CN115010091A - 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 292
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 290
- 239000012535 impurity Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 72
- 238000000746 purification Methods 0.000 title claims description 20
- 238000005406 washing Methods 0.000 claims abstract description 170
- 239000007789 gas Substances 0.000 claims abstract description 158
- 239000007788 liquid Substances 0.000 claims abstract description 153
- -1 ammonium ions Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 22
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 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 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 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
- 239000002244 precipitate Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 description 43
- 239000002253 acid Substances 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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 11
- 239000006227 byproduct Substances 0.000 description 10
- 238000005507 spraying Methods 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 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
- 238000001914 filtration Methods 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 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 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-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
- 239000003054 catalyst Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 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
- 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
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 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
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000004140 cleaning Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 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
- 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
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 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
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
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 production of inorganic chemical products. The impurity removal method of hydrogen fluoride comprises the following steps: washing the crude hydrogen fluoride gas by using a washing solution; the washing liquid is mainly composed 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 the hydrogen fluoride adopts the method that H is mainly used 2 The washing liquid composed of O-HF azeotrope is used to wash crude hydrogen fluoride gas, so as to avoid the introduction of foreign impurities such as sulfate radical, and efficiently remove NH in crude hydrogen fluoride material 4 + 、PO 4 3‑ 、SO 4 2‑ And the like, and 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, belonging to the technical field of production of inorganic chemical products.
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 other materials. The fluorine chemical industry in China is rapidly developed in recent years, the annual capacity of hydrogen fluoride in China currently reaches more than 200 ten thousand tons, and most of the hydrogen fluoride is produced by adopting a fluorite method. The fluorite method is to prepare hydrogen fluoride gas by reacting fluorite and sulfuric acid, but is limited by the limited exploitation of the national tactical resource fluorite, the price of the fluorite gradually rises in China, and the search of a new fluorine source becomes the focus of industrial attention. SO is contained in raw material hydrogen fluoride gas prepared by fluorite method 4 2- 、PO 4 3- 、H 2 O、SO 2 、As 3+ And the like.
The content of fluorine as one of the associated elements of phosphorus ore serving as a raw material of phosphorus chemical industry is about 3-4%, which is 10-20 times of the reserve of fluorite. A large amount of silicon tetrafluoride gas is produced as a byproduct 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 has rich resources and low price. In recent years, a great deal of research has been carried out in China on the efficient high-value utilization of industrial by-product fluosilicic acid, particularly, the process development of preparing anhydrous hydrogen fluoride by fluosilicic acid has been carried out successively by the technology of preparing anhydrous hydrogen fluoride by a fluosilicic acid ammoniation sulfuric acid decomposition method, a fluosilicic acid concentrated sulfuric acid method, a hydrogen fluoride (such as sodium hydrogen fluoride) pyrolysis method and the like, but the hydrogen fluoride gas prepared by the fluosilicic acid ammonization sulfuric acid decomposition method or the hydrogen fluoride pyrolysis method by using the fluosilicic acid as a raw material contains NH 4 + 、PO 4 3- 、SO 4 2- 、As 3+ And the impurity components are different from the impurities contained in the hydrogen fluoride prepared by using fluorite as the raw material, butThe hydrogen fluoride prepared by the two methods contains SO 2 、PO 4 3- 、SO 4 2- And the like water-soluble impurities. For example, in the pyrolysis of hydrogen fluoride to produce anhydrous hydrogen fluoride, ammonium fluoride and/or ammonium bifluoride is first converted to an alkali metal hydrogen fluoride, and then the hydrogen fluoride is pyrolyzed. When the fluosilicic acid is decomposed by the ammonified sulfuric acid to prepare the anhydrous hydrogen fluoride, the 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 the ammonium fluoride solution and the silicon dioxide precipitate are filtered 4 F filtrate is evaporated, concentrated, pre-reacted and premixed to form hydrogen fluoride ammonia reaction liquid, the 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 components SiF with low boiling point are removed 4 、SO 2 、CO 2 Equal impurities, and heavy component H with high boiling point 2 SO 4 、H 2 O and the like. But due to SO 2 And NH 4 + And the catalyst is mutually soluble with water, and is easily mixed with heavy component impurities such as sulfuric acid, water and the like, so that the limitation of rectification phase balance is aggravated, and further, the deep impurity removal of HF is difficult to realize through rectification. Chinese patent application CN112744788A discloses a method for deeply dehydrating and purifying refined FTrPSA by fluorosilicic acid method to produce anhydrous HF, which comprises the following steps: the raw material HF gas is subjected to cold-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 the adsorption step, the other adsorption towers are in desorption steps of different stages including pressure reduction reverse release or vacuumizing, pressurization or final charging, and the raw material HF gas subjected to medium-temperature pressure swing adsorption is further purified and decontaminated by rectification to obtain the hydrogen fluoride. However, 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.
