CN107055477A - The method and its device of hydrogen fluoride are prepared by fluosilicic acid - Google Patents
The method and its device of hydrogen fluoride are prepared by fluosilicic acid Download PDFInfo
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- CN107055477A CN107055477A CN201710280854.3A CN201710280854A CN107055477A CN 107055477 A CN107055477 A CN 107055477A CN 201710280854 A CN201710280854 A CN 201710280854A CN 107055477 A CN107055477 A CN 107055477A
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 78
- 239000002253 acid Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 180
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007787 solid Substances 0.000 claims abstract description 30
- 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 claims abstract description 29
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000012452 mother liquor Substances 0.000 claims abstract description 16
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 14
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 3
- 238000004176 ammonification Methods 0.000 claims description 46
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 34
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 28
- 238000004821 distillation Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- 235000013024 sodium fluoride Nutrition 0.000 claims description 17
- 239000011775 sodium fluoride Substances 0.000 claims description 17
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- -1 ammonium fluorosilicate Chemical compound 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 11
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical group C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 abstract 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 150000004673 fluoride salts Chemical class 0.000 description 4
- 239000010436 fluorite Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910017665 NH4HF2 Inorganic materials 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 description 2
- 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
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004590 computer program Methods 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 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
- C01B7/193—Preparation from silicon tetrafluoride, fluosilicic acid or fluosilicates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention proposes a kind of method and its device that hydrogen fluoride is prepared by fluosilicic acid, and preparation includes fluosilicic acid with ammonia by two-stage aminating reaction, ammonium fluoride solution and silica solid are obtained after separation；Ammonium fluoride solution is concentrated, crystallized, separated, and obtains ammonium hydrogen fluoride solid and mother liquor；Ammonium hydrogen fluoride solid is reacted with fluoride, obtains hydrogen fluoride thing solid and ammonia；Hydrogen fluoride thing solid is heated, and is allowed to decompose, is obtained hydrogen fluoride gas and potassium fluoride.Device includes, one-level aminating reaction kettle, secondary amine reactor, the first separator, condensing crystallizing kettle, ammonia destilling tower, heat energy supply equipment, the second separator, reactor and decomposer.The present invention utilizes the hydrogen fluoride of byproduct fluosilicic acid industrialized production, and purity can reach more than 99.96%, and other impurities meet national standard technical grade index request, and low production cost.
Description
Technical Field
The invention belongs to the field of hydrogen fluoride preparation and devices thereof, and particularly relates to a method for preparing hydrogen fluoride from fluosilicic acid and a device thereof.
Background
Hydrogen Fluoride (Hydrogen Fluoride) has a chemical formula of HF and a molecular weight of 20.01, and is easily soluble in water and ethanol. Anhydrous Hydrogen Fluoride (AHF) is a colorless transparent liquid at low temperature or pressure, with a boiling point of 19.4 ℃, a melting point of-83.37 ℃, and a density of 1.008g/cm3 (water ═ 1). It is very volatile to white smoke at room temperature and normal temperature. It is chemically very reactive and can react with alkali, metals, oxides and silicates. Hydrogen fluoride is the basis of modern fluorine chemical industry and is the most basic raw material for preparing elemental fluorine, various fluorine refrigerants, novel fluorine-containing materials, inorganic fluoride salts, various organic fluorides and the like. Hydrofluoric acid is mainly used in the semiconductor industry and glass etchants because silicon is chemically inert, and does not react with water, air, acids, and strong bases at room temperature. Can react with HF at 200-400 ℃: the Si +4HF ═ SiF4+2H2 ≠ reaction rate is quite fast and complete. Also used for producing organic or inorganic fluorides such as fluorocarbons, sodium fluoride, aluminum fluoride, uranium hexafluoride and cryolite; hydrofluoric acid can be used as an important raw material in the fluorine chemical industry to produce fluorine refrigerant, fluorine-containing polymer and fluorine-containing medicine, and aluminum fluoride and cryolite produced by the hydrofluoric acid are necessary additives in the aluminum refining industry; the cleaning agent is also an alkylation catalyst of an oil refinery, and is used as a surface rust remover in the steel industry, as a catalyst in the petrochemical industry, and as a dirt corrosion cleaning agent or an outer wall cleaning agent in the cleaning service industry; in addition, fluoride salts produced by hydrofluoric acid are widely applied to food protection, special smelting, leather and textile treatment, specimen preservation, nuclear industry and the like.
