CN116618069A - Preparation method and application of catalyst for catalytic oxidation of fluorine-containing hydrogen chloride - Google Patents
Preparation method and application of catalyst for catalytic oxidation of fluorine-containing hydrogen chloride Download PDFInfo
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- CN116618069A CN116618069A CN202310907039.0A CN202310907039A CN116618069A CN 116618069 A CN116618069 A CN 116618069A CN 202310907039 A CN202310907039 A CN 202310907039A CN 116618069 A CN116618069 A CN 116618069A
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- catalyst
- hydrogen chloride
- fluorine
- containing hydrogen
- catalytic oxidation
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 86
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 47
- 239000011737 fluorine Substances 0.000 title claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 45
- 230000003647 oxidation Effects 0.000 title claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000011259 mixed solution Substances 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 19
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 10
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims description 51
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 49
- 229910052801 chlorine Inorganic materials 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 238000009495 sugar coating Methods 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- -1 phosphorus compound Chemical class 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 150000002909 rare earth metal compounds Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 241000219793 Trifolium Species 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000010953 base metal Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 16
- 238000005303 weighing Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000001103 potassium chloride Substances 0.000 description 8
- 235000011164 potassium chloride Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 150000001879 copper Chemical class 0.000 description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 150000003017 phosphorus Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002603 lanthanum Chemical class 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 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
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940059864 chlorine containing product ectoparasiticides Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- 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
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application relates to the technical field of catalyst preparation, and particularly discloses a preparation method and application of a catalyst for catalytic oxidation of fluorine-containing hydrogen chloride. According to the application, copper element, alkali metal element, rare earth metal element and phosphorus element are sequentially dissolved in a mixed solution, the mixed solution is added into a carrier in batches, and the catalyst for catalyzing and oxidizing fluorine-containing hydrogen chloride is obtained through a natural drying mode. The catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride realizes high catalytic activity of the catalyst at a lower reaction temperature, and the hydrogen chloride conversion rate can reach 94.37% at a reaction temperature of 340 ℃; in addition, magnesium fluoride is used as a carrier, so that the magnesium fluoride can resist hydrogen fluoride corrosion, and base metals such as copper, rare earth metals and the like are used for replacing noble metals, so that the cost is saved.
Description
Technical Field
The application belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a catalyst for fluorine-containing hydrogen chloride catalytic oxidation.
Background
Chlorine is an important chemical basic raw material for industries such as metallurgy, pharmacy, synthetic materials, leather making and the like. With the increasing demand of industry users for chlorine-containing products, the chlorine-alkali industry is solely developed to supplement the deficiency of chlorine supply, which is unfavorable for the balance of consumption of chlorine alkali. Therefore, searching for new chlorine sources is a breaking strategy.
Hydrogen chloride is one of the basic chemical raw materials and is widely used in the fields of pharmacy, dyes, chemical industry and the like. In many processes using chlorine as a raw material, hydrogen chloride is by-produced, and the demand for chlorine is increasing, and the amount of hydrogen chloride by-produced is also increasing. At present, the byproduct hydrogen chloride in industrial treatment is mainly absorbed by water to be prepared into cheap hydrochloric acid for sale, but the byproduct hydrogen chloride generally contains more impurities, especially contains more organic impurities, so that the quality of the hydrochloric acid prepared by water absorption is lower, the transportation cost is increased, in addition, the current market demand of the hydrochloric acid is very limited, and the treatment of the byproduct hydrogen chloride is further limited. If the byproduct hydrogen chloride is converted into chlorine, not only can the waste of byproduct hydrogen chloride resources be solved, but also the closed cycle utilization of the chlorine resources can be realized, and the method is the most effective method for treating and recycling the byproduct hydrogen chloride.
