CN112520770B - Comprehensive utilization method of atmospheric condensate - Google Patents
Comprehensive utilization method of atmospheric condensate Download PDFInfo
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- CN112520770B CN112520770B CN202011497148.2A CN202011497148A CN112520770B CN 112520770 B CN112520770 B CN 112520770B CN 202011497148 A CN202011497148 A CN 202011497148A CN 112520770 B CN112520770 B CN 112520770B
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- hydrochloric acid
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- 238000000034 method Methods 0.000 title claims abstract description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000706 filtrate Substances 0.000 claims abstract description 58
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 46
- 238000001914 filtration Methods 0.000 claims abstract description 42
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000012065 filter cake Substances 0.000 claims abstract description 35
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 28
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000002674 ointment Substances 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 13
- 238000010517 secondary reaction Methods 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229940104869 fluorosilicate Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 13
- 229910001514 alkali metal chloride Inorganic materials 0.000 abstract description 10
- 229910004074 SiF6 Inorganic materials 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 239000002002 slurry Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- -1 calcium fluorosilicate Chemical compound 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- APURLPHDHPNUFL-UHFFFAOYSA-M fluoroaluminum Chemical compound [Al]F APURLPHDHPNUFL-UHFFFAOYSA-M 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 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 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a comprehensive utilization method of a large gas condensate, which comprises the following steps: carrying out primary reaction on the atmospheric condensate and primary hydrochloric acid to obtain primary reaction liquid, and filtering to obtain primary filtrate and primary filter cake; carrying out secondary reaction on the primary filter cake and secondary hydrochloric acid to obtain secondary reaction liquid, and filtering to obtain secondary filtrate and a secondary filter cake; the atmospheric condensate is formed in the production process of aluminum fluoride; washing, drying and calcining the secondary filter cake to obtain high-purity aluminum fluoride; reacting the primary filtrate with alkali metal chloride and an auxiliary agent to remove impurities, filtering, neutralizing and filtering again to obtain filtrate and ointment; washing and drying the ointment to obtain aluminum hydroxide; the filtrate was concentrated to give ammonium chloride. The invention has more complete reaction by the reaction of the primary hydrochloric acid and the secondary hydrochloric acid, and can solve the problem of SiF6 by adding the alkali metal chloride impurity removal process 2‑ 、PO4 3‑ And SO4 2‑ The problem is accumulated in the system, and products such as aluminum fluoride, aluminum hydroxide and ammonium chloride are obtained.
Description
Technical Field
The invention relates to the technical field of fluorine chemical industry, in particular to a comprehensive utilization method of a large gas condensate.
Background
Aluminum fluoride (AlF) 3 ) Colorless or white crystal, stable chemical property, difficult dissolution in water, acid and alkali and stable property. It is decomposed by water at high temperature, and can be heated at normal pressure without melting and sublimated at high temperature (without direct liquid vaporization). Mainly used as an additive of cryolite-alumina fused salt electrolysis (Hall-Heroult method) and used in the electrolytic aluminum industry. In addition, the compound can be used as a catalyst in the synthesis of organic compounds and organic fluorides, a component of ceramic and enamel cosolvents and enamels, an improving agent of the refractive index of lenses and prisms, a fluorinated glass for manufacturing infrared spectra, an inhibitor in the alcohol production process and the like.
At present, various aluminum fluoride production at home and abroad is divided into three major categories, namely wet aluminum fluoride, dry aluminum fluoride and high-purity aluminum fluoride according to the process. The dry-method aluminum fluoride process mainly takes raw material of unpurified hydrogen fluoride gas produced by fluorite as raw material to directly enter a fluidized bed gas-solid reaction with aluminum hydroxide to produce aluminum fluoride products, the tail gas produced in the production process is carried with aluminum fluoride and aluminum oxide materials, after most particles are removed by a cyclone dust collection device, high-temperature tail gas enters an atmosphere condensation spray tower to be cooled and absorbed, a part of fine materials still exist in absorption liquid, and the fine materials are deposited to form the atmosphere condensation material. According to the statistics of industrialized production, about 10-15kg of atmosphere condensate generated by producing 1 ton of dry-method aluminum fluoride, wherein the fluorine content is 45-55%, the aluminum content is 28-31%, the silicon dioxide content is 1-4%, and the sulfate radical content is 0.5-2.5%, and the indexes far do not meet the national standard requirements, so that the materials cannot be sold outside, and the resources are wasted due to long-term stacking.