In recent years, with the development of fluorine chemical industry in China, series products such as fluoride salt, fluorinated aromatic hydrocarbon, fluorine-containing resin and the like are developed rapidly, and the demand for anhydrous hydrogen fluoride is increased rapidly. In addition, with the continuous emergence of fluorine-containing pesticides and fluorine-containing medical intermediates, the demand of anhydrous hydrogen fluoride is continuously increased due to the application of electronic grade fluorine products; in addition, many foreign merchants purchase hydrogen fluoride and fluoride salt in vain, and the vigorous development of the hydrogen fluoride production industry in China is promoted.
China mainly adopts fluorite and sulfuric acid to react to prepare and produce AHF, although the hydrogen fluoride production technology of China is in the leading level of the world, the problems of the production process of the fluorite-sulfuric acid method exist, such as: low energy utilization rate, high production cost, difficult fluorgypsum treatment, serious dust pollution and the like, which are still not ignored. In the era of global advocating energy conservation, consumption reduction and low-carbon economy development, the exploration of new production technology and process becomes a consensus of the people in the industry. In addition, fluorite is an important and strategic non-renewable resource required to be controlled by the nation, in recent years, the government has more and more strict control on the mining amount of fluorite ore, the more and more the policy is tightened, and the price of fluorite fluorine resource is bound to be higher and higher. Therefore, it has been more and more important to develop a technology for producing hydrogen fluoride from by-product fluosilicic acid with high efficiency, low consumption and environmental protection.
Disclosure of Invention
The invention provides a method and a device for preparing hydrogen fluoride from fluosilicic acid, which solve the problems of excessive by-product fluosilicic acid and possible environmental pollution caused by the excessive by-product fluosilicic acid in the prior art.
The invention also solves the problem of high preparation cost of the hydrogen fluoride and the problem of high configuration requirement of the existing hydrogen fluoride preparation equipment.
A method for preparing hydrogen fluoride from fluosilicic acid comprises the following steps,
1) performing two-stage ammoniation reaction on fluosilicic acid and ammonia, and separating to obtain an ammonium fluoride solution and a silicon dioxide solid;
2) concentrating, crystallizing and separating the ammonium fluoride solution obtained in the step 1) to obtain ammonium bifluoride solid and mother liquor;
3) reacting the ammonium bifluoride solid obtained in the step 2) with fluoride to obtain a hydrogen fluoride solid and ammonia gas; recycling ammonia gas to the step 1); the fluoride is potassium fluoride or sodium fluoride; the hydrogen fluoride is potassium hydrogen fluoride or sodium hydrogen fluoride;
4) heating the solid hydrogen fluoride obtained in the step 3) to decompose the solid hydrogen fluoride to obtain hydrogen fluoride gas and fluoride; recycling fluoride to step 3);
wherein, the ammonia added in the first reaction in the step 1) is purchased liquid ammonia; the fluoride added in the first reaction in the step 3) is purchased fluoride; continuously mixing the mother liquor obtained in the step 2) with the ammonium fluoride solution obtained in the step 1), and repeating the operation of the step 2).
As a preferred technical scheme, the molar ratio of the fluosilicic acid to the liquid ammonia in the step 1) is 1: 6-6.02; the reaction temperature is 75-95 ℃; the two-stage ammoniation reaction is continuous, and the silicon dioxide separated after the reaction is also continuously and directly separated; the purity of the obtained silicon dioxide is more than or equal to 99.5 percent.