Currently, the methods for preparing chlorine by using hydrogen chloride mainly comprise a direct oxidation method, an electrolytic method and a catalytic oxidation method. The catalytic oxidation method for preparing chlorine by using hydrogen chloride and oxygen as raw materials has the advantages of simple operation, low energy consumption, no side reaction, low equipment cost and the like, and is an optimal way for treating byproduct hydrogen chloride and realizing chlorine resource utilization. The method comprises the following steps:
2HCl+1/2O 2 →Cl 2 +H 2 O-57.7kJ/mol。
the reaction of preparing chlorine by hydrogen chloride catalytic oxidation belongs to reversible exothermic reaction, and although the reaction rate can be increased by increasing the reaction temperature, the equilibrium conversion rate of hydrogen chloride can be reduced. Therefore, the development of a catalyst with high activity at low temperature is a technical key to achieve efficient conversion of hydrogen chloride into chlorine. Since copper-based catalysts were used in the catalytic oxidation of hydrogen chloride to produce chlorine, iron-based, chromium-based, and other transition metal catalysts have been developed in succession, and in recent years, highly active ruthenium-based (CN 111013614 a), cerium-based, and composite metal oxide catalysts have been developed (Acs Catalysis, 2013, 3 (5): 1034-1046). Although these catalysts have excellent application effects in the catalytic oxidation of hydrogen chloride to produce chlorine, there are few applications in the catalytic oxidation of fluorine-containing hydrogen chloride to produce chlorine, not only because of the strong corrosiveness of the fluoride but also because of the good stability of the fluoride in hydrogen chloride, and the difficulty in complete removal from hydrogen chloride, even though the fluoride can be removed from hydrogen chloride, is very energy-consuming. For this reason, chinese patent CN101722019a discloses a ruthenium-based metal oxide catalyst for preparing chlorine by catalytic oxidation of fluorine-containing hydrogen chloride, which, although solving the problem of catalyst deactivation, has a hydrogen chloride conversion rate of less than 10%; chinese patent CN111013614a discloses an aluminum-containing catalyst support and ruthenium oxide catalyst supported thereon, which have high hydrogen chloride conversion rate and low space-time yield even though the conversion rate is high, in the case of filling a large amount of catalyst. Therefore, for the aspect that the catalyst with high activity and fluoride corrosion resistance is applied to the preparation of chlorine by the catalytic oxidation of fluorine-containing hydrogen chloride, a large blank is still left in China.
Disclosure of Invention
Aiming at the defects or shortcomings in the background art, the application provides a preparation method and application of a catalyst for fluorine-containing hydrogen chloride catalytic oxidation, which has high activity, low cost, long service life and hydrogen fluoride corrosion resistance.
In order to achieve the above purpose, the application adopts the following technical scheme:
the preparation method of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride comprises the following specific steps:
(1) Sequentially dissolving an active component copper element, an alkali metal element, a rare earth metal element and a phosphorus element in a solvent to obtain a mixed solution;
(2) Adding the mixed solution into the carrier in batches, wherein the addition amount of each mixed solution is 20-25wt% of the total mass of the mixed solution until the active component solution is completely added, so as to obtain the impregnated carrier;
(3) Sealing the impregnated carrier and drying under natural conditions;
(4) And then roasting for 6-8 hours at the temperature of 350-440 ℃ to obtain the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride.
Preferably, the solvent in step (1) is water.
Preferably, in the step (2), the total time of soaking the carrier in the mixed solution is 15-60 minutes;
specifically, in the step (2), the adding method of the mixed solution is as follows:
(a) Throwing the carrier into a sugar coating machine;
(b) Adding 20-25wt% of mixed solution into a sugar coating machine, and stirring until the mixed solution is completely absorbed;
(c) Repeating the step (b) until the mixed solution is completely added to obtain the impregnated carrier.
Preferably, the drying mode in the step (3) is that the drying mode is placed for 15-24 hours under natural conditions, and compared with other drying modes, the drying mode under natural conditions is more prone to completely absorbing the active components on the carrier, and the phenomenon that the active component salt falls off in a large amount does not occur.
The catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride comprises the following active components based on the total weight of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride: 2 to 24wt%, preferably 5 to 20wt%, more preferably 5 to 15wt% of copper element; 0.1 to 12wt%, preferably 1 to 10wt%, more preferably 2 to 6wt% of an alkali metal element; 0.5 to 25wt%, preferably 2 to 20wt%, more preferably 5 to 20wt% of one or more rare earth metal elements; 0.1 to 3wt%, preferably 0.2 to 2.5wt%, more preferably 0.5 to 2wt% of an element selected from phosphorus; 60 to 90wt% of a carrier, preferably 60 to 85wt% of a carrier; the total weight of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride refers to the weight of the carrier plus the active components.