In contrast, there is a report on using hydrofluoric acid to treat the atmospheric condensate to improve the product purity, but the process is high in temperature, the hydrofluoric acid is seriously volatilized, the material is sticky and difficult to filter, the working condition is severe, and the equipment is seriously corroded. Specifically, the hydrofluoric acid process has the disadvantages that: 1) Hydrofluoric acid is weak in acidity, and after hydrofluoric acid is added, incomplete reaction occurs, materials are sticky and difficult to filter, so that the quality of aluminum fluoride products is not obviously improved; 2) The hydrofluoric acid process produces SiF6 2- 、PO4 3- And SO4 2- The phenomenon is accumulated in the system, so the mother liquor after treatment can not be recycled, but the direct discharge can generate secondary pollution.
Therefore, it is urgently needed to develop a green environmental protection process for treating the large gas condensate so as to realize the high-efficiency and high-value utilization of resources and the clean production of fluorine chemical industry.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a comprehensive utilization method of an atmosphere condensate, which solves the problem of difficult treatment of fluorine-containing waste residues generated in the dry-process aluminum fluoride preparation process, and realizes clean production of fluorine chemical industry and efficient utilization of fluorine resources.
The invention provides a comprehensive utilization method of a large gas condensate, which comprises the following steps:
a) Carrying out primary reaction on the atmospheric condensate and primary hydrochloric acid to obtain primary reaction liquid, and filtering to obtain primary filtrate and primary filter cake;
carrying out secondary reaction on the primary filter cake and secondary hydrochloric acid to obtain secondary reaction liquid, and filtering to obtain secondary filtrate and a secondary filter cake; the atmospheric condensate is formed in the production process of aluminum fluoride;
b) Washing, drying and calcining the secondary filter cake to obtain high-purity aluminum fluoride;
reacting the primary filtrate with alkali metal chloride and an auxiliary agent to remove impurities, filtering, neutralizing and filtering again to obtain filtrate and ointment; washing and drying the ointment to obtain aluminum hydroxide; the filtrate was concentrated to give ammonium chloride.
Preferably, the concentration of the primary hydrochloric acid is 100 g/L-300 g/L; the concentration of the secondary hydrochloric acid is 100 g/L-300 g/L; the hydrochloric acid can be an industrial byproduct or a commodity sold in the market.
Preferably, the reaction temperature of the first-stage reaction is 40-70 ℃; the reaction time is 0.5 to 1 hour; the temperature of the second-stage reaction is 40-70 ℃; the reaction time is 0.5-1 h.
Preferably, the Al content in the first-stage filtrate is (0.23-0.24) C HCl g/L, the first-stage filtrate is used for preparing the aluminum hydroxide by the reaction in the step B).
Preferably, the alkali metal chloride is one or more of calcium chloride, magnesium chloride or barium chloride, and the adding amount is excessive adding amount, and the judgment standard of the excessive adding amount is as follows: the method is based on that new precipitates are not generated when the catalyst is added; the precipitate is specifically the precipitate of calcium fluorosilicate, calcium sulfate and calcium phosphate. The auxiliary agent is polyacrylamide, and the dosage is 0.05-0.5mg/L. Preferably, the neutralization in the step B) is specifically performed by ammonia water/ammonia gas; wherein Al is 3+ And NH 3 The molar ratio is 1: (3-3.05).
Preferably, the reaction temperature of the step B) is 20-50 ℃; the reaction time is 0.5-2 h.
Preferably, the mass percentage of each component in the big gas condensate is as follows: 45-55% of fluorine, 28-31% of aluminum, 1-4% of silicon dioxide and 0.5-2.5% of sulfate radical.
Preferably, the mass concentration of the first-stage reaction liquid in the step A) is 20-50%; the mass concentration of the secondary reaction liquid is 20-50%.