As a preferred technical scheme, in the first-stage ammoniation reaction of the two-stage ammoniation reaction, ammonium fluorosilicate is generated from fluorosilicic acid and liquid ammonia; and the ammonium fluosilicate and liquid ammonia are subjected to secondary ammoniation reaction to generate ammonium fluoride.
As a preferable technical scheme, the concentration temperature of the ammonium fluoride in the step 2) is 65-180 ℃, and the pressure is-0.07-0.2 Mpa.
As a preferable technical scheme, the reaction temperature in the step 3) is 115-225 ℃.
As a preferable technical scheme, the decomposition temperature in the step 4) is 150-420 ℃, and the pressure is-0.05-0.15 MPa.
Preferably, the decomposition temperature of the sodium fluoride in the step 4) is 160-210 ℃.
As a preferable technical scheme, the decomposition temperature of the potassium bifluoride in the step 4) is 360-380 ℃. As a preferable technical scheme, the method also comprises the step of condensing the hydrogen fluoride obtained in the step 4) to prepare anhydrous hydrogen fluoride; or absorbing with water to obtain hydrofluoric acid.
Preferably, the method further comprises the step of washing the hydrogen fluoride obtained in the step 4) with concentrated sulfuric acid, and then condensing or absorbing with water.
Preferably, the evaporated water in the concentration of the ammonium fluoride solution in the step 2) contains 1 to 40% of ammonia, the ammonia is recovered from the evaporated water by an ammonia distillation column, the recovered ammonia may be ammonia gas or aqueous ammonia, and the recovered ammonia is returned to the 1 st-stage and 2 nd-stage ammonification reactions. The water after ammonia recovery can be directly discharged.
A device for preparing hydrogen fluoride from fluosilicic acid comprises,
the device comprises a primary ammonification reaction kettle, a secondary ammonification reaction kettle, a first separator, a concentration crystallization kettle, an ammonia distillation tower, heat energy supply equipment, a second separator, a reactor and a decomposer; the primary ammonification reaction kettle, the secondary ammonification reaction kettle, the first separator, the concentration crystallization kettle, the second separator, the reactor and the decomposer are communicated in sequence;
the primary ammonification reaction kettle is provided with a fluosilicic acid feeding port;
the primary ammonification reaction kettle and the secondary ammonification reaction kettle are respectively provided with an ammonia feeding pipe orifice;
the feed inlet of the ammonia distillation tower is communicated with the evaporation steam outlet of the concentration crystallization kettle, and the ammonia gas outlet of the ammonia distillation tower is respectively communicated with the ammonia gas feed pipe orifices of the primary ammonification reaction kettle and the secondary ammonification reaction kettle so as to realize the cyclic utilization of ammonia;
the ammonia distillation tower is also provided with a wastewater discharge port;
the reactor also comprises a feed inlet for supplementing fluoride and an ammonia gas outlet, wherein the ammonia gas outlet is respectively communicated with the ammonia gas feed pipe orifices of the primary ammonification reaction kettle and the secondary ammonification reaction kettle so as to realize the cyclic utilization of ammonia;
the heat energy supply device is respectively connected with the concentration crystallization kettle, the ammonia distillation tower, the reactor and the decomposer to provide heat energy.
Preferably, the system further comprises a condenser which is communicated with the decomposer.
As a preferable technical scheme, a mother liquor outlet of the second separator is communicated with the concentration crystallization kettle through a pipeline.
The invention relates to a chemical reaction formula:
H2SiF6+2NH3→(NH4)2SiF6………………………………(1)
(NH4)2SiF6+4NH3→6NH4F………………………………(2)
2NH4F→NH4HF2+NH3………………………………(3)
NH4HF2+2KF→2KHF2+NH3………………………………(4)
NH4HF2+2NaF→2NaHF2+NH3………………………………(5)
KHF2→HF+KF………………………………(6)
NaHF2→HF+NaF………………………………(7)
advantageous effects
(1) The invention adopts two-stage ammoniation reaction of fluosilicic acid and ammonia, so the operation has 5 advantages: a. the adding amount of ammonia can be saved, and the ammonia does not need to be excessive; b. the silicon dioxide is quickly precipitated; c. the silica is easy to separate; d. the content of silicon dioxide in ammonium fluoride is very low; e. the heat exchange effect is good.