Wherein the alkali metal element is one of lithium, sodium, potassium and cesium, and preferably sodium or potassium.
Wherein the rare earth metal element is one or more of lanthanoid elements, preferably one or more of lanthanum, cerium, praseodymium, neodymium and samarium.
The support is preferably magnesium fluoride.
The shape of the magnesium fluoride is one of a sphere, a pentadentate sphere, a clover and a Raschig ring, and is preferably a sphere or a pentadentate sphere.
The copper element is selected from soluble salts of copper, namely one of copper chloride, copper sulfate, copper nitrate, copper acetate or copper carbonate, preferably copper chloride or copper nitrate;
the alkali metal element is from an alkali metal compound, and the alkali metal compound is one of chloride, nitrate, acetate or carbonate in lithium, sodium, potassium and cesium, preferably sodium or potassium chloride or nitrate;
the rare earth element is from rare earth metal compound, the rare earth metal compound is one or more of nitrate or chloride of lanthanum, cerium, praseodymium, neodymium and samarium, preferably one or more of nitrate or chloride of lanthanum, samarium and neodymium;
the phosphorus element is derived from a phosphorus compound which is one of a chloride, nitrate, acetate or carbonate of phosphorus, preferably a chloride or nitrate of phosphorus.
The application of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride comprises the following specific processes: the fluorine-containing hydrogen chloride gas and oxygen respectively enter the top of the reactor after the flow rates are controlled by a mass flow controller, and enter a catalyst bed layer for reaction after being preheated to obtain the mixed gas containing chlorine.
The catalyst bed layer is provided with the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride.
The reactor is a fixed tubular reactor, and the size is as follows: the phi 600mm is multiplied by 60mm, an upper section heating furnace, a middle section heating furnace and a lower section heating furnace are arranged outside the reactor, and the temperature difference in the reaction area is +/-2 ℃.
Wherein the volume fraction of hydrogen fluoride in the fluorine-containing hydrogen chloride gas is 0.2-5%;
wherein the molar ratio of the fluorine-containing hydrogen chloride gas to the oxygen is (1-4): (1-2);
wherein the reaction temperature of the fluorine-containing hydrogen chloride and the oxygen is 320-400 ℃, and is preferably 320-380 ℃; the reaction pressure is 1 to 4atm, preferably 1 to 2atm;
wherein the fluorine-containing hydrogen chloride is catalyzed and oxidized to obtain a mixed gas containing chlorine, and the components and the volume fractions thereof are as follows: 85-95% of chlorine, 0.2-5% of hydrogen fluoride and 1-14% of hydrogen chloride;
the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride has the characteristics of simple preparation process, and the metal salts adopted by the active components are all base metals, so that the cost is low. The preparation method of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride is simple, the catalyst does not need to be dried after impregnation, the preparation cost of the catalyst is saved, and the prepared catalyst can effectively improve the conversion rate of hydrogen chloride under a larger hydrogen chloride airspeed.
The technical scheme of the application has the following advantages:
(1) The catalyst for the fluorine-containing hydrogen chloride catalytic oxidation provided by the application realizes high catalytic activity of the catalyst at a lower reaction temperature by adjusting the active component, the impregnation mode of the active component and the drying mode, and the hydrogen chloride conversion rate can reach 94.37% at the reaction temperature of 340 ℃; the high catalytic activity and the high conversion rate under the low temperature condition greatly reduce the energy consumption of industrial production and improve the service life of the catalyst.
(2) The catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride provided by the application takes magnesium fluoride as a carrier and can resist the corrosion of hydrogen fluoride.
(3) The application adopts base metals such as copper, rare earth metal and the like to replace noble metals, thereby saving the cost.
Drawings
FIG. 1 is an SEM image of a catalyst for catalytic oxidation of fluorine-containing hydrogen chloride prepared in example 1.
Detailed Description
The following examples are provided for a better understanding of the present application and are not limited to the preferred embodiments described herein, but are not intended to limit the scope and breadth of the present application. The procedures, conditions, experimental methods, etc. for carrying out the present application are common knowledge and common knowledge in the art, except for the following specific matters, and the present application is not limited in particular. The reagents or apparatus used were conventional reagents or apparatus commercially available without the manufacturer's knowledge.
