, and simultaneously has the advantages of simple operation, low production cost and high comprehensive utilization degree of raw materials.
In the invention, the liquid hydrogen fluoride can be subjected to impurity removal reaction with the impurity removing agent first, then subjected to impurity removal reaction with the ozone, or subjected to impurity removal reaction with the ozone first, then subjected to impurity removal reaction with the impurity removing agent, or subjected to impurity removal reaction simultaneously with the impurity removing agent and the ozone.
Preferably, in the method for purifying hydrogen fluoride, the metal element in the metal oxide or the metal fluoride is independently selected from the group consisting of iron element, aluminum element and calcium element.
Preferably, the condensation is carried out at a temperature of-5 to 15 ℃.
Preferably, the impurity removing agent is used in an excess amount.
Preferably, when the impurity removing agent is selected from one or any combination of ferric oxide, aluminum oxide, ferric fluoride and aluminum fluoride, the mole ratio of the iron element and/or aluminum element in the impurity removing agent to phosphate radical in the liquid hydrogen fluoride is (1-1.05): 1.
Preferably, when the impurity removing agent is calcium oxide and/or calcium fluoride, the molar ratio of the calcium element in the impurity removing agent to the phosphate radical in the liquid hydrogen fluoride is (3-3.05): 2.
Preferably, after the reaction is finished, carrying out solid-liquid separation on the system after the reaction is finished, wherein the liquid obtained by the solid-liquid separation is the liquid hydrogen fluoride after impurity removal. The solid obtained by solid-liquid separation is phosphate, and can be sold as a byproduct after being treated.
Preferably, as in the ozone and liquid hydrogen fluoride 3+ The molar ratio of (1) to (1.1): 1.
Preferably, the temperature of the reaction is 0-15 ℃, and the reaction time is 1-2 h.
Preferably, the bottom temperature of the rectifying tower used for rectification is 20-25 ℃, and the top temperature of the rectifying tower is 10-15 ℃.
Preferably, the reflux ratio of the rectifying tower used for rectification is 1.5-2.0.
The tail gas generated by the purification method of hydrogen fluoride enters the tail gas absorption device, and the fluorine-containing solution generated by tail gas treatment is used for preparing fluoride, so that the comprehensive utilization of process byproducts can be realized, and the requirements of national clean production development are met.
The technical scheme adopted by the purifying device of the hydrogen fluoride is as follows:
a purifying device of hydrogen fluoride comprises a washing unit, a condensing unit, a reaction unit, a solid-liquid separation unit and a rectifying unit which are sequentially connected in the material flow direction;
the washing unit is used for providing H 2 The O-HF azeotrope is used for washing the crude hydrogen fluoride gas;
the condensing unit is a place for condensing the crude hydrogen fluoride gas washed by the washing unit into liquid hydrogen fluoride;
the reaction unit is a place for providing precipitated phosphate ions and oxidized trivalent arsenic;
the solid-liquid separation unit is used for carrying out solid-liquid separation on the liquid hydrogen fluoride material reacted by the reaction unit;
the rectifying unit is a place for rectifying the liquid hydrogen fluoride material separated by the solid-liquid separation unit.
The purification device of the hydrogen fluoride is simple and effective, and can effectively remove NH in the raw material hydrogen fluoride 4 + 、PO4 3- 、SO 4 2- 、As 3+ And the impurities are removed, and the purified hydrogen fluoride has the advantages of high purity and low impurity content. Meanwhile, the purifying device of hydrogen fluoride has the advantages of simple operation, low production cost and high comprehensive utilization degree of raw materials.
Preferably, a sedimentation unit is further arranged upstream of the washing unit; the sedimentation unit is a place for sedimentation of solid particle impurities in the crude hydrogen fluoride gas.
Drawings
FIG. 1 is a schematic structural view of a purification apparatus for hydrogen fluoride according to the present invention; wherein, the reference numerals are as follows: 1-settling tank, 2-washing tower, 3-condenser, 4-impurity removing tank, 5-filter, 6-rectifying tower and 7-aerator.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The raw material hydrogen fluoride gas used in examples 1 to 4 and examples 6 to 9 of the present invention was derived from an unrefined hydrogen fluoride gas produced by a hydrogen fluoride pyrolysis method using fluosilicic acid as a raw material.