(2) The method adopts solid-phase reaction of ammonium bifluoride solid and fluoride to obtain ammonia; ammonia is more easily recovered than in a liquid phase reaction in which an ammonium fluoride solution is reacted with a fluoride to produce a potassium hydrogen fluoride solution; can save cost, is beneficial to protecting environment and realizes green production.
(3) The invention utilizes the byproduct fluosilicic acid to industrially produce the hydrogen fluoride, the purity can reach more than 99.96 percent, other impurities meet the national standard industrial grade index requirements, and the production cost is low.
(4) After the potassium fluoride (or sodium fluoride) is decomposed at the temperature of 160-380 ℃, 2-5% of potassium hydrogen fluoride (or sodium hydrogen fluoride) in a potassium fluoride (or sodium fluoride) product is not decomposed, and the mixture is recycled to the step 3 without influence on the reaction, but the energy can be effectively saved.
(5) The equipment realizes the recycling of the raw materials, the water discharged by the process does not need to be treated again, and the combination of resource recycling and environmental protection is realized. The equipment layout is reasonable, the occupied area is small, and the method is suitable for industrial popularization and application.
(6) The primary ammonification reaction kettle, the secondary ammonification reaction kettle, the first separator, the concentration crystallization kettle, the ammonia distillation tower, the heat energy supply equipment, the second separator, the reactor, the decomposer and the condenser of the equipment are hermetically connected through pipelines, and all recycled materials also form a closed recycling pipeline, so the equipment is easy to realize sealing; the process operation is automatically operated according to set process parameters under the control of a computer program.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive exercise.
Fig. 1 is a schematic structural diagram of an apparatus for fluorosilicic acid preparation of hydrogen fluoride in example 1.
FIG. 2 is a process flow diagram of a method for preparing hydrogen fluoride from fluorosilicic acid.
Wherein,
a first-stage ammoniation reaction kettle 11, a second-stage ammoniation reaction kettle 12, a first separator 13, a concentration crystallization kettle 14, an ammonia distillation tower 15, a heat energy supply device 16, a second separator 17, a reactor 18, a decomposer 19 and a condenser 20.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, the apparatus for preparing hydrogen fluoride from fluorosilicic acid comprises a primary ammonification reaction kettle 11, a secondary ammonification reaction kettle 12, a first separator 13, a concentration crystallization kettle 14, an ammonia distillation tower 15, a heat energy supply device 16, a second separator 17, a reactor 18 and a decomposer 19. Wherein the primary ammonification reaction kettle 11, the secondary ammonification reaction kettle 12, the first separator 13, the concentration crystallization kettle 14, the second separator 17, the reactor 18 and the decomposer 19 are communicated in sequence through pipelines and valves. The first-stage ammonification reaction kettle 11 is provided with a fluosilicic acid feeding port, and the first-stage ammonification reaction kettle 11 and the second-stage ammonification reaction kettle 12 are respectively provided with an ammonia feeding pipeline. The feed inlet of the ammonia distillation tower 15 is communicated with the evaporation water vapor outlet of the concentration crystallization kettle 14, and is used for introducing the ammonia-containing water vapor generated during the concentration of the concentration crystallization kettle 14 into the ammonia distillation tower 15. The ammonia gas outlet of the ammonia distillation tower 15 is respectively communicated with the ammonia feeding pipelines of the first-stage ammonification reaction kettle 11 and the second-stage ammonification reaction kettle 12 so as to realize the recycling of the ammonia gas. The ammonia distillation tower 15 is also provided with a wastewater discharge port, and redundant water