All embodiments operate according to the operating steps of the above technical solutions.
The method for testing the conversion rate of hydrogen chloride comprises the following steps:
(1) Principle of detection
Cl 2 + 2KI = 2KCl + I 2 ；
I 2 + 2Na 2 S 2 O 3 = 2NaI + Na 2 S 4 O 6 ；
HCl + NaOH = NaCl + H 2 O；
(2) 1.0mol/L sodium thiosulfate (Na 2 S 2 O 3 ) Preparation of standard solution
158.12g of anhydrous Na is accurately weighed 2 S 2 O 3 Dissolving in distilled water immediately boiled and cooled, adding Na 2 CO 3 Constant volume in a 1L brown volumetric flask to obtain 1.0mol/L Na 2 S 2 O 3 The solution is stored in a sealed dark place;
(3) Preparation of 1.0mol/L NaOH standard solution
Accurately weighing 40.00g of NaOH, dissolving in distilled water, fixing the volume in a 1L volumetric flask to obtain 1.0mol/L NaOH solution, and sealing and preserving;
(4) KI solution configuration at 1.708mol/L
Weighing 283.46g of KI, dissolving in distilled water, fixing the volume in a 1L brown volumetric flask to obtain a KI solution with the concentration of 1.708mol/L, and preserving in a sealed dark place;
(5) The specific operation steps are as follows: after the reaction system is stable, preparing a part of KI solution every other day, taking out 100mL for standby, introducing the reacted chlorine-containing gas mixture into the standby 100mL of KI solution, and absorbing for 2min; the sample bottle after absorbing the mixed gas is firstly treated with 1mol/L Na 2 S 2 O 3 Titrating a standard solution, and taking starch as an indicator; then, continuing to titrate by using 1mol/L NaOH standard solution, and taking phenolphthalein as an indicator;
HCl conversion = V b /(V b +V d )×100%；
Wherein V is b Na indicating titration consumption 2 S 2 O 3 Amount of standard solution, mL;
V d the amount of NaOH standard solution consumed by titration is indicated as mL.
Example 1:
(1) Respectively weigh 47.72kg of CuCl 2 •2H 2 O、18.60kg KCl、38.96kg LaCl 3 •nH 2 O、34.4kg SmCl 3 And 1.72kg PCl 3 Sequentially dissolved in 121m 3 To obtain a mixed solution of copper element, alkali metal element, rare earth metal element and phosphorus element.
(2) Weighing 250kg of spherical magnesium fluoride carrier, placing the spherical magnesium fluoride carrier in a sugar coating machine, then adding the mixed solution into the sugar coating machine, and stirring until the added mixed solution is completely absorbed; the addition amount of the mixed solution is 20wt% of the total mass of the mixed solution;
(3) Repeating the step (2) until the active component solution is completely absorbed, so as to obtain an impregnated carrier;
(4) And taking out the impregnated carrier, sealing and placing the carrier for 20 hours under natural conditions, and finally placing the carrier in a muffle furnace at 400 ℃ for roasting for 7 hours, and cooling the carrier to obtain the catalyst for catalyzing and oxidizing fluorine-containing hydrogen chloride.
Wherein, the soaking time required in the steps (2) and (3) is 30 minutes.
SEM diagram of the prepared catalyst for catalyzing and oxidizing fluorine-containing hydrogen chloride is shown in figure 1.
The prepared catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride is filled into a fixed bed reactor, the reactor is heated by using a three-stage furnace to control the temperature, oxygen and hydrogen chloride containing 2 percent (volume fraction) of hydrogen fluoride are introduced after the catalyst is preheated and stabilized, the flow rate of the fluorine-containing hydrogen chloride is 2000L/min, the flow rate of the oxygen is 1000L/min, the reaction temperature is 370 ℃, and the reaction pressure is 1.5atm. After 150 hours of reaction, the chlorine yield is 94.37%, after 500 hours of reaction, the chlorine yield is 93.86%, and the catalyst has good stability and high activity.