1. Specific examples of the impurity removal method of hydrogen fluoride of the present invention are as follows:
example 1
The impurity removal method for hydrogen fluoride in the embodiment specifically comprises the following steps:
introducing raw material hydrogen fluoride gas with the temperature of 220 ℃ into a settling tank, settling particulate matters in the raw material hydrogen fluoride gas to the bottom of the settling tank under the action of gravity, and settling coarse hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5 percent)Overflowing from the top of the drop tank, and then entering a washing tower (the height of the washing tower is 5m, the diameter of the washing tower is 0.7m, and plastic Raschig rings are adopted as filler) from the bottom of the washing tower, H 2 And (3) spraying a washing liquid consisting of the O-HF azeotrope from the top of the washing tower to wash the crude hydrogen fluoride gas, controlling the temperature of the washing liquid to be 90 ℃ and the liquid-gas ratio to be 2.3, and overflowing the washed crude hydrogen fluoride gas from the top of the washing tower to finish the impurity removal of the crude hydrogen fluoride gas.
In this embodiment, H 2 The mass fraction of HF in the O-HF azeotrope was 35%. The washing liquid is firstly formed by H 2 And (3) the O-HF azeotrope is formed, after the crude hydrogen fluoride gas is washed, the crude hydrogen fluoride gas is recycled until the mass fraction of ammonium ions in the washing liquid is 9.5%, and then the washing liquid is discharged from a washing tower and reacts with a proper amount of ammonia gas to prepare an ammonium bifluoride product.
Example 2
The impurity removal method for hydrogen fluoride in the embodiment specifically comprises the following steps:
introducing raw material hydrogen fluoride gas with the temperature of 180 ℃ into a settling tank, settling particles in the raw material hydrogen fluoride gas to the bottom of the settling tank under the action of gravity, overflowing crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) from the top of the settling tank, then entering a washing tower (the height of the washing tower is 5m, the diameter of the tower is 0.7m, and a plastic Raschig ring is adopted as a filler), and introducing H into the washing tower from the bottom of the washing tower 2 And (3) spraying a washing liquid consisting of the O-HF azeotrope from the top of the washing tower to wash the crude hydrogen fluoride gas, controlling the temperature of the washing liquid to be 75 ℃, and controlling the liquid-gas ratio to be 2.5, wherein the washed crude hydrogen fluoride gas overflows from the top of the washing tower to finish the impurity removal of the crude hydrogen fluoride gas.
In this embodiment, H 2 The mass fraction of HF in the O-HF azeotrope was 38%. The washing liquid is firstly formed by H 2 And (3) the O-HF azeotrope is formed, after the crude hydrogen fluoride gas is washed, the crude hydrogen fluoride gas is recycled until the mass fraction of ammonium ions in the washing liquid is 9.8%, and then the washing liquid is discharged from a washing tower and reacts with a proper amount of ammonia gas to prepare an ammonium bifluoride product.
Example 3
The impurity removal method for hydrogen fluoride in the embodiment specifically comprises the following steps:
introducing raw material hydrogen fluoride gas with the temperature of 100 ℃ into a settling tank, settling particles in the raw material hydrogen fluoride gas to the bottom of the settling tank under the action of gravity, overflowing crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) from the top of the settling tank, then entering a washing tower (the height of the washing tower is 5m, the diameter of the tower is 0.7m, and a plastic Raschig ring is adopted as a filler) from the bottom of the washing tower, and carrying out H 2 And (3) spraying a washing liquid consisting of the O-HF azeotrope from the top of the washing tower to wash the crude hydrogen fluoride gas, controlling the temperature of the washing liquid to be 50 ℃ and the liquid-gas ratio to be 2.2, and overflowing the washed crude hydrogen fluoride gas from the top of the washing tower to finish the impurity removal of the crude hydrogen fluoride gas.
In this embodiment, H 2 The mass fraction of HF in the O-HF azeotrope was 35%. The washing liquid is firstly formed by H 2 And (3) the O-HF azeotrope is formed, after the crude hydrogen fluoride gas is washed, the crude hydrogen fluoride gas is recycled until the mass fraction of ammonium ions in the washing liquid is 9.9%, and then the washing liquid is discharged from a washing tower and reacts with a proper amount of ammonia gas to prepare an ammonium bifluoride product.