after ammonia distillation can be directly discharged. The reactor 18 further comprises a feed inlet for supplementing fluoride and an ammonia gas outlet, wherein the ammonia gas outlet is respectively communicated with ammonia gas feed pipelines of the primary ammonification reaction kettle 11 and the secondary ammonification reaction kettle 12 so as to realize the cyclic utilization of ammonia gas. The thermal energy supply device 16 is connected to the concentration crystallization tank 14, the ammonia distillation column 15, the reactor 18, and the decomposer 19, respectively, to supply thermal energy. In order to recover the hydrogen fluoride produced, a condenser 20 is also provided in this embodiment, which communicates with the decomposer 19. In order to utilize the raw materials to the maximum extent and reduce the discharge of waste, the second separator 17 is communicated with the concentration crystallization kettle 14, and the mother liquor in the separator is refluxed into the concentration crystallization kettle 14 through a pipeline for recycling. The primary ammonification reaction kettle, the secondary ammonification reaction kettle, the first separator, the concentration crystallization kettle, the ammonia distillation tower, the heat energy supply equipment, the second separator, the reactor, the decomposer and the condenser of the equipment are hermetically connected through pipelines, and all recycled materials also form a closed recycling pipeline, so that the equipment is easy to seal; the process operation is automatically operated according to set process parameters under the control of a computer program.
Example 2
Hydrogen fluoride was produced using the apparatus of example 1.
Raw materials: 1000kg of 30% fluosilicic acid, 20kg of liquid ammonia and 75kg of potassium fluoride.
The method comprises the following specific steps:
(1) fluosilicic acid and liquid ammonia are added into a first-stage ammoniation reaction kettle 11, the reaction condition is controlled at 80 ℃, after the reaction is completed, the mixture is introduced into a second-stage ammoniation reaction kettle 12, and the reaction is continued to obtain a silicon dioxide and ammonium fluoride solution. The silica and ammonium fluoride solution is separated via a first separator 13. Wherein the content of silicon dioxide is 99.6 percent, and the content of silicon dioxide in the ammonium fluoride solution is less than 0.3 percent.
(2) And (2) introducing the ammonium fluoride solution separated in the step (1) into a concentration crystallization kettle 14, controlling the reaction condition at 95 ℃, and separating ammonium bifluoride and mother liquor through a second separator 17 after the reaction is completed. Wherein the mother liquor is returned to the concentration crystallization kettle 14 for continuous use. The ammonia water-containing steam is introduced into an ammonia distillation tower 15, and the purified ammonia gas is introduced into a primary ammonification reaction kettle 11 and a secondary ammonification reaction kettle 12. In this example, the ammonia gas returned in the last cycle was absorbed as ammonia water to obtain 300kg of 6% ammonia water; in this way, the ammonia consumption per ton of hydrogen fluoride prepared by the method is only 8.1 kg.
(3) And (3) mixing and reacting the separated ammonium bifluoride solid and potassium fluoride in a reactor 18, wherein the reaction condition is controlled at 170 ℃ to obtain the potassium bifluoride solid and ammonia gas. And (4) recycling ammonia gas to the step (1).
(4) And (3) feeding the potassium bifluoride solid into a decomposition reactor 18, controlling the temperature at 420 ℃, and decomposing for 1 hour to generate hydrogen fluoride and potassium fluoride. After the hydrogen fluoride was condensed by a condenser at-5 ℃, 246.6kg of anhydrous hydrogen fluoride liquid was obtained. The purity of the prepared hydrogen fluoride is more than 99.96 percent.
The weight of the residual potassium fluoride is 74.5 kg; in this way, the consumption of potassium fluoride per ton of hydrogen fluoride prepared by the method is only 2 kg.
Example 3
Hydrogen fluoride was produced using the apparatus of example 1.