Preferably, the calcining temperature in the step B) is 400-700 ℃; the calcination time is 1-3 h. Compared with the prior art, the invention provides a comprehensive utilization method of a large gas condensate, which comprises the following steps: a) Carrying out primary reaction on the atmospheric condensate and primary hydrochloric acid to obtain primary reaction liquid, and filtering to obtain primary filtrate and primary filter cake; the first-stage filter cake and second-stage hydrochloric acid are subjected to second-stage reaction to obtain second-stage reaction liquid, and second-stage filtrate and second-stage filter cake are obtained through filtration; the atmospheric condensate is formed in the production process of aluminum fluoride; b) The second mentionedWashing, drying and calcining the grade filter cake to obtain high-purity aluminum fluoride; reacting the primary filtrate with calcium chloride to remove impurities, filtering, neutralizing, and filtering again to obtain filtrate and ointment; washing and drying the ointment to obtain aluminum hydroxide; the filtrate was concentrated to give ammonium chloride. The invention makes the reaction more complete by the reaction of the primary hydrochloric acid and the secondary hydrochloric acid, and simultaneously adds the alkali metal chloride impurity removal process, thereby solving the problem of SiF6 2- 、PO4 3- And SO4 2- The problem is accumulated in the system, and the product quality is further improved. The products with different purities, such as high-purity aluminum fluoride, industrial-grade aluminum hydroxide, ammonium chloride and the like, can be applied to different fields, and the resource recycling value is improved.
Detailed Description
The invention provides a comprehensive utilization method of a large gas condensate, and a person skilled in the art can use the contents to reference the contents and appropriately improve the process parameters to realize the comprehensive utilization method. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a comprehensive utilization method of a large gas condensate, which comprises the following steps:
a) Carrying out primary reaction on the atmospheric condensate and primary hydrochloric acid to obtain primary reaction liquid, and filtering to obtain primary filtrate and primary filter cake;
carrying out secondary reaction on the primary filter cake and secondary hydrochloric acid to obtain secondary reaction liquid, and filtering to obtain secondary filtrate and a secondary filter cake; the atmospheric condensate is formed in the production process of aluminum fluoride;
b) Washing, drying and calcining the secondary filter cake to obtain high-purity aluminum fluoride;
reacting the primary filtrate with alkali metal chloride and an auxiliary agent to remove impurities, filtering, neutralizing and filtering again to obtain filtrate and ointment; washing and drying the ointment to obtain aluminum hydroxide; the filtrate was concentrated to give ammonium chloride.
The dry aluminum fluoride process mainly takes unpurified hydrogen fluoride gas produced by fluorite as a raw material to directly enter a fluidized bed gas-solid reaction with aluminum hydroxide to produce an aluminum fluoride product, the tail gas produced in the production process is carried with aluminum fluoride and aluminum oxide materials, most of particles are removed by a cyclone dust collection device, the high-temperature tail gas enters an atmosphere condensation spray tower to be cooled and absorbed, a part of fine materials still exist in absorption liquid, and the fine materials are deposited to form an atmosphere condensation material. According to the statistics of industrialized production, about 10-15kg of atmosphere condensed material is generated by producing 1 ton of dry-method aluminum fluoride, wherein the fluorine content is 45-55%, the aluminum content is 28-31%, the silicon dioxide content is 1-4%, and the sulfate radical content is 0.5-2.5%.
The comprehensive utilization method of the atmospheric condensate provided by the invention firstly carries out primary reaction on the atmospheric condensate and primary hydrochloric acid to obtain primary reaction liquid.
The concentration of the primary hydrochloric acid is preferably 100 g/L-300 g/L; specifically, the concentration may be 100g/L, 200g/L or 300g/L.
The temperature of the first-order reaction is preferably 40-70 ℃; the reaction time is 0.5-1 h.
The mass concentration of the first-stage reaction liquid is preferably 20-50%.
Filtering the first-stage reaction liquid to obtain first-stage filtrate and first-stage filter cake. The present invention is not limited to the specific filtration method, and those skilled in the art will be familiar with the method.
The first-stage filtrate of the invention contains 0.23-0.24 percent of C HCl g/L, the first-stage filtrate is used for preparing the aluminum hydroxide by the reaction of the step B). Wherein C is HCl The concentration of hydrochloric acid is defined as above in the present invention.
Meanwhile, the first-stage filter cake continues to a second-stage hydrochloric acid device for second-stage reaction. At this time, new hydrochloric acid is injected into the primary hydrochloric acid apparatus. The new atmospheric condensate is preferentially reacted in the secondary hydrochloric acid so as to make the hydrochloric acid fully utilized, and the invention can make the primary filtrate and the secondary filtrate circularly treat the atmospheric condensate.