Example 4
The impurity removal method for hydrogen fluoride in the embodiment specifically comprises the following steps:
introducing raw material hydrogen fluoride gas with the temperature of 130 ℃ into a settling tank, settling particles in the raw material hydrogen fluoride gas to the bottom of the settling tank under the action of gravity, overflowing crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) from the top of the settling tank, then entering a washing tower (the height of the washing tower is 5m, the diameter of the tower is 0.7m, and a plastic Raschig ring is adopted as a filler), and introducing H into the washing tower from the bottom of the washing tower 2 And (3) spraying a washing liquid consisting of the O-HF azeotrope from the top of the washing tower to wash the crude hydrogen fluoride gas, controlling the temperature of the washing liquid to be 65 ℃ and the liquid-gas ratio to be 2.6, and overflowing the washed crude hydrogen fluoride gas from the top of the washing tower to finish the impurity removal of the crude hydrogen fluoride gas.
In this embodiment, H 2 The mass fraction of HF in the O-HF azeotrope was 37%. The washing liquid is firstly formed by H 2 The O-HF azeotrope consists of the following steps of washing crude hydrogen fluoride gas, recycling the gas until the mass fraction of ammonium ions in the washing liquid is 10%, and then removing the washing liquid from the gasAnd discharging the mixture from the washing tower and reacting the mixture with a proper amount of ammonia gas to prepare an ammonium bifluoride product.
2. Specific examples of the purification apparatus for hydrogen fluoride according to the present invention are as follows:
example 5
The structure of the purification apparatus of hydrogen fluoride of this embodiment is schematically shown in FIG. 1, and comprises a settling tank 1, a washing column 2, a condenser 3, a impurity removal tank 4, a filter 5, and a rectifying column 6. Wherein the sedimentation tank 1 forms a sedimentation unit, the washing tower 2 forms a washing unit, the condenser 3 forms a condensing unit, the impurity removal tank 4 forms a reaction unit, the filter 5 forms a solid-liquid separation unit, and the rectifying tower 6 forms a rectifying unit.
The sedimentation tank 1 is provided with a raw material hydrogen fluoride gas inlet, and a gas outlet of the sedimentation tank 1 is connected with a gas inlet of the washing tower 2; the upper part of the washing tower 2 is provided with a spraying device for spraying the washing liquid from the top of the washing tower 2 downwards, and the sprayed washing liquid is in countercurrent contact with the crude hydrogen fluoride gas flowing upwards from the bottom of the washing tower 2, so that the crude hydrogen fluoride gas is washed. The gas outlet of the washing tower 2 is connected with the gas inlet of the condenser 3, and the discharge port of the condenser 3 is connected with the feed inlet of the impurity removal tank 4. The washed crude hydrogen fluoride gas is condensed in a condenser 3 to obtain liquid hydrogen fluoride, and the liquid hydrogen fluoride flows out from a discharge hole of the condenser 3 and enters a impurity removal tank 4.
The interior of the impurity removal tank 4 is provided with a stirring device, the bottom of the impurity removal tank 4 is provided with an aerator 7, and the aerator 7 is provided with an ozone gas inlet for introducing ozone into the impurity removal tank 4. The discharge port of the impurity removal tank 4 is connected with the feed inlet of the filter 5, and the discharge port of the filter 5 is connected with the feed inlet of the rectifying tower 6. The rectifying column 6 is provided with a hydrogen fluoride product outlet.
The purification method of hydrogen fluoride of examples 6 to 9 below uses the purification apparatus of example 5 to purify the raw material hydrogen fluoride gas.