A second object of the present invention is to provide a method for purifying hydrogen fluoride.
The third purpose of the invention is to provide a hydrogen fluoride purification device.
In order to achieve the purpose, the technical scheme adopted by the impurity removal method of the hydrogen fluoride is as follows:
an impurity removal method of hydrogen fluoride comprises the following steps: washing the crude hydrogen fluoride gas by using 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 the hydrogen fluoride adopts the method that H is mainly used 2 The washing liquid composed of O-HF azeotrope can wash crude hydrogen fluoride gas, avoid the introduction of foreign impurities such as sulfate radical and the like, and can efficiently remove NH in the crude hydrogen fluoride raw material 4 + 、PO 4 3- 、SO 4 2- And the like, and has the advantages of simple operation and lower cost.
Preferably, said 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 present 2 When the mass fraction of HF in the O-HF azeotrope is 35-40%, H is mainly used 2 The cleaning solution composed of the O-HF azeotrope washes the crude hydrogen fluoride gas, so that the use of a strong corrosive concentrated sulfuric acid raw material can be avoided, on one hand, the introduction of new impurities is avoided, on the other hand, the production cost of the raw material is reduced, and the beneficial effects of high impurity removal efficiency and good product quality are achieved.
It will be appreciated that the main component in the wash liquor is H 2 The O-HF azeotrope, the scrubbing solution also contains small amounts of impurities, mainly H-soluble in the crude hydrogen fluoride gas 2 Substances of O-HF azeotropes, e.g. NH 4 + 、PO 4 3- 、SO 4 2- And the like.
To avoid H 2 The O-HF azeotrope forms a gas, and preferably, the temperature of the washing 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 a countercurrent manner, and the hydrogen fluoride gasThe body is easy to overflow from the washing liquid, and water and NH 4 + 、PO 4 3- And SO 4 2- And the solubility of the soluble impurities in the washing liquid is higher, so that the efficient washing and separation are 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 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 subjected to gas-solid separation is washed. Preferably, the crude hydrogen fluoride gas is obtained by dedusting a raw material hydrogen fluoride gas. Preferably, the dust removal is achieved by sedimentation. The method adopts a settling process to naturally settle the particles 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 unpurified hydrogen fluoride gas obtained by reaction in the process of preparing anhydrous hydrogen fluoride by adopting a fluorosilicic acid method or a fluorite method. For example, the raw material hydrogen fluoride gas is an unpurified hydrogen fluoride gas produced by a fluorosilicic acid ammonolysis method and/or a hydrogen fluoride pyrolysis method using fluorosilicic acid as a raw material. Preferably, the temperature of the raw material hydrogen fluoride gas is 100-220 ℃.
In the washing, the washing liquid may be brought into contact with the crude hydrogen fluoride gas in any manner, for example, the crude hydrogen fluoride gas may be bubbled into the washing liquid to be washed, or the washing liquid may be brought into counter-current contact with the crude hydrogen fluoride gas to wash the crude hydrogen fluoride gas. Preferably, the washing is carried out by counter-current contacting of the washing liquid with crude hydrogen fluoride gas. For example, the washing may be performed in a washing column, and the washing liquid is brought into countercurrent contact with the crude hydrogen fluoride gas during the washing to wash 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 is understood that when the raw hydrogen fluoride gas is an unpurified hydrogen fluoride gas produced by fluorosilicic acid ammonolysis and/or hydrogen fluoride pyrolysis using fluorosilicic acid as a raw material, the raw hydrogen fluoride gas containsNH 4 + 、PO4 3- 、SO 4 2- 、As 3+ And the like.