A method for preparing hydrogen fluoride from fluorosilicic acid comprises,
1) introducing fluorosilicic acid and liquid ammonia into a first-stage reaction kettle according to a molar ratio of 1:1.8, controlling the temperature to be 75 ℃, obtaining ammonium fluorosilicate after complete reaction, and introducing the ammonium fluorosilicate into a second-stage reaction kettle, wherein the molar ratio of the ammonium fluorosilicate to the liquid ammonia is 1: 4.22, continuing the reaction to obtain the silicon dioxide and ammonium fluoride solution. The silica and ammonium fluoride solution is separated via a first separator 13. The purity of the obtained silicon dioxide is more than 99.5 percent.
2) Introducing the ammonium fluoride solution obtained in the step 1) into a concentration crystallization kettle 14, controlling the reaction condition at 65 ℃ and the pressure of-0.07 Mpa, and separating ammonium bifluoride and mother liquor through a second separator 17 after the reaction is completed. Wherein the mother liquor is returned to the concentration crystallization kettle 14 for continuous use. The ammonia and the vapor escaped during the concentration are introduced into an ammonia distillation tower 15, and the purified ammonia is introduced into a primary ammonification reaction kettle 11 and a secondary ammonification reaction kettle 12. The water after ammonia distillation directly reaches the standard and is discharged. In this example, the ammonia gas returned in the last cycle was absorbed as ammonia water to obtain 300kg of 6% ammonia water; in this way, the ammonia consumption per ton of hydrogen fluoride prepared by the method is only 8.1 kg.
3) And mixing the ammonium bifluoride solid obtained by separation and sodium fluoride in a reactor 18 for reaction, wherein the reaction condition is controlled at 125 ℃ to obtain sodium bifluoride solid and ammonia gas. Ammonia gas is recycled to step 1).
4) The sodium fluoride solid is sent into a decomposition reactor 18, the temperature is controlled at 150 ℃, and decomposition is carried out for 1.5 hours, and hydrogen fluoride and sodium fluoride are generated by reaction. The hydrogen fluoride is passed into a condenser 20 and cooled with-5 ℃ brine to obtain anhydrous hydrogen fluoride liquid. The purity of the prepared hydrogen fluoride is more than 99.96 percent.
Example 4
Hydrogen fluoride was produced using the apparatus of example 1.
A method for preparing hydrogen fluoride from fluorosilicic acid comprises,
1) introducing fluorosilicic acid and liquid ammonia into a first-stage reaction kettle according to a molar ratio of 1:2.2, controlling the temperature to be 95 ℃, obtaining ammonium fluorosilicate after complete reaction, and introducing the ammonium fluorosilicate into a second-stage reaction kettle, wherein the molar ratio of the ammonium fluorosilicate to the liquid ammonia is 1: and 3.8, continuing the reaction to obtain a silicon dioxide and ammonium fluoride solution. The silica and ammonium fluoride solution is separated via a first separator 13. The purity of the obtained silicon dioxide is more than 99.5 percent.
2) Introducing the ammonium fluoride solution obtained in the step 1) into a concentration crystallization kettle 14, controlling the reaction condition at 180 ℃ and the pressure at 0.2Mpa, and separating ammonium bifluoride and mother liquor through a second separator 17 after the reaction is completed. Wherein the mother liquor is returned to the concentration crystallization kettle 14 for continuous use. The ammonia and the vapor escaped during the concentration are introduced into an ammonia distillation tower 15, and the purified ammonia is introduced into a primary ammonification reaction kettle 11 and a secondary ammonification reaction kettle 12. The water after ammonia distillation directly reaches the standard and is discharged.
3) And mixing the ammonium bifluoride solid obtained by separation and sodium fluoride in a reactor 18 for reaction, wherein the reaction condition is controlled at 115 ℃ to obtain sodium bifluoride solid and ammonia gas. Ammonia gas is recycled to step 1).