3. Specific examples of the purification method of hydrogen fluoride of the present invention are as follows:
example 6
The purification method of hydrogen fluoride in this embodiment specifically includes the following steps:
(1) Introducing raw material hydrogen fluoride gas with the temperature of 220 ℃ into a settling tank, settling particles in the raw material hydrogen fluoride gas to the bottom of the settling tank under the action of gravity, overflowing crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) from the top of the settling tank, then entering a washing tower (the height of the washing tower is 5m, the diameter of the tower is 0.7m, and a plastic Raschig ring is adopted as a filler) from the bottom of the washing tower, and carrying out H 2 The washing liquid composed of the O-HF azeotrope is sprayed from the top of the washing tower to wash the crude hydrogen fluoride gas, the temperature of the washing liquid is controlled to be 90 ℃, the liquid-gas ratio is 2.3, and the washed crude hydrogen fluoride gas overflows from the top of the washing tower. H 2 The mass fraction of HF in the O-HF azeotrope was 35%. The washing liquid is firstly formed by H 2 And (3) an O-HF azeotrope is formed, after the crude hydrogen fluoride gas is washed, recycling until the mass fraction of ammonium ions in the washing liquid is 9.5%, discharging the washing liquid from a washing tower, introducing ammonia gas into the washing liquid until the pH value of the washing liquid is 2, enabling the HF and the ammonia gas to react, and concentrating and crystallizing after the reaction is finished to obtain an ammonium bifluoride product.
(2) Introducing the washed crude hydrogen fluoride gas into a condenser, controlling the temperature of the condenser to be 15 ℃, condensing to obtain liquid hydrogen fluoride, introducing the liquid hydrogen fluoride into a impurity removing tank, introducing ozone into the impurity removing tank through an aerator at the bottom of the impurity removing tank, carrying out impurity removing reaction on the liquid hydrogen fluoride after entering the impurity removing tank, aluminum fluoride in the impurity removing tank and ozone at 15 ℃ under the stirring condition for 1h, filtering by a filter to obtain the liquid hydrogen fluoride after impurity removing, and introducing exhaust gas discharged from the impurity removing tank into a tail gas absorbing device. The solid obtained by filtration is aluminum phosphate, and can be sold as a byproduct after being treated. The mole ratio of aluminum element in aluminum fluoride to phosphate radical in liquid hydrogen fluoride is 1:1, ozone and As in liquid hydrogen fluoride are introduced into the impurity removing tank 3+ The molar ratio of (2) is 1:1.
(3) And (3) delivering the liquid hydrogen fluoride after impurity removal into a rectifying tower, controlling the temperature of the bottom of the rectifying tower to be 20 ℃, controlling the temperature of the top of the rectifying tower to be 10 ℃, controlling the reflux ratio to be 1.6, and enabling the liquid obtained by condensing the top of the rectifying tower to be hydrogen fluoride and enabling uncondensed gas to enter a tail gas absorption device.
Example 7
The purification method of hydrogen fluoride in this embodiment specifically includes the following steps:
(1) Introducing raw material hydrogen fluoride gas with the temperature of 180 ℃ into a settling tank, settling particles in the raw material hydrogen fluoride gas to the bottom of the settling tank under the action of gravity, overflowing crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) from the top of the settling tank, then entering a washing tower (the height of the washing tower is 5m, the diameter of the tower is 0.7m, and a plastic Raschig ring is adopted as a filler), and introducing H into the washing tower from the bottom of the washing tower 2 The washing liquid composed of the O-HF azeotrope is sprayed from the top of the washing tower to wash the crude hydrogen fluoride gas, the temperature of the washing liquid is controlled to be 75 ℃, the liquid-gas ratio is 2.5, and the washed crude hydrogen fluoride gas overflows from the top of the washing tower. H 2 The mass fraction of HF in the O-HF azeotrope was 38%. The washing liquid is firstly formed by H 2 And (3) an O-HF azeotrope is formed, after the crude hydrogen fluoride gas is washed, recycling until the mass fraction of ammonium ions in the washing liquid is 9.8%, discharging the washing liquid from a washing tower, introducing ammonia gas into the washing liquid until the pH value of the washing liquid is 2.5, reacting the HF with the ammonia gas, and concentrating and crystallizing after the reaction is finished to obtain an ammonium bifluoride product.
(2) Introducing the washed crude hydrogen fluoride gas into a condenser, controlling the temperature of the condenser to be 10 ℃, condensing to obtain liquid hydrogen fluoride, introducing ozone into the impurity removal tank through an aerator at the bottom of the impurity removal tank, carrying out impurity removal reaction on the liquid hydrogen fluoride after entering the impurity removal tank, ferric oxide in the impurity removal tank and ozone at the temperature of 10 ℃ for 1.5 hours under the stirring condition, filtering by a filter to obtain the liquid hydrogen fluoride after impurity removal, and introducing exhaust gas discharged from the impurity removal tank into a tail gas absorption device. The solid obtained by filtration is ferric phosphate, and can be sold as a byproduct after being treated. The mole ratio of iron element in ferric oxide to phosphate radical in liquid hydrogen fluoride is 1.05:1, ozone and As in liquid hydrogen fluoride are introduced into the impurity removing tank 3+ The molar ratio of (2) is 1.1:1.