The crude hydrogen fluoride gas is washed by using the washing liquid, the washing liquid can be recycled, the concentration of ammonium ions in the washing liquid is detected, and preferably, when the mass fraction of the ammonium ions in the washed washing liquid is more than 10%, the washing liquid reacts 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 percent, the main component in the washing liquid is NH 4 HF 2 、HF、H 2 O, etc., the washing liquid can react with ammonia gas to prepare a byproduct ammonium bifluoride, and the obtained ammonium bifluoride can be sold or returned to a fluosilicic acid production line for preparing anhydrous hydrofluoric acid.
The technical scheme adopted by the purification method of hydrogen fluoride comprises the following steps:
a method for purifying hydrogen fluoride, comprising the steps of: condensing the crude hydrogen fluoride gas washed in the hydrogen fluoride impurity removal method, mixing an impurity removal agent and an oxidant into the liquid hydrogen fluoride obtained by condensation to react, 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 metal fluoride in liquid hydrogen fluoride can generate phosphate precipitates with phosphate radicals; the oxidant is ozone.
The method for purifying the hydrogen fluoride firstly adopts the method of mainly using H 2 The crude hydrogen fluoride gas is washed by the washing liquid consisting of the O-HF azeotrope, so that most of water-soluble impurities can be removed, then phosphate impurities are removed by adopting an impurity removing agent, and trivalent arsenic is oxidized by adopting ozone, so that oxidants such as highly toxic fluorine gas and potassium permanganate can be avoided, the working environment of production personnel is improved, and the safety of the production process is improved; on the other hand, foreign impurity ions can be prevented from being introduced, the subsequent purification difficulty is reduced, and the product quality can be further improved. The method for purifying the hydrogen fluoride can effectively remove NH in the raw material hydrogen fluoride 4 + 、PO4 3- 、SO 4 2- 、As 3+ 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 and the impurity removing agent are subjected to impurity removing reaction firstly and then are subjected to impurity removing reaction with the ozone, or the liquid hydrogen fluoride and the impurity removing agent are subjected to impurity removing reaction firstly and then are subjected to impurity removing reaction with the impurity removing agent, or the liquid hydrogen fluoride, the impurity removing agent and the ozone are subjected to impurity removing reaction simultaneously.
Preferably, in the method for purifying hydrogen fluoride, the metal element in the metal oxide or metal fluoride is independently selected from iron, aluminum or calcium.
Preferably, the temperature adopted by the condensation is-5-15 ℃.
Preferably, the impurity removal agent is used in excess.
Preferably, when the impurity removing agent is selected from one or any combination of iron oxide, aluminum oxide, iron fluoride and aluminum fluoride, the molar ratio of the iron element and/or the aluminum element in the impurity removing agent to the 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 calcium element in the impurity removing agent to phosphate radical in the liquid hydrogen fluoride is (3-3.05): 2.
Preferably, after the reaction is finished, the system after the reaction is subjected to solid-liquid separation, and 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 which can be sold as a byproduct after treatment.
Preferably, As in the ozone and liquid hydrogen fluoride 3+ The molar ratio of (1-1.1): 1.
Preferably, the reaction temperature is 0-15 ℃, and the reaction time is 1-2 h.
Preferably, the temperature of the bottom of a rectifying tower used for rectification is 20-25 ℃, and the temperature of the top of the rectifying tower is 10-15 ℃.
Preferably, the reflux ratio of the rectifying tower for rectifying is 1.5-2.0.
The tail gas generated by the hydrogen fluoride purification method enters a 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 hydrogen fluoride purification device is as follows:
a hydrogen fluoride purification device comprises a washing unit, a condensation unit, a reaction unit, a solid-liquid separation unit and a rectification unit which are sequentially connected in the material flowing direction;
the washing unit is used for providing H 2 A location where the O-HF azeotrope washes the crude hydrogen fluoride gas;
the condensing unit is used for condensing the crude hydrogen fluoride gas washed by the washing unit into liquid hydrogen fluoride;
the reaction unit is a site for providing precipitated phosphate ions and oxidizing trivalent arsenic;
the solid-liquid separation unit is a place for carrying out solid-liquid separation on the liquid hydrogen fluoride material after the reaction of the reaction unit;
the rectification 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 purified hydrogen fluoride has the advantages of high purity and low impurity content. Meanwhile, the hydrogen fluoride purification device has the advantages of simple operation, low production cost and high comprehensive utilization degree of raw materials.