And carrying out secondary reaction on the primary filter cake and secondary hydrochloric acid to obtain secondary reaction liquid, and filtering to obtain secondary filtrate and a secondary filter cake.
The concentration of the secondary hydrochloric acid is preferably 100 g/L-300 g/L; specifically, the concentration may be 100g/L, 200g/L or 300g/L.
The reaction temperature of the secondary reaction is preferably 40-70 ℃; the reaction time is 0.5-1 h.
The mass concentration of the secondary reaction liquid is preferably 20-50%.
The secondary filter cake is washed, dried and calcined to obtain the high-purity aluminum fluoride.
Wherein the calcining temperature is 400-700 ℃; the calcination time is 1-3 h. (ii) a
The first-stage filtrate reacts with alkali metal chloride and an auxiliary agent to remove impurities.
The alkali metal chloride is one or more of calcium chloride, magnesium chloride or barium chloride, the adding amount is excessive, and the excessive judgment standard is as follows: the method is based on that new precipitates are not generated when the catalyst is added; the precipitate is specifically the precipitate of fluorosilicate, sulfate and phosphate. The auxiliary agent is polyacrylamide, and the dosage is 0.05-0.5mg/L.
Filtering after removing impurities, and then neutralizing. The temperature of the neutralization reaction is preferably 20-50 ℃; the reaction time is 1-2 h.
The invention preferably adopts ammonia water/ammonia gas for neutralization; wherein Al is 3+ And NH 3 The molar ratio is 1: (3-3.05).
Neutralizing, and filtering again to obtain filtrate and ointment; the present invention is not limited to the specific filtration method, and those skilled in the art will be familiar with the method.
Wherein, the ointment is washed and dried to obtain the aluminum hydroxide.
The present invention is not limited to the specific washing and drying operations, and those skilled in the art will be familiar with the present invention.
The filtrate was concentrated to give ammonium chloride. Can be sold directly. The present invention is not limited to the specific procedure for the concentration, and those skilled in the art will be familiar with the present invention. Can be concentrated under reduced pressure.
The invention can also adopt fluorine chemical by-product fluorine-containing hydrochloric acid to react with the atmospheric condensate, and the reaction effect is the same.
The chemical reaction equation related by the invention mainly comprises:
Al 2 O 3 +6HCl→2AlCl 3 +3H 2 O
SiF 6 2- +2PO 4 3- +SO 4 2- +5Ca 2+ →CaSiF 6 ↓+Ca 3 (PO 4 ) 2 ↓+CaSO 4 ↓
AlCl 3 +3NH 3 .H 2 O→Al(OH) 3 ↓+3NH 4 Cl
according to the invention, by utilizing the property that aluminum fluoride is difficult to dissolve in an acidic solution and the solubility of impurities such as silicon, phosphorus, sulfate radicals and the like is increased in a strong acidic solution, the content of each impurity is effectively removed, and the superfine high-purity aluminum fluoride is prepared and used in high-end fields such as optical coating materials, ternary lithium battery material coating and the like. The method adopts alkali chloride to remove impurities such as silicon, phosphorus, sulfate radical and the like in the mother liquor, the prepared aluminum hydroxide has high purity and low impurity content, meets the production requirement of dry aluminum fluoride, and solves the problem of SiF6 2- 、PO4 3- And SO4 2- Problems that accumulate in the system. The method has the advantages of simple process, environmental protection, no secondary pollution, realization of high-efficiency and high-value comprehensive utilization of resources and creation of maximum value of resources.
The invention provides a comprehensive utilization method of a large gas condensate, which comprises the following steps: a) Carrying out primary reaction on the atmospheric condensate and primary hydrochloric acid to obtain primary reaction liquid, and filtering to obtain primary filtrate and primary filter cake; the first-stage filter cake and second-stage hydrochloric acid are subjected to second-stage reaction to obtain second-stage reaction liquid, and second-stage filtrate and second-stage filter cake are obtained through filtration; the atmospheric condensate is formed in the production process of aluminum fluoride; b) Washing, drying and calcining the secondary filter cake to obtain high-purity aluminum fluoride; reacting the primary filtrate with alkali metal chloride to remove impurities, filtering, neutralizing, and filtering again to obtain filtrate and ointment; washing and drying the ointment to obtain the aluminum hydroxide(ii) a The filtrate was concentrated to give ammonium chloride. The invention makes the reaction more complete by the reaction of the primary hydrochloric acid and the secondary hydrochloric acid, and simultaneously adds the alkali metal chloride impurity removal process, thereby solving the problem of SiF6 2- 、PO4 3- And SO4 2- The problem is accumulated in the system, and the product quality is further improved. The products with different purities, such as high-purity aluminum fluoride, industrial-grade aluminum hydroxide, ammonium chloride and the like, can be applied to different fields, and the resource recycling value is improved.