(3) And (3) delivering the liquid hydrogen fluoride after impurity removal into a rectifying tower, controlling the temperature of the bottom of the rectifying tower to be 22 ℃, controlling the temperature of the top of the rectifying tower to be 15 ℃, controlling the reflux ratio to be 1.5, and enabling the liquid obtained by condensing the top of the rectifying tower to be hydrogen fluoride and enabling uncondensed gas to enter a tail gas absorption device.
Example 8
The purification method of hydrogen fluoride in this embodiment specifically includes the following steps:
(1) Introducing raw material hydrogen fluoride gas with the temperature of 100 ℃ into a settling tank, settling particles in the raw material hydrogen fluoride gas to the bottom of the settling tank under the action of gravity, overflowing crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) from the top of the settling tank, then entering a washing tower (the height of the washing tower is 5m, the diameter of the tower is 0.7m, and a plastic Raschig ring is adopted as a filler) from the bottom of the washing tower, and carrying out H 2 The washing liquid composed of the O-HF azeotrope is sprayed from the top of the washing tower to wash the crude hydrogen fluoride gas, the temperature of the washing liquid is controlled to be 50 ℃, the liquid-gas ratio is 2.2, and the washed crude hydrogen fluoride gas overflows from the top of the washing tower. H 2 The mass fraction of HF in the O-HF azeotrope was 35%. The washing liquid is firstly formed by H 2 And (3) after washing the crude hydrogen fluoride gas, recycling until the mass fraction of ammonium ions in the washing liquid is 9.9%, discharging the washing liquid from the washing tower, introducing ammonia gas into the washing liquid until the pH value of the washing liquid is 3, so that the HF and the ammonia gas react, and concentrating and crystallizing after the reaction is finished to obtain an ammonium bifluoride product.
(2) Introducing the washed crude hydrogen fluoride gas into a condenser, controlling the temperature of the condenser to be minus 5 ℃, condensing to obtain liquid hydrogen fluoride, introducing the liquid hydrogen fluoride into a impurity removing tank, introducing ozone into the impurity removing tank through an aerator at the bottom of the impurity removing tank, carrying out impurity removing reaction on the liquid hydrogen fluoride after entering the impurity removing tank, calcium fluoride and ozone in the impurity removing tank at 0 ℃ under the stirring condition for 2 hours, filtering by a filter to obtain the liquid hydrogen fluoride after impurity removing, and introducing exhaust gas discharged from the impurity removing tank into a tail gas absorbing device. The solid obtained by filtration is calcium phosphate, and can be sold as a byproduct after being treated. The molar ratio of the calcium element in the calcium fluoride to the phosphate radical in the liquid hydrogen fluoride is 3.05:1, and ozone and As in the liquid hydrogen fluoride are introduced into the impurity removal tank 3+ The molar ratio of (2) was 1.05:1.
(3) And (3) delivering the liquid hydrogen fluoride after impurity removal into a rectifying tower, controlling the temperature of the bottom of the rectifying tower to be 25 ℃, controlling the temperature of the top of the rectifying tower to be 12 ℃, controlling the reflux ratio to be 1.8, and enabling the liquid obtained by condensing the top of the rectifying tower to be hydrogen fluoride and enabling uncondensed gas to enter a tail gas absorption device.