Preferably, a settling unit is further arranged upstream of the washing unit; the sedimentation unit is used for settling solid particle impurities in the crude hydrogen fluoride gas.
Drawings
FIG. 1 is a schematic view showing the structure of a hydrogen fluoride purification apparatus according to the present invention; wherein the reference numbers are as follows: 1-a settling tank, 2-a washing tower, 3-a condenser, 4-an impurity removal tank, 5-a filter, 6-a rectifying tower and 7-an aerator.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
The raw hydrogen fluoride gas used in examples 1 to 4 and examples 6 to 9 of the present invention was derived from an unpurified hydrogen fluoride gas prepared by a hydrogen fluoride pyrolysis method using fluorosilicic acid as a raw material.
The specific embodiment of the impurity removal method of hydrogen fluoride of the invention is as follows:
example 1
The method for removing impurities from hydrogen fluoride in the embodiment specifically comprises the following steps:
introducing a raw material hydrogen fluoride gas with the temperature of 220 ℃ into a settling tank, wherein particles in the raw material hydrogen fluoride gas are settled to the bottom of the settling tank under the action of gravity, the crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) overflows from the top of the settling tank, and then enters 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 H is introduced 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 90 ℃, controlling the liquid-gas ratio to be 2.3, and overflowing the washed crude hydrogen fluoride gas from the top of the washing tower to complete impurity removal of the crude hydrogen fluoride gas.
In this example, H 2 The mass fraction of HF in the O-HF azeotrope was 35%. The washing liquid is initially composed of H 2 And (3) O-HF azeotrope composition, 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 the washing liquid is discharged from the washing tower and reacts with a proper amount of ammonia gas to prepare an ammonium bifluoride product.
Example 2
The method for removing impurities from hydrogen fluoride in this embodiment specifically includes the following steps:
introducing a raw material hydrogen fluoride gas with the temperature of 180 ℃ into a settling tank, wherein particles in the raw material hydrogen fluoride gas are settled to the bottom of the settling tank under the action of gravity, and the crude hydrogen fluoride gas (the mass fraction of solid particles)The number is not more than 0.5 percent) overflows from the top of the settling tank, and then enters a washing tower (the height of the washing tower is 5m, the diameter of the tower is 0.7m, and a filler adopts a plastic Raschig ring), 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 75 ℃, controlling the liquid-gas ratio to be 2.5, and overflowing the washed crude hydrogen fluoride gas from the top of the washing tower to complete impurity removal of the crude hydrogen fluoride gas.
In this example, H 2 The mass fraction of HF in the O-HF azeotrope was 38%. The washing liquid is initially composed of H 2 And (3) O-HF azeotrope composition, 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 the washing liquid is discharged from the washing tower and reacts with a proper amount of ammonia gas to prepare an ammonium bifluoride product.
Example 3
The method for removing impurities from hydrogen fluoride in this embodiment specifically includes the following steps:
introducing a raw material hydrogen fluoride gas with the temperature of 100 ℃ into a settling tank, wherein particles in the raw material hydrogen fluoride gas are settled to the bottom of the settling tank under the action of gravity, the crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) overflows from the top of the settling tank, and then the crude hydrogen fluoride gas enters a washing tower (the height of the washing tower is 5m, the diameter of the washing tower is 0.7m, a plastic Raschig ring is adopted as a filler), H is 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 ℃, controlling the liquid-gas ratio to be 2.2, and overflowing the washed crude hydrogen fluoride gas from the top of the washing tower to complete impurity removal of the crude hydrogen fluoride gas.