In order to further illustrate the present invention, the comprehensive utilization method of the atmospheric condensate provided by the present invention is described in detail with reference to the following examples.
Example 1
The method comprises the following steps: preparation of aluminium fluoride
100g of atmospheric condensate (F53.7%, al 29.22%, siO2 3.72%, SO 4) 2- 1.42%) into 100g/L primary hydrochloric acid solution, preparing slurry with mass concentration of 20%, and reacting at 70 deg.C for 0.5h; and after filtering, adding the primary filter cake into a 100g/L secondary hydrochloric acid solution, preparing slurry with the mass concentration of 20%, reacting for 0.5h at 70 ℃, filtering the reacted slurry, and washing, drying and calcining the obtained secondary filter cake to obtain 78.3g of high-purity aluminum fluoride.
Circularly treating the atmospheric condensate by the primary filtrate and the secondary filtrate until the Al content in the primary filtrate is as follows: 23.65g/L, and then entering the second step to prepare the aluminum hydroxide.
Step two: preparation of aluminium hydroxide
And (3) adding the primary filtrate generated in the first step into a synthesis kettle, adding polyacrylamide and excessive calcium chloride under stirring for reaction, and filtering to remove fluorine silicate, phosphate radical and sulfate radical. Adding ammonia water or ammonia gas and Al into the obtained mother liquor 3+ And NH 3 The molar ratio is 1: stirring and reacting at 3,20 ℃ for 2h, filtering to obtain ointment, washing and drying to obtain 26.80g of aluminum hydroxide. The obtained filtrate is concentrated to obtain ammonium chloride which can be directly sold for external use.
Example 2
The method comprises the following steps: preparation of aluminium fluoride
200g of atmospheric condensate is added into 200g/L of primary hydrochloric acid solution, slurry with the mass concentration of 35% is prepared, and the reaction is carried out for 0.5h at the temperature of 55 ℃; and after filtering, adding the primary filter cake into 200g/L of secondary hydrochloric acid solution, preparing slurry with the mass concentration of 35%, reacting for 0.5h at 55 ℃, filtering the reacted slurry, and washing, drying and calcining the obtained secondary filter cake to obtain 156.5g of high-purity aluminum fluoride.
Circularly treating the atmospheric condensate by the primary filtrate and the secondary filtrate until the Al content in the primary filtrate is as follows: 48.00g/L, and then the step II is carried out to prepare the aluminum hydroxide.
Step two: preparation of aluminium hydroxide
And (3) adding the primary filtrate generated in the first step into a synthesis kettle, adding polyacrylamide and excessive magnesium chloride under stirring for reaction, and filtering to remove fluorine silicate, phosphate radical and sulfate radical. Adding ammonia water or ammonia gas and Al into the obtained mother liquor 3+ And NH 3 The molar ratio is 1:3.05 Stirring and reacting for 1h at 35 ℃, filtering to obtain ointment, washing and drying to obtain 50.8g of aluminum hydroxide. The obtained filtrate is concentrated to obtain ammonium chloride which can be directly sold.
Example 3
The method comprises the following steps: preparation of aluminium fluoride
Adding 150g of atmospheric condensate into 300g/L of primary hydrochloric acid solution, preparing slurry with the mass concentration of 50%, and reacting for 1h at 40 ℃; and after filtering, adding the primary filter cake into 300g/L of secondary hydrochloric acid solution, preparing slurry with the mass concentration of 50%, reacting for 1h at 40 ℃, filtering the reacted slurry, and washing, drying and calcining the obtained secondary filter cake to obtain 117.4g of high-purity aluminum fluoride.
Circularly treating the atmospheric condensate by using the obtained primary filtrate and secondary filtrate until the Al content in the primary filtrate is as follows: 69.00g/L, and then entering the second step to prepare the aluminum hydroxide.