Example 2:
weighing 250kg of spherical magnesium fluoride carrier, placing into a sugar coating machine, and weighing 47.72kg of CuCl respectively 2 •2H 2 O、18.60kg KCl、38.96kg LaCl 3 •nH 2 O and 1.72kg PCl 3 Dissolved in 121m 3 The obtained mixed solution of copper salt, potassium salt, lanthanum salt and phosphorus salt is added into a sugar coating machine in batches, the addition amount of the mixed solution in each batch is 25 weight percent of the total mass of the mixed solution, and the soaking time of the carrier in the mixed solution is 30 minutes. And taking out the impregnated carrier, sealing and placing the carrier for 20 hours under natural conditions, and finally, placing the impregnated carrier in a muffle furnace at 400 ℃ for roasting for 7 hours, and cooling to obtain the required catalyst. Under the reaction conditions of example 1, the chlorine yield after 150 hours of reaction is 90.13%, the chlorine yield after 500 hours of reaction is 90.19%, and the catalyst has good stability.
As can be seen from examples 1 and 2: the addition of the rare earth samarium element can greatly reduce the loss of copper element and obviously improve the activity of the catalyst.
Example 3:
weighing 250kg of spherical carrier, placing into sugar coating machine, and weighing 42.60kg of CuCl respectively 2 •2H 2 O、14.20kg KCl、28.40kg LaCl 3 •nH 2 O、28.40kg SmCl 3 And 1.28kg PCl 3 Dissolved in 105m 3 Adding the obtained mixed solution of copper salt, potassium salt, rare earth metal salt and phosphorus salt into a sugar coating machine in batches, wherein the addition amount of the mixed solution in each batch is 20wt% of the total mass of the mixed solution; the immersion time of the support in the mixed solution was 30 minutes in total. And taking out the impregnated carrier, sealing and placing the carrier for 20 hours under natural conditions, and finally, placing the carrier in a muffle furnace at 400 ℃ for roasting for 7 hours, and cooling to obtain the required catalyst. Under the reaction conditions of example 1, the chlorine yield after 150 hours of reaction was 89.31%, the chlorine yield after 500 hours of reaction was 88.99%, and the catalyst had good activity.
Comparative example 1:
weighing 250kg of spherical carrier, placing into sugar coating machine, and weighing 42.60kg of CuCl respectively 2 •2H 2 O、14.20kg KCl、28.40kg LaCl 3 •nH 2 O、28.40kg SmCl 3 Dissolving in waterSolution to 105m 3 Adding the obtained mixed solution of copper salt, potassium salt and rare earth metal salt into a sugar coating machine in batches, wherein the addition amount of the mixed solution in each batch is 20wt% of the total mass of the mixed solution; the time for immersing the support in the mixed solution was 30 minutes in total. And taking out the impregnated carrier, sealing and placing the carrier for 20 hours under natural conditions, and finally, placing the carrier in a muffle furnace at 400 ℃ for roasting for 7 hours, and cooling to obtain the required catalyst. Under the reaction conditions of example 1, the chlorine yield after 150 hours of reaction is 87.64%, the chlorine yield after 500 hours of reaction is 87.55%, and the catalyst has better stability.
As can be seen from example 3 and comparative example 1: the addition of phosphorus can improve the activity of the catalyst to a certain extent.
Example 4:
weighing 250kg of spherical carrier, placing into sugar coating machine, and weighing 47.72kg of CuCl respectively 2 •2H 2 O、18.60kg KCl、38.96kg LaCl 3 •nH 2 O、34.4kg SmCl 3 And 1.72kg PCl 3 Dissolved in 124m 3 The obtained mixed solution of copper salt, potassium salt and lanthanum salt is added into a sugar coating machine in batches, the addition amount of the mixed solution in each batch is 20wt% of the total mass of the mixed solution, and the soaking time of the carrier in the mixed solution is 30 minutes. And taking out the impregnated carrier, sealing and placing the carrier for 20 hours under natural conditions, and finally, placing the carrier in a muffle furnace at 380 ℃ for roasting for 8 hours, and cooling to obtain the required catalyst. Under the reaction conditions of example 1, the chlorine yield after 150 hours of reaction was 94.15%, the chlorine yield after 500 hours of reaction was 93.87%, and the catalyst had excellent activity.