In this example, H 2 The mass fraction of HF in the O-HF azeotrope was 35%. The washing liquid is initially composed of H 2 And (3) O-HF azeotrope composition, 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 the washing liquid is discharged from the washing tower and reacts with a proper amount of ammonia gas to prepare an ammonium bifluoride product.
Example 4
The method for removing impurities from hydrogen fluoride in this embodiment specifically includes the following steps:
introducing a raw material hydrogen fluoride gas with the temperature of 130 ℃ into a settling tank, wherein particles in the raw material hydrogen fluoride gas are settled to the bottom of the settling tank under the action of gravity, the crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) overflows from the top of the settling tank, and then enters 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 H is introduced 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 complete impurity removal of the crude hydrogen fluoride gas.
In this example, H 2 The mass fraction of HF in the O-HF azeotrope was 37%. The washing liquid is initially composed of 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 10%, and the washing liquid is discharged from the washing tower and reacts with a proper amount of ammonia gas to prepare an ammonium bifluoride product.
Secondly, the specific embodiment of the hydrogen fluoride purification apparatus of the present invention is as follows:
example 5
The schematic structural diagram of the hydrogen fluoride purification apparatus of this embodiment is shown in fig. 1, and includes a settling tank 1, a washing column 2, a condenser 3, an impurity removal tank 4, a filter 5, and a rectification column 6. Wherein, the settling tank 1 constitutes a settling unit, the washing tower 2 constitutes a washing unit, the condenser 3 constitutes a condensing unit, the impurity removing tank 4 constitutes a reaction unit, the filter 5 constitutes a solid-liquid separation unit, and the rectifying tower 6 constitutes a rectifying unit.
The settling tank 1 is provided with a raw material hydrogen fluoride gas inlet, and a gas outlet of the settling 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 which is used for spraying the washing liquid downwards from the top of the washing tower 2, 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 hole of the condenser 3 is connected with the feed inlet of the impurity removing groove 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 of a discharge hole of the condenser 3 and then enters an impurity removal tank 4.
A stirring device is arranged in the impurity removing tank 4, an aerator 7 is arranged at the bottom of the impurity removing tank 4, and the aerator 7 is provided with an ozone gas inlet for introducing ozone into the impurity removing tank 4. The discharge hole of the impurity removing groove 4 is connected with the feed inlet of the filter 5, and the discharge hole of the filter 5 is connected with the feed inlet of the rectifying tower 6. The rectifying tower 6 is provided with a hydrogen fluoride product outlet.
The following methods for purifying hydrogen fluoride according to examples 6 to 9 were used to purify a raw material hydrogen fluoride gas by using the purification apparatus of example 5.
Thirdly, the specific embodiment of the method for purifying hydrogen fluoride of the present invention is as follows:
example 6
The method for purifying hydrogen fluoride in the embodiment specifically includes the following steps:
(1) introducing a raw material hydrogen fluoride gas with the temperature of 220 ℃ into a settling tank, wherein particles in the raw material hydrogen fluoride gas are settled to the bottom of the settling tank under the action of gravity, the crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) overflows from the top of the settling tank, and then enters 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 H is introduced 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 90 ℃, and controlling the liquid-gas ratio to be 2.3, wherein 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 initially composed of H 2 And (3) O-HF azeotrope composition, after washing the crude hydrogen fluoride gas, recycling the crude hydrogen fluoride gas until the mass fraction of ammonium ions in the washing liquid is 9.5%, discharging the washing liquid from the washing tower, introducing ammonia gas into the washing liquid until the pH value of the washing liquid is 2 so as to enable HF and the ammonia gas to react, and after the reaction is finished, performing concentration and crystallization to obtain an ammonium hydrogen fluoride product.
