CN109675582B - Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof - Google Patents

Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof Download PDF

Info

Publication number
CN109675582B
CN109675582B CN201811588792.3A CN201811588792A CN109675582B CN 109675582 B CN109675582 B CN 109675582B CN 201811588792 A CN201811588792 A CN 201811588792A CN 109675582 B CN109675582 B CN 109675582B
Authority
CN
China
Prior art keywords
component
catalyst
hydrogen chloride
preparing chlorine
oxidation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811588792.3A
Other languages
Chinese (zh)
Other versions
CN109675582A (en
Inventor
惠丰
吕剑
杨建明
袁俊
余秦伟
赵锋伟
石坚
李亚妮
张前
梅苏宁
王为强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Modern Chemistry Research Institute
Original Assignee
Xian Modern Chemistry Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Modern Chemistry Research Institute filed Critical Xian Modern Chemistry Research Institute
Priority to CN201811588792.3A priority Critical patent/CN109675582B/en
Publication of CN109675582A publication Critical patent/CN109675582A/en
Application granted granted Critical
Publication of CN109675582B publication Critical patent/CN109675582B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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 invention discloses a catalyst for preparing chlorine by oxidizing hydrogen chloride and a preparation method thereof. The invention relates to a catalyst roasting precursor for preparing chlorine by hydrogen chloride oxidation, which comprises the following components in percentage by mass: and (2) component A: 80% -82%; and (B) component: 8% -10%; and (3) component C: 8 percent; and (3) component D: 2 percent. Wherein the component A is gamma-alumina and the component B is copper Cu2+Chromium Cr3+Ruthenium Ru3+Component C is zirconium oxychloride and component D is silicon oxide. The preparation method of the catalyst comprises the following steps: firstly, preparing an aqueous solution of nitrate or chloride of one or more of copper, chromium and ruthenium; adding gamma-alumina powder and regulating with ammonia water to neutrality; adding zirconium oxychloride into the solution, heating, stirring, refluxing, adjusting to alkalescence by using ammonia water, filtering and drying; and finally, mixing the solid material with silicon oxide, forming, and roasting at 500 ℃ to obtain the hydrogen chloride oxidation catalyst. The catalyst is mainly applied to the reaction process of preparing chlorine by catalytic oxidation of hydrogen chloride and oxygen.