4) The sodium fluoride solid is sent into a decomposition reactor 18, the temperature is controlled at 210 ℃, the pressure is 0.15Mpa, the decomposition is carried out for 1.0 hour, and hydrogen fluoride and sodium fluoride are generated by the reaction. The hydrogen fluoride is firstly cleaned by concentrated sulfuric acid and then absorbed by water to be hydrofluoric acid. After the sodium fluoride is decomposed at the temperature of 160-210 ℃, 2-5% of sodium fluoride in the sodium fluoride product is not decomposed, and the mixture is recycled to the step 3 without influence on the reaction, but the energy can be effectively saved.
Example 5
Hydrogen fluoride was produced using the apparatus of example 1.
1) Introducing fluorosilicic acid and liquid ammonia into a first-stage reaction kettle according to a molar ratio of 1:2, controlling the temperature to be 90 ℃, obtaining ammonium fluorosilicate after complete reaction, and introducing the ammonium fluorosilicate into a second-stage reaction kettle, wherein the molar ratio of the ammonium fluorosilicate to the liquid ammonia is 1: and 4, continuing the reaction to obtain a silicon dioxide and ammonium fluoride solution. The silica and ammonium fluoride solution is separated via a first separator 13. The purity of the obtained silicon dioxide is more than 99.5 percent.
2) Introducing the ammonium fluoride solution obtained in the step 1) into a concentration crystallization kettle 14, controlling the reaction condition at 100 ℃ and the pressure at 0.1Mpa, and separating ammonium bifluoride and mother liquor through a second separator 17 after the reaction is completed. Wherein the mother liquor is returned to the concentration crystallization kettle 14 for continuous use. The ammonia gas is introduced into an ammonia distillation tower 15, and the purified ammonia gas is introduced into a primary ammonification reaction kettle 11 and a secondary ammonification reaction kettle 12. And directly discharging the waste liquid.
3) And (3) mixing and reacting the separated ammonium bifluoride solid and potassium fluoride in a reactor 18, and controlling the reaction condition at 150 ℃ to obtain the potassium bifluoride solid and ammonia gas. Ammonia gas is recycled to step 1).
4) The potassium bifluoride solid is sent into a decomposition reactor 18, the temperature is controlled at 360 ℃, the pressure is minus 0.05Mpa, and the reaction is carried out for 1.5 hours to generate hydrogen fluoride and potassium fluoride. Cleaning hydrogen fluoride with concentrated sulfuric acid, introducing into a condenser 20, and cooling with-5 deg.C saline water to obtain anhydrous hydrogen fluoride liquid; the purity of the prepared hydrogen fluoride is more than 99.96 percent. Wherein the decomposition is carried out at the temperature of 360-380 ℃, potassium fluoride products contain 2-5% of potassium bifluoride which is not decomposed, and the mixture is recycled to the step 3 without influence on the reaction, but the energy can be effectively saved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for preparing hydrogen fluoride from fluosilicic acid is characterized by comprising the following steps,
1) performing two-stage ammoniation reaction on fluosilicic acid and ammonia, and separating to obtain an ammonium fluoride solution and a silicon dioxide solid;
2) concentrating, crystallizing and separating the ammonium fluoride solution obtained in the step 1) to obtain ammonium bifluoride solid and mother liquor;
3) reacting the ammonium bifluoride solid obtained in the step 2) with fluoride to obtain a hydrogen fluoride solid and ammonia gas; recycling ammonia gas to the step 1); the fluoride is potassium fluoride or sodium fluoride; the hydrogen fluoride is potassium hydrogen fluoride or sodium hydrogen fluoride;
4) heating the solid hydrogen fluoride obtained in the step 3) to decompose the solid hydrogen fluoride to obtain hydrogen fluoride gas and fluoride; recycling fluoride to step 3);
wherein, the ammonia added in the first reaction in the step 1) is purchased liquid ammonia; the fluoride added in the first reaction in the step 3) is purchased fluoride; continuously mixing the mother liquor obtained in the step 2) with the ammonium fluoride solution obtained in the step 1), and repeating the operation of the step 2).