Example 9
The purification method of hydrogen fluoride in this embodiment specifically includes the following steps:
(1) Introducing raw material hydrogen fluoride gas with the temperature of 130 ℃ into a settling tank, settling particles in the raw material hydrogen fluoride gas to the bottom of the settling tank under the action of gravity, overflowing crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) from the top of the settling tank, then entering a washing tower (the height of the washing tower is 5m, the diameter of the tower is 0.7m, and a plastic Raschig ring is adopted as a filler), and introducing H into the washing tower from the bottom of the washing tower 2 The washing liquid composed of the O-HF azeotrope is sprayed from the top of the washing tower to wash the crude hydrogen fluoride gas, the temperature of the washing liquid is controlled to be 65 ℃, the liquid-gas ratio is 2.6, and the washed crude hydrogen fluoride gas overflows from the top of the washing tower. H 2 The mass fraction of HF in the O-HF azeotrope was 37%. The washing liquid is firstly formed by H 2 And (3) an O-HF azeotrope is formed, after the crude hydrogen fluoride gas is washed, recycling until the mass fraction of ammonium ions in the washing liquid is 10%, discharging the washing liquid from a washing tower, introducing ammonia gas into the washing liquid until the pH value of the washing liquid is 2, so that HF and ammonia gas react, and concentrating and crystallizing after the reaction is finished to obtain an ammonium bifluoride product.
(2) Introducing the washed crude hydrogen fluoride gas into a condenser, controlling the temperature of the condenser to be 0 ℃, condensing to obtain liquid hydrogen fluoride, introducing the liquid hydrogen fluoride into a impurity removal tank, introducing ozone into the impurity removal tank through an aerator at the bottom of the impurity removal tank, carrying out impurity removal reaction on the liquid hydrogen fluoride after entering the impurity removal tank, calcium fluoride in the impurity removal tank and ozone at the temperature of 0 ℃ under the stirring condition for 2 hours, and then filtering through a filter to obtain the liquid hydrogen fluoride after impurity removal. The solid obtained by filtration is calcium phosphate, and can be sold as a byproduct after being treated. The molar ratio of the calcium element in the calcium fluoride to the phosphate radical in the liquid hydrogen fluoride is 3:2, and ozone and As in the liquid hydrogen fluoride are introduced into the impurity removal tank 3+ The molar ratio of (2) was 1.05:1.
(3) And (3) delivering the liquid hydrogen fluoride after impurity removal into a rectifying tower, controlling the temperature of the bottom of the rectifying tower to be 23 ℃, controlling the temperature of the top of the rectifying tower to be 13 ℃, controlling the reflux ratio to be 2.0, and enabling the liquid obtained by condensing the top of the rectifying tower to be hydrogen fluoride and enabling uncondensed gas to enter a tail gas absorption device.
Comparative example
The purification method of hydrogen fluoride of this comparative example differs from the purification method of hydrogen fluoride of example 6 only in that the washing liquid used in step (1) of the purification method of hydrogen fluoride of this comparative example is concentrated sulfuric acid (98% by mass).
Experimental example
The raw material hydrogen fluoride gas, the washed crude hydrogen fluoride gas (represented by gas A) overflowed from the top of the washing column in comparative examples and examples 6 to 9, and the hydrogen fluoride (represented by gas B) purified in comparative examples and examples 6 to 9 were tested for HF mass fraction, moisture mass fraction, fluorosilicic acid mass fraction, sulfur dioxide mass fraction, nonvolatile acid (represented by H) in accordance with the method prescribed in standard GB/T33337-2016, respectively 2 SO 4 Calculated as P) by mass fraction of phosphorus 2 O 5 Calculated) and arsenic mass fractions, and the test results are shown in table 1.
TABLE 1 raw material hydrogen fluoride gas, crude hydrogen fluoride gas after washing in examples 6 to 9, HF mass fraction and other impurities mass fraction in hydrogen fluoride obtained by purification in examples 6 to 9
The results show that the method mainly comprises the steps of H 2 The washing liquid composed of the O-HF azeotrope washes the crude hydrogen fluoride gas, has better washing effect, and can particularly remove NH in the crude hydrogen fluoride raw material with high efficiency 4 + 、PO 4 3- 、SO 4 2- And soluble impurities are removed, the subsequent rectifying and purifying difficulty is reduced, and the product quality is further improved by hydrogen fluoride. Examples 6 to 9 purification of the resulting hydrogen fluorideThe purity of the (gas B) is high, the impurity content is low, and the index is superior to the national standard I type requirement.
Claims (9)
1. The impurity removal method for the hydrogen fluoride is characterized by comprising the following steps of: washing the crude hydrogen fluoride gas by adopting a washing liquid; the washing liquid mainly consists of H 2 O-HF azeotrope composition; the mass fraction of ammonium ions in the washing liquid is less than 10%; the H is 2 The mass fraction of HF in the O-HF azeotrope is 35-40%.