Example 5:
weighing 250kg of spherical carrier, placing into sugar coating machine, and weighing 47.72kg of CuCl respectively 2 •2H 2 O、18.60kg KCl、38.96kg LaCl 3 •nH 2 O、34.4kg SmCl 3 And 1.72kg PCl 3 Dissolved in 124m 3 Adding the obtained mixed solution of copper salt, potassium salt and lanthanum salt into sugar coating machine in batches, and mixing in each batchThe addition amount of the solution is 20wt% of the total mass of the mixed solution; the time for immersing the support in the mixed solution was 30 minutes in total. And taking out the impregnated carrier, sealing and placing the carrier for 20 hours under natural conditions, and finally, placing the carrier in a muffle furnace at 410 ℃ for roasting for 6.5 hours, and cooling to obtain the required catalyst. Under the reaction conditions of example 1, the chlorine yield after 150 hours of reaction was 92.46%, and the chlorine yield after 500 hours of reaction was 92.08%, and the catalyst had excellent stability.
Comparative example 2:
the comparative example used a calcination time of 5 hours at 480℃and the remaining preparation components and methods were the same as in example 4.
Under the reaction conditions of example 1, the chlorine yield was 85.62% after 150 hours of reaction and 84.29% after 500 hours of reaction.
As can be seen from examples 4, 5 and comparative example 2: the catalyst obtained by slightly lower roasting temperature and longer roasting time has higher activity.
Comparative example 3:
this comparative example will weigh 47.72kg of CuCl separately 2 •2H 2 O、18.60kg KCl、38.96kg LaCl 3 •nH 2 O、34.4kg SmCl 3 And 1.72kg PCl 3 Dissolving in 121m according to the addition sequence of phosphorus element, copper element, alkali metal element and rare earth metal 3 To obtain a mixed solution of copper element, alkali metal element, rare earth metal element and phosphorus element. The comparative example was conducted by adjusting the addition sequence of the copper element, the alkali metal element, the rare earth metal element and the phosphorus element to be phosphorus element, copper element, alkali metal element and rare earth metal, and the other preparation components and methods were the same as in example 1.
Under the reaction conditions of example 1, the chlorine yield after 150 hours was 87.92%, and the chlorine yield after 500 hours was 87.24%.
As can be seen from example 1 and comparative example 3: the phosphorus salt is dissolved first and then other active metal salts are dissolved, so that the phosphorus salt is difficult to dissolve out, and the active components loaded on the surface of the carrier are not as much as the added amount, so that the activity of the catalyst is low. Thus, the order in which the active ingredients are dissolved in water is also important.
Comparative example 4:
in this comparative example, copper element, alkali metal element, rare earth metal element and phosphorus element were dissolved in 30.25m 3 After the water in (a) is treated, a copper element solution, an alkali metal element solution, a rare earth element solution and a phosphorus element solution are respectively obtained, all the copper element solution is added into a sugar coating machine at one time until the copper element solution is completely absorbed, then the alkali metal element solution, the rare earth element solution and the phosphorus element solution are respectively added into a carrier at one time according to the sequence, and the rest components and the method are the same as in the embodiment 1.
Under the reaction conditions of example 1, the chlorine yield was 76.40% after 150 hours of reaction and 74.33% after 500 hours of reaction.
The chlorine yield of the present application is greatly reduced compared to example 1, probably because: the active components added at one time can lead the active components which are added later to drop the active components which are impregnated on the carrier, and further lead the load of the active components to be reduced.
Comparative example 5:
in this comparative example, a mixed solution of copper element, alkali metal element, rare earth metal element, and phosphorus element was added to a carrier solvent at one time, and the other preparation components and methods were the same as in example 1.
Under the reaction conditions of example 1, the chlorine yield was 88.69% after 150 hours of reaction and 87.95% after 500 hours of reaction.
The chlorine yield of the present application is greatly reduced compared to example 1, probably because: the active components on the surface of the catalyst are not uniformly distributed on the carrier, some of the active components loaded on the carrier are more easy to fall off, some of the active components loaded on the carrier are less, and the conversion rate of HCl is not high. The uniformly mixed solution is added to the carrier for a plurality of times in a small amount, so that the active components can be uniformly loaded on the carrier to the greatest extent, and the conversion rate of the catalyst to HCl is high.
Comparative example 6:
the impregnated carrier prepared in example 1 was dried in an oven at 110 ℃ for 7 hours, then placed in a muffle furnace at 400 ℃ for roasting for 7 hours, and cooled to obtain the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride.