2. A method for preparing hydrogen fluoride from fluosilicic acid according to claim 1, wherein the molar ratio of the fluosilicic acid to the liquid ammonia in the step 1) is 1: 6-6.02; the reaction temperature is 75-95 ℃; the two-stage ammoniation reaction is continuous, and the silicon dioxide separated after the reaction is also continuously and directly separated; the purity of the obtained silicon dioxide is more than or equal to 99.5 percent.
3. A process for preparing hydrogen fluoride from fluorosilicic acid as set forth in claim 2,
in the first-stage ammoniation reaction, the ammonium fluorosilicate is generated from the fluosilicic acid and the liquid ammonia; and the ammonium fluosilicate and liquid ammonia are subjected to secondary ammoniation reaction to generate ammonium fluoride.
4. The method for preparing hydrogen fluoride from fluosilicic acid according to claim 1, wherein the concentration temperature of the ammonium fluoride in the step 2) is 65 to 180 ℃, and the pressure is-0.07 to 0.2 Mpa; the reaction temperature in the step 3) is 115-225 ℃; in the step 4), the decomposition temperature is 150-420 ℃, and the pressure is-0.05-0.15 Mpa.
5. The method for preparing hydrogen fluoride from fluosilicic acid as claimed in claim 1, further comprising condensing the hydrogen fluoride obtained in step 4) to obtain anhydrous hydrogen fluoride; or absorbing with water to obtain hydrofluoric acid with water; the decomposition temperature of the sodium fluoride in the step 4) is 160-210 ℃; the decomposition temperature of the potassium bifluoride in the step 4) is 360-380 ℃.
6. The method for preparing hydrogen fluoride from fluosilicic acid according to claim 1, further comprising washing the hydrogen fluoride obtained in step 4) with concentrated sulfuric acid, and then condensing or absorbing with water.
7. The method for preparing hydrogen fluoride from fluosilicic acid according to claim 1, wherein the evaporation water during the concentration of the ammonium fluoride solution in the step 2) contains 1-40% of ammonia, the ammonia is recovered through an ammonia distillation column, and the recovered ammonia is returned to the two-stage ammoniation reaction; and directly discharging the water after ammonia recovery.
8. A device for preparing hydrogen fluoride from fluosilicic acid is characterized by comprising,
the device comprises a primary ammonification reaction kettle, a secondary ammonification reaction kettle, a first separator, a concentration crystallization kettle, an ammonia distillation tower, heat energy supply equipment, a second separator, a reactor and a decomposer; the primary ammonification reaction kettle, the secondary ammonification reaction kettle, the first separator, the concentration crystallization kettle, the second separator, the reactor and the decomposer are communicated in sequence;
the primary ammonification reaction kettle is provided with a fluosilicic acid feeding pipe orifice; the primary ammonification reaction kettle and the secondary ammonification reaction kettle are respectively provided with an ammonia feeding pipeline;
the feed inlet of the ammonia distillation tower is communicated with the steam outlet of the concentration crystallization kettle, and the ammonia gas outlet of the ammonia distillation tower is respectively communicated with the ammonia gas feed pipelines of the primary ammonification reaction kettle and the secondary ammonification reaction kettle so as to realize the cyclic utilization of ammonia gas;
the ammonia distillation tower is also provided with a wastewater discharge port;
the reactor also comprises a feed inlet for supplementing fluoride and an ammonia gas outlet, wherein the ammonia gas outlet is respectively communicated with ammonia gas feed pipelines of the primary ammonification reaction kettle and the secondary ammonification reaction kettle so as to realize the cyclic utilization of ammonia gas;
the heat energy supply device is respectively connected with the concentration crystallization kettle, the ammonia distillation tower, the reactor and the decomposer to provide heat energy.
9. The apparatus for preparing hydrogen fluoride from fluorosilicic acid as set forth in claim 8, further comprising a condenser in communication with said decomposer.
10. The device for preparing hydrogen fluoride by using fluosilicic acid according to claim 8, wherein a mother liquor outlet of the second separator is communicated with the concentrated crystallization kettle through a pipeline.
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