(2) Introducing the washed crude hydrogen fluoride gas into a condenser, controlling the temperature of the condenser to be 15 ℃, and condensing to obtain liquid hydrogen fluoride and liquid fluorineThe hydrogen fluoride gets into the edulcoration groove, lets in ozone in to the edulcoration groove through the aerator of edulcoration tank bottom portion simultaneously, and the liquid hydrogen fluoride after the edulcoration groove of entering carries out edulcoration reaction 1h with aluminium fluoride and ozone in the edulcoration groove under the stirring condition at 15 ℃, then filters through the filter, obtains the liquid hydrogen fluoride after the edulcoration, and exhaust waste gas gets into tail gas absorbing device in the edulcoration groove. The solid obtained by filtering is aluminum phosphate which can be sold as a byproduct after being treated. The mol ratio of aluminum element in the aluminum fluoride to phosphate radical in the liquid hydrogen fluoride is 1:1, ozone is introduced into the impurity removing groove, and the As in the liquid hydrogen fluoride 3+ In a molar ratio of 1: 1.
(3) And (3) feeding the liquid hydrogen fluoride after impurity removal into a rectifying tower, controlling the temperature of the bottom of the rectifying tower to be 20 ℃, the temperature of the top of the rectifying tower to be 10 ℃, and the reflux ratio to be 1.6, condensing the liquid obtained at the top of the rectifying tower to be the hydrogen fluoride, and feeding the uncondensed gas into a tail gas absorption device.
Example 7
The method for purifying hydrogen fluoride in the embodiment specifically includes the following steps:
(1) introducing a raw material hydrogen fluoride gas with the temperature of 180 ℃ into a settling tank, wherein particles in the raw material hydrogen fluoride gas are settled to the bottom of the settling tank under the action of gravity, the crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) overflows from the top of the settling tank, and then enters 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 H is introduced 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. H 2 The mass fraction of HF in the O-HF azeotrope was 38%. The washing liquid is initially composed of H 2 And (2) O-HF azeotrope composition, after washing the crude hydrogen fluoride gas, recycling the crude hydrogen fluoride gas until the mass fraction of ammonium ions in the washing liquid is 9.8%, discharging the washing liquid from the washing tower, introducing ammonia gas into the washing liquid until the pH value of the washing liquid is 2.5 so as to enable the HF and the ammonia gas to react, and after the reaction is finished, performing concentration crystallization to obtain an ammonium bifluoride product.
(2) The crude hydrogen fluoride after washing is carried outThe body lets in the condenser, the temperature of control condenser is 10 ℃, the condensation obtains liquid hydrogen fluoride, liquid hydrogen fluoride gets into the edulcoration groove, simultaneously let in ozone to the edulcoration groove through the aerator of edulcoration tank bottom, liquid hydrogen fluoride after the entering edulcoration groove and iron oxide and ozone in the edulcoration groove carry out the edulcoration reaction 1.5h under the stirring condition at 10 ℃, then filter through the filter, obtain the liquid hydrogen fluoride after the edulcoration, exhaust waste gas gets into tail gas absorbing device in the edulcoration groove. The solid obtained by filtering is ferric phosphate which can be sold as a byproduct after being processed. The mol ratio of iron element in the ferric oxide to phosphate radical in the liquid hydrogen fluoride is 1.05:1, ozone is introduced into the impurity removing groove, and the As in the liquid hydrogen fluoride 3+ Is 1.1: 1.
(3) And (3) feeding the liquid hydrogen fluoride after impurity removal into a rectifying tower, controlling the temperature of the bottom of the rectifying tower to be 22 ℃, the temperature of the top of the rectifying tower to be 15 ℃, and the reflux ratio to be 1.5, condensing the top of the rectifying tower to obtain liquid, namely hydrogen fluoride, and feeding uncondensed gas into a tail gas absorption device.
Example 8
The method for purifying hydrogen fluoride in the embodiment specifically includes the following steps:
(1) introducing a raw material hydrogen fluoride gas with the temperature of 100 ℃ into a settling tank, wherein particles in the raw material hydrogen fluoride gas are settled to the bottom of the settling tank under the action of gravity, the crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) overflows from the top of the settling tank, and then the crude hydrogen fluoride gas enters a washing tower (the height of the washing tower is 5m, the diameter of the washing tower is 0.7m, a plastic Raschig ring is adopted as a filler), H is 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 controlling the liquid-gas ratio to be 2.2, wherein 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 initially composed of H 2 The O-HF azeotrope is formed by washing 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 as to enable HF and ammonia gas to react, and concentrating and binding after the reaction is finishedCrystallizing to obtain the ammonium bifluoride product.