Description

Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a catalyst for preparing chlorine by hydrogen chloride oxidation with long service life and without loss of active components and a preparation method thereof.
Background
Chlorine is an important chemical basic raw material and is widely applied to the fields of polyurethane, organic silicon, chlorinated hydrocarbon, epoxy resin, chlorinated rubber, chlorinated high polymer and the like.
If the byproduct hydrogen chloride can be directly prepared into chlorine, the closed-loop circulation of chlorine can be realized, thereby fundamentally solving two bottlenecks at the upstream and the downstream of the chlorine consumption industry. The chlorine is produced by oxidizing hydrogen chloride with oxygen or air
Figure BDA0001919742460000011
A good approach. Its stoichiometric formula can be represented as:
currently, there are three types of industrial processes that can achieve this process, namely catalytic oxidation, cyclic oxidation, and oxidative electrolysis. The typical representative of the cyclic oxidation method is DuPont, sulfuric acid is used as a cyclic oxidation medium, and nitric acid is used as a catalyst, so that the equipment investment is very large, the operation is complex, the operation cost is high, and the flexibility is poor. The oxidation electrolysis method can well relieve the problem of unbalance of chlor-alkali in the chlor-alkali industry at present, but the power consumption still exceeds 1700 kWh/ton, the problem of high power consumption in chlorine production is not fundamentally solved, and compared with the ionic membrane electrolysis, the method for oxidizing and electrolyzing hydrochloric acid has more complex equipment and no advantages in economy and operability. This technology is currently held by only bayer companies, but is itself being more actively promoted outward and introduced into catalytic oxidation technology of japanese sumitomo.
Although the equipment investment of the hydrogen chloride catalytic oxidation technology is also larger, the hydrogen chloride catalytic oxidation technology has the greatest advantages of low power consumption and environmental protection, and the hydrogen chloride oxidation catalyst is the core technology of the catalytic oxidation method.
In the reported hydrogen chloride oxidation catalyst, metals such as copper, chromium, ruthenium and the like are mainly used as active components, and the active components exist in the form of oxides in the catalyst. The catalyst (CN1475434A) prepared by sumitomo chemical corporation using a ruthenium compound had good reactivity, but had problems of loss of active components and reduction of reactivity after a long-time reaction. In the reaction process, the active component can be in a strong oxidation state and can be subjected to chemical reaction with hydrogen chloride or impurities (such as sulfur and the like) in a reaction system, and the formed metal chloride is dissolved in water in a reaction material, so that the active component is lost; since the reaction is mostly carried out at high temperature, the active components of the catalyst have the problem of direct gasification loss at high temperature (CN87104744A, CN1475434A, CN101125297A, CN202236397A and CN102000583A), thereby causing the reduction of the activity of the catalyst and the shortening of the catalytic life.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the background technology and provide a long-life hydrogen chloride oxidation catalyst without loss of active components and a preparation method thereof. The catalyst is mainly applied to the reaction process of preparing chlorine by catalytic oxidation of hydrogen chloride and oxygen.
The main technical concept of the invention is as follows:
zirconium oxychloride can be hydrolyzed under the alkalescent condition to generate zirconium hydroxide, and the zirconium hydroxide with weak acidity is formed after high-temperature roasting. The compound is easy to have strong interaction with catalytic active components such as copper, chromium, ruthenium and the like at high temperature, and the zirconium oxide has stable chemical property and is difficult to lose in the hydrogen chloride oxidation reaction environment, so that the zirconium oxide is adopted to coat the active components, the acidity and alkalinity of the catalyst are adjusted, the metal loss caused by the chemical reaction of the active components and hydrogen chloride is remarkably reduced, and the catalytic reaction activity and the stability of the catalytic reaction activity are remarkably enhanced.
The catalyst for preparing chlorine by oxidizing hydrogen chloride is characterized in that a catalyst roasting precursor comprises the following components in percentage by mass:
and (2) component A: 80% -82%;
and (B) component: 8% -10%;
and (3) component C: 8 percent;
and (3) component D: 2 percent.
Wherein the component A is gamma-alumina and the component B is copper Cu2+Chromium Cr3+Ruthenium Ru3+Component C is zirconium oxychloride and component D is silicon oxide.
The catalyst for preparing chlorine by oxidizing hydrogen chloride is prepared by the following method:
a) nitrate or chloride containing one or more of copper, chromium and ruthenium is prepared into aqueous solution with the concentration of 1 mol/L;
b) b, adding the dried gamma-alumina powder into the aqueous solution obtained in the step a according to the mass ratio of the component A to the component B of 8-10:1, and adjusting the mixture to be neutral by using ammonia water under the stirring condition;
c) b, adding zirconium oxychloride into the solution obtained in the step b according to the mass ratio of the component C to the component A of 1:10, heating, stirring and refluxing for 8 hours, adjusting to alkalescence by using ammonia water, continuing stirring for 2 hours, filtering, washing and drying;
d) and c, uniformly mixing the solid material obtained in the step c with silicon oxide, granulating, pressing and forming, and roasting the catalyst precursor at the temperature of 500 ℃ for 12 hours to obtain the catalyst for preparing chlorine by oxidizing hydrogen chloride.
The invention has the following advantages:
the catalyst for preparing chlorine by hydrogen chloride oxidation has the advantages of no loss of active components of the catalyst and long catalytic life. After the reaction is carried out for 1000 hours, the loss rate of the active components of the catalyst is lower than 0.5%, the reaction activity is not obviously reduced, and the catalytic life is obviously prolonged compared with that of the catalyst prepared by the prior art (referring to the CN1475434A, the loss rate of the active components of the catalyst is 7.6% after the reaction is carried out for 1000 hours, and the reaction activity is reduced by 23% compared with that of the catalyst prepared in the initial reaction period).
Detailed Description
In the invention, the activity evaluation device of the catalyst for preparing chlorine by oxidizing hydrogen chloride is a common fixed bed tubular reactor, and the size of the reactor is
Figure BDA0001919742460000031
The particles are
Figure BDA0001919742460000032
Is charged into a reactor, heated to the reaction temperature, the gas is passed through a pressure-reducing valve andfeeding after a flowmeter, and sampling and analyzing after stable reaction.