Under the reaction conditions of example 1, the chlorine yield after 150 hours of reaction was 91.56%, and the chlorine yield after 500 hours of reaction was 91.42%.
The chlorine yield of the present application is slightly reduced compared to example 1, probably because: a carrier that is slowly impregnated under natural conditions is more likely to allow the active component to be fully impregnated into the pores of the carrier than a carrier that is dried in an oven.
Comparative example 7:
in this comparative example, the carrier was added to a mixed solution of copper element, alkali metal element, rare earth metal element, and phosphorus element at one time, and the other preparation components and methods were the same as in example 1.
Under the reaction conditions of example 1, the chlorine yield was 88.62% after 150 hours of reaction and 88.36% after 500 hours of reaction.
The chlorine yield of the present application was greatly reduced compared to example 1, for reasons consistent with comparative example 5.
While the foregoing is directed to the preferred embodiments of the present application, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present application, and such modifications and adaptations are intended to be comprehended within the scope of the present application.
Claims (10)
1. The preparation method of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride is characterized by comprising the following specific steps:
(1) Sequentially dissolving an active component copper element, an alkali metal element, a rare earth metal element and a phosphorus element in a solvent to obtain a mixed solution;
(2) Adding the mixed solution into the carrier in batches, wherein the addition amount of each mixed solution is 20-25wt% of the total mass of the mixed solution until the active component solution is completely added, so as to obtain the impregnated carrier;
(3) Sealing the impregnated carrier and drying under natural conditions;
(4) And then roasting for 6-8 hours at the temperature of 350-440 ℃ to obtain the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride.
2. The method for preparing a catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride according to claim 1,
in the step (2), the adding method of the mixed solution comprises the following steps:
(a) Throwing the carrier into a sugar coating machine;
(b) Adding 20-25wt% of mixed solution into a sugar coating machine, and stirring until the mixed solution is completely absorbed;
(c) Repeating the step (b) until the mixed solution is completely added to obtain the impregnated carrier.
3. The method for preparing a catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride according to claim 1,
in the step (2), the total time of soaking the carrier in the mixed solution is 15-60 minutes.
4. The method for preparing a catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride according to claim 1,
the drying mode in the step (3) is that the drying is carried out for 15-24 hours under natural conditions.
5. The method for preparing a catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride according to claim 1,
the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride comprises the following active components based on the total weight of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride: 2-24wt% of copper element; 0.1-12 wt% of an alkali metal element; 0.5-25 wt% of rare earth metal element; 0.1-3wt% of phosphorus element; 60-90 wt% of a carrier;
wherein the total weight of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride refers to the weight of the carrier plus the active components.
6. The method for preparing a catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride according to claim 1,
the alkali metal element is one of lithium, sodium, potassium and cesium;
the rare earth metal element is one or more of lanthanoid elements;
the support is preferably magnesium fluoride.
7. The method for preparing a catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride according to claim 6,
the shape of the magnesium fluoride is one of a ball shape, a five-tooth ball shape, a clover shape, a four-leaf grass shape and a Raschig ring shape.
8. The method for preparing a catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride according to claim 1,
the copper element is from soluble salt of copper, and the soluble salt of copper is one of copper chloride, copper sulfate, copper nitrate, copper acetate or copper carbonate;
the alkali metal element is from an alkali metal compound, and the alkali metal compound is one of chloride, nitrate, acetate or carbonate of lithium, sodium, potassium and cesium;
the rare earth element is from rare earth metal compound, which is one or more of nitrate or chloride of lanthanum, cerium, praseodymium, neodymium and samarium;
the phosphorus element is from a phosphorus compound, and the phosphorus compound is one of chloride, nitrate, acetate or carbonate of phosphorus.
9. The use of the catalyst for catalytic oxidation of fluorine-containing hydrogen chloride according to any one of claims 1 to 8 in the preparation of chlorine.
10. The use of the catalyst for the catalytic oxidation of fluorine-containing hydrogen chloride in the preparation of chlorine according to claim 9, wherein the specific process comprises:
the fluorine-containing hydrogen chloride gas and oxygen respectively enter the top of the reactor after the flow rates are controlled by a mass flow controller, and enter a catalyst bed layer for reaction after being preheated to obtain the mixed gas containing chlorine.
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