2. The method for removing impurities from hydrogen fluoride according to claim 1, wherein the temperature of the washing liquid is 50 to 90 ℃.
3. The method for removing impurities from hydrogen fluoride according to claim 1, wherein the mass fraction of solid particles in the crude hydrogen fluoride gas is not more than 0.5%.
4. The method for removing impurities from hydrogen fluoride according to claim 1, wherein the washing is performed by countercurrent contact of the washing liquid with crude hydrogen fluoride gas.
5. A method for purifying hydrogen fluoride, comprising the steps of: condensing the crude hydrogen fluoride gas washed in the impurity removal method of hydrogen fluoride according to any one of claims 1 to 4, mixing an impurity removing agent and an oxidizing agent into the liquid hydrogen fluoride obtained by condensation for reaction, carrying out solid-liquid separation, and rectifying the liquid obtained by the solid-liquid separation to obtain hydrogen fluoride;
the impurity removing agent is metal oxide and/or metal fluoride, and metal ions formed by metal elements in the metal oxide and/or the metal fluoride in liquid hydrogen fluoride can form phosphate precipitation with phosphate;
the oxidant is ozone.
6. The method for purifying hydrogen fluoride according to claim 5, wherein the metal element in the metal oxide or the metal fluoride is independently selected from the group consisting of iron element, aluminum element and calcium element.
7. The method for purifying hydrogen fluoride according to claim 5 or 6, wherein the reaction temperature is 0 to 15℃and the reaction time is 1 to 2 hours.
8. The purifying device for the hydrogen fluoride is characterized by comprising a washing unit, a condensing unit, a reaction unit, a solid-liquid separation unit and a rectifying unit which are sequentially connected in the material flow direction;
the washing unit is used for providing H 2 The O-HF azeotrope is used for washing the crude hydrogen fluoride gas;
the condensing unit is a place for condensing the crude hydrogen fluoride gas washed by the washing unit into liquid hydrogen fluoride;
the reaction unit is a place for providing precipitated phosphate ions and oxidized trivalent arsenic;
the solid-liquid separation unit is used for carrying out solid-liquid separation on the liquid hydrogen fluoride material reacted by the reaction unit;
the rectifying unit is a place for rectifying the liquid hydrogen fluoride material separated by the solid-liquid separation unit.
9. The purification apparatus for hydrogen fluoride according to claim 8, wherein a sedimentation unit is further provided upstream of the washing unit; the sedimentation unit is a place for sedimentation of solid particle impurities in the crude hydrogen fluoride gas.
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|---|---|---|---|---|
| US3004829A (en) * | 1960-05-23 | 1961-10-17 | Chemical Construction Corp | Hydrogen fluoride process |
| GB1421646A (en) * | 1972-10-11 | 1976-01-21 | Du Pont | Purification of hydrogen fluoride |
| CN101214926A (en) * | 2007-12-28 | 2008-07-09 | 华陆工程科技有限责任公司 | Technique for producing anhydrous hydrofluoric acid |
| CN104973573A (en) * | 2015-06-18 | 2015-10-14 | 多氟多化工股份有限公司 | Preparation method of highly pure hydrogen fluoride and preparation method of highly pure hydrofluoric acid |
| CN109678114A (en) * | 2019-02-19 | 2019-04-26 | 苏州晶瑞化学股份有限公司 | The minimizing technology of arsenic impurities in a kind of electronic grade hydrochloric acid |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3004829A (en) * | 1960-05-23 | 1961-10-17 | Chemical Construction Corp | Hydrogen fluoride process |
| GB1421646A (en) * | 1972-10-11 | 1976-01-21 | Du Pont | Purification of hydrogen fluoride |
| CN101214926A (en) * | 2007-12-28 | 2008-07-09 | 华陆工程科技有限责任公司 | Technique for producing anhydrous hydrofluoric acid |
| CN104973573A (en) * | 2015-06-18 | 2015-10-14 | 多氟多化工股份有限公司 | Preparation method of highly pure hydrogen fluoride and preparation method of highly pure hydrofluoric acid |
| CN109678114A (en) * | 2019-02-19 | 2019-04-26 | 苏州晶瑞化学股份有限公司 | The minimizing technology of arsenic impurities in a kind of electronic grade hydrochloric acid |
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