(2) Introducing the washed crude hydrogen fluoride gas into a condenser, controlling the temperature of the condenser to be-5 ℃, condensing to obtain liquid hydrogen fluoride, introducing the liquid hydrogen fluoride into an impurity removal groove, introducing ozone into the impurity removal groove through an aerator at the bottom of the impurity removal groove, carrying out impurity removal reaction for 2h at 0 ℃ under the stirring condition on the liquid hydrogen fluoride entering the impurity removal groove, calcium fluoride and ozone in the impurity removal groove, filtering by a filter to obtain the liquid hydrogen fluoride after impurity removal, and introducing exhaust waste gas into a tail gas absorption device. The solid obtained by filtering is calcium phosphate which can be sold as a byproduct after being processed. The mol ratio of calcium element in the calcium fluoride to phosphate radical in the liquid hydrogen fluoride is 3.05:1, ozone is introduced into the impurity removing groove, and the As in the liquid hydrogen fluoride 3+ Is 1.05: 1.
(3) And (3) feeding the liquid hydrogen fluoride after impurity removal into a rectifying tower, controlling the tower bottom temperature of the rectifying tower to be 25 ℃, the tower top temperature to be 12 ℃, the reflux ratio to be 1.8, condensing the tower top to obtain liquid, namely hydrogen fluoride, and feeding uncondensed gas into a tail gas absorption device.
Example 9
The method for purifying hydrogen fluoride in the embodiment specifically comprises the following steps:
(1) introducing a raw material hydrogen fluoride gas with the temperature of 130 ℃ into a settling tank, wherein particles in the raw material hydrogen fluoride gas are settled to the bottom of the settling tank under the action of gravity, the crude hydrogen fluoride gas (the mass fraction of solid particles is not more than 0.5%) overflows from the top of the settling tank, and then enters 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 H is introduced 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. H 2 The mass fraction of HF in the O-HF azeotrope was 37%. The washing liquid is initially composed of H 2 The O-HF azeotrope is used to wash coarse hydrogen fluoride gas and the washed liquid is exhausted from the washing tower and fed to the washing liquid after the ammonium radical ion content in the washing liquid reaches 10 wt%And (3) introducing ammonia gas until the pH value of the washing liquid is 2 so as to enable the HF and the ammonia gas to react, and after the reaction is finished, concentrating and crystallizing to obtain an ammonium bifluoride product.
(2) The method comprises the steps of introducing crude hydrogen fluoride gas after washing into a condenser, controlling the temperature of the condenser to be 0 ℃, condensing to obtain liquid hydrogen fluoride, introducing the liquid hydrogen fluoride into an impurity removal groove, introducing ozone into the impurity removal groove through an aerator at the bottom of the impurity removal groove, carrying out impurity removal reaction for 2h at 0 ℃ under the stirring condition on the liquid hydrogen fluoride after entering the impurity removal groove, calcium fluoride in the impurity removal groove and ozone, and filtering through a filter to obtain the liquid hydrogen fluoride after impurity removal. The solid obtained by filtering is calcium phosphate which can be sold as a byproduct after being processed. The molar ratio of calcium element in the calcium fluoride to 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+ Is 1.05: 1.
(3) And (3) feeding the liquid hydrogen fluoride after impurity removal into a rectifying tower, controlling the temperature of the bottom of the rectifying tower to be 23 ℃, the temperature of the top of the rectifying tower to be 13 ℃, and the reflux ratio to be 2.0, condensing the top of the rectifying tower to obtain liquid, namely hydrogen fluoride, and feeding uncondensed gas into a tail gas absorption device.
Comparative example
The method for purifying hydrogen fluoride of this comparative example differs from the method for purifying hydrogen fluoride of example 6 only in that the washing liquid used in step (1) of the method for purifying hydrogen fluoride of this comparative example is concentrated sulfuric acid (mass fraction is 98%).