Step two: preparation of aluminium hydroxide
And (3) adding the primary filtrate generated in the step one into a synthesis kettle, adding polyacrylamide and excess barium chloride under stirring for reaction, and filtering to remove fluorine silicate, phosphate radical and sulfate radical. Adding ammonia water or ammonia gas into the obtained mother liquor，Al 3+ And NH 3 The molar ratio is 1:3.05 Stirring and reacting at 50 ℃ for 0.5h, filtering to obtain ointment, washing and drying to obtain 29.4g of aluminum hydroxide. The obtained filtrate is concentrated to obtain ammonium chloride which can be directly sold for external use.
Examples of the experiments
The high-purity aluminum fluoride and industrial aluminum hydroxide products prepared in the patent examples 1-3 are respectively detected, and the detection results are shown in tables 1-2.
TABLE 1 detection results of high-purity aluminum fluoride products obtained in examples 1 to 3
TABLE 2 detection results of the industrial aluminum hydroxide products obtained in examples 1 to 3
As can be seen from the data in tables 1-2, the aluminum fluoride product obtained by the invention has high purity and low impurity content, and the index meets the national standard requirement; the industrial aluminum hydroxide index meets the preparation requirement of dry-method aluminum fluoride.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A comprehensive utilization method of a large gas condensate is characterized by comprising the following steps:
a) Carrying out primary reaction on the atmospheric condensate and primary hydrochloric acid to obtain primary reaction liquid, and filtering to obtain primary filtrate and primary filter cake; the mass percentage of each component in the big gas condensate is as follows: 45-55% of fluorine, 28-31% of aluminum, 1-4% of silicon dioxide and 0.5-2.5% of sulfate radical;
the first-stage filter cake and second-stage hydrochloric acid are subjected to second-stage reaction to obtain second-stage reaction liquid, and second-stage filtrate and second-stage filter cake are obtained through filtration; the atmospheric condensate is formed in the production process of aluminum fluoride; the concentration of the primary hydrochloric acid is 100-300 g/L; the concentration of the secondary hydrochloric acid is 100 g/L-300 g/L;
b) Washing, drying and calcining the secondary filter cake to obtain high-purity aluminum fluoride; the calcination temperature is 400 to 700 ℃, and the calcination time is 1 to 3h;
reacting the primary filtrate with alkaline earth metal chloride and an auxiliary agent to remove impurities, filtering, neutralizing and filtering again to obtain filtrate and ointment; washing and drying the ointment to obtain aluminum hydroxide; concentrating the filtrate to obtain ammonium chloride; the alkaline earth metal chloride is one or more of calcium chloride, magnesium chloride or barium chloride, the adding amount is excessive, and the excessive judgment standard is as follows: the new precipitate is not generated when the catalyst is added; the precipitate is specifically the precipitate of fluorosilicate, sulfate and phosphate; the auxiliary agent is polyacrylamide, and the dosage is 0.05-0.5mg/L.
2. The method of claim 1, wherein the temperature of the primary reaction is 40 ℃ to 70 ℃; the reaction time is 0.5 to 1 hour; the temperature of the secondary reaction is 40-70 ℃; the reaction time is 0.5 to 1 hour.
3. The method as claimed in claim 1, wherein the content of Al in the primary filtrate is (0.23 to 0.24) C HCl g/L, the first-stage filtrate is used for preparing the aluminum hydroxide by the reaction of the step B).
4. The method according to claim 1, characterized in that the neutralization of step B) is in particular with ammonia/ammonia neutralization; wherein Al is 3+ And NH 3 The molar ratio is 1: (3 to 3.05).
5. The process of claim 1, wherein the temperature of the reaction of step B) is 20 ℃ to 50 ℃; the reaction time is 0.5 to 2 hours.
6. The method according to claim 1, wherein the mass concentration of the primary reaction liquid in the step A) is 20-50%; the mass concentration of the secondary reaction liquid is 20-50%.
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Denomination of invention: A comprehensive utilization method of atmospheric condensate Granted publication date: 20230407 Pledgee: Bank of China Limited Sanmenxia Hubin Branch Pledgor: Henan Dongfang Shaoxing Industrial Co.,Ltd. Registration number: Y2024980012021 |