Examples of the experiments
The raw hydrogen fluoride gas, the crude hydrogen fluoride gas (represented by gas A) overflowing from the top of the washing column in the comparative example and examples 6 to 9, and the hydrogen fluoride (represented by gas B) purified in the comparative example and examples 6 to 9 were each tested for its HF mass fraction, moisture mass fraction, fluorosilicic acid mass fraction, sulfur dioxide mass fraction, and non-volatile acid (represented by H) by the method prescribed in GB/T33337 to 2016 2 SO 4 In terms of P) of phosphorus (in terms of P) 2 O 5 Meter) and arsenic, the test results are shown in table 1.
TABLE 1 Mass fraction of HF and mass fractions of other impurities in the raw hydrogen fluoride gas, the crude hydrogen fluoride gas after washing in examples 6 to 9, and the hydrogen fluoride purified in examples 6 to 9
The results show that the main component of the catalyst is H 2 The washing liquid composed of O-HF azeotrope can wash crude hydrogen fluoride gas with better washing effect, especially can efficiently remove NH in crude hydrogen fluoride raw material 4 + 、PO 4 3- 、SO 4 2- And the subsequent rectification and purification difficulty is reduced by using soluble impurities, and the product quality is further improved by using the hydrogen fluoride. The hydrogen fluoride (gas B) obtained by purification in examples 6 to 9 has high purity and low impurity content, and the index is superior to the national standard class I requirement.
Claims (10)
1. An impurity removal method for hydrogen fluoride is characterized by comprising the following steps: washing the crude hydrogen fluoride gas by using a washing solution; the washing liquid is mainly composed of H 2 O-HF azeotrope composition; the mass fraction of ammonium ions in the washing liquid is less than 10%.
2. The method for removing impurities of hydrogen fluoride according to claim 1, wherein the H is 2 The mass fraction of HF in the O-HF azeotrope is 35-40%.
3. An impurity removal method for hydrogen fluoride according to claim 1 or 2, wherein the temperature of the washing solution is 50 to 90 ℃.
4. The method for removing impurities from hydrogen fluoride according to claim 1 or 2, wherein the mass fraction of solid particles in the crude hydrogen fluoride gas is not more than 0.5%.
5. The method for removing impurities from hydrogen fluoride according to claim 1 or 2, wherein the washing is carried out by contacting a washing liquid with a crude hydrogen fluoride gas in a counter-current manner.
6. A method for purifying hydrogen fluoride, comprising the steps of: condensing the crude hydrogen fluoride gas washed in the method for removing impurities from hydrogen fluoride according to any one of claims 1 to 5, mixing an impurity removing agent and an oxidizing agent into the liquid hydrogen fluoride obtained by condensation to react, 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 metal fluoride in liquid hydrogen fluoride can generate phosphate precipitates with phosphate radicals;
the oxidant is ozone.
7. The method of purifying hydrogen fluoride according to claim 6, wherein the metal element in the metal oxide or the metal fluoride is independently selected from the group consisting of iron, aluminum and calcium.
8. The method for purifying hydrogen fluoride according to claim 6 or 7, wherein the reaction temperature is 0 to 15 ℃ and the reaction time is 1 to 2 hours.
9. A hydrogen fluoride purification device is characterized by comprising a washing unit, a condensation unit, a reaction unit, a solid-liquid separation unit and a rectification unit which are sequentially connected in the material flowing direction;
the washing unit is used for providing H 2 A location where the O-HF azeotrope washes the crude hydrogen fluoride gas;
the condensing unit is used for condensing the crude hydrogen fluoride gas washed by the washing unit into liquid hydrogen fluoride;
the reaction unit is a site for providing precipitated phosphate ions and oxidizing trivalent arsenic;
the solid-liquid separation unit is a place for carrying out solid-liquid separation on the liquid hydrogen fluoride material after the reaction of the reaction unit;
the rectification unit is a place for rectifying the liquid hydrogen fluoride material separated by the solid-liquid separation unit.
10. The apparatus for purifying hydrogen fluoride according to claim 9, wherein a settling unit is further provided upstream of the scrubbing unit; the settling unit is a place for settling solid particle impurities in the crude hydrogen fluoride gas.
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| CN117208852A (en) * | 2023-10-07 | 2023-12-12 | 福建天甫电子材料有限公司 | Purification control system and method for preparing electronic grade hydrofluoric acid |
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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 |
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