Catalyst activity evaluation experimental conditions: the reaction temperature is 300-.
The outlet of the oxidation reactor is mainly a mixture of chlorine, oxygen, hydrogen chloride and water vapor, the conversion rate of the oxidation reaction can be calculated by analyzing the chlorine content and calculating the generation amount of the chlorine within a certain time interval, so as to investigate the activity of the catalyst and the influence rule of the oxidation reaction condition.
The amount of chlorine having oxidizing property is measured based on the principle that chlorine is easily absorbed by a potassium iodide solution or the reducing property of iodide ions. When the gas sample is introduced into potassium iodide solution, chlorine is absorbed and iodine is displaced out, and the separated iodine is titrated with standard sodium thiosulfate solution, namely iodometry (or indirect iodometry or titration iodometry).
The titration process used starch as an indicator. Since HCl is very soluble in water, it is in Cl2The HCl is absorbed by the KI solution at the same time. After titration with sodium thiosulfate solution is complete, the amount of HCl can be titrated with a sodium hydroxide standard solution, which titration assay uses phenolphthalein as an indicator.
The specific operation steps are as follows: after the system is stably operated, preparing 100ml of 20% KI solution at regular intervals, switching an outlet three-way valve of an oxidation reactor, introducing the mixed gas after reaction into a constant volume (100ml) potassium iodide solution, absorbing for 3 minutes, transferring the absorbing solution into a conical flask after absorption, titrating by using 0.1mol/l sodium thiosulfate standard solution, and using starch as an indicator; then, unreacted HC1 was titrated with 0.1mol/l sodium hydroxide standard solution using phenolphthalein as an indicator.
Conversion of HCl:
Conv％＝b/(b+d)*100％
b represents the titration overhead Na2S2O3Ml of solution
d represents the number of ml of NaOH solution consumed for titration, and ml
X fluorescence element analysis is carried out on catalyst samples with different reaction times, and the method for calculating the loss rate of active components after the catalyst is used for 1000 hours is as follows:
active component loss rate (active component content before catalyst use-active component content after catalyst use)/active component content before catalyst use
The present invention will be described in further detail with reference to examples.
Example 1
The invention relates to a catalyst for preparing chlorine by hydrogen chloride oxidation, which comprises the following roasting precursors in percentage by mass:
and (2) component A: 80 percent;
and (B) component: 10 percent;
and (3) component C: 8 percent;
and (3) component D: 2 percent.
Wherein the component A is gamma-alumina, the component B is copper nitrate and ruthenium chloride, the component C is zirconium oxychloride, and the component D is silicon oxide.
The catalyst for preparing chlorine by oxidizing hydrogen chloride is prepared by the following method:
a) preparing an aqueous solution with the concentration of 1mol/L from copper nitrate and ruthenium chloride in a mass ratio of 1: 2;
b) b, adding the dried gamma-alumina powder into the aqueous solution obtained in the step a according to the mass ratio of the component A to the component B of 8:1, and adjusting the mixture to be neutral by using ammonia water under the stirring condition;
c) b, adding zirconium oxychloride into the solution obtained in the step b according to the mass ratio of the component C to the component A of 1:10, heating, stirring and refluxing for 8 hours, adjusting to alkalescence by using ammonia water, continuing stirring for 2 hours, filtering, washing and drying;
d) and c, uniformly mixing the solid material obtained in the step c with silicon oxide, granulating, pressing and forming, and roasting the catalyst precursor for 12 hours at the temperature of 500 ℃ to obtain the catalyst for preparing chlorine by hydrogen chloride oxidation, wherein the label is A.
Example 2
The invention relates to a catalyst for preparing chlorine by hydrogen chloride oxidation, which comprises the following roasting precursors in percentage by mass:
and (2) component A: 82%;
and (B) component: 8 percent;
and (3) component C: 8 percent;
and (3) component D: 2 percent.
Wherein the component A is gamma-alumina, the component B is chromium nitrate and ruthenium chloride, the component C is zirconium oxychloride, and the component D is silicon oxide.
The preparation of the catalyst for preparing chlorine by hydrogen chloride oxidation is the same as that in example 1, except that the mass ratio of chromium nitrate to aluminum chloride in the step a is 1:1, and the mass ratio of the component A to the component B in the step B is 10:1, so that the catalyst for preparing chlorine by hydrogen chloride oxidation is obtained and is marked as B.
Example 3
The invention relates to a catalyst for preparing chlorine by hydrogen chloride oxidation, which comprises the following roasting precursors in percentage by mass:
and (2) component A: 82%;
and (B) component: 9 percent;
and (3) component C: 8 percent;
and (3) component D: 2 percent.
Wherein the component A is gamma-alumina, the component B is ruthenium chloride, the component C is zirconium oxychloride, and the component D is silicon oxide.
The preparation of the catalyst for preparing chlorine by hydrogen chloride oxidation is the same as that in example 1, except that the step a is a ruthenium chloride solution, and the mass ratio of the component A to the component B in the step B is 9:1, so that the catalyst for preparing chlorine by hydrogen chloride oxidation is obtained and is marked as C.
The application of the hydrogen chloride oxidation catalyst of the invention comprises the following steps:
the catalyst A, B, C for preparing chlorine by hydrogen chloride oxidation prepared in the example 1-3 is filled into a fixed bed tubular reactor, the filling amount of the catalyst is 30mL, the reaction temperature is 360 ℃, the molar ratio/volume ratio of hydrogen chloride to oxygen is 1:2, the reaction pressure is normal pressure, and the feeding rate of hydrogen chloride is 100 mL/min. Sampling and analyzing after 24h of stable reaction and 1000h of reaction, and calculating the conversion rate. And (3) carrying out X fluorescence element analysis on the catalyst samples before use and after 1000h of reaction, and calculating the loss rate of the active component according to the analysis result. The results are shown in the following table:
TABLE 1 catalyst conversion of hydrogen chloride to chlorine
Figure BDA0001919742460000051

Claims (1)

1. The catalyst for preparing chlorine by oxidizing hydrogen chloride is characterized in that a catalyst calcination precursor comprises the following components in percentage by mass:
and (2) component A: 80% -82%;
and (B) component: 8% -10%;
and (3) component C: 8 percent;
and (3) component D: 2 percent.
Wherein the component A is gamma-alumina and the component B is copper Cu2+Chromium Cr3+Ruthenium Ru3+One or more of (1), component C is zirconium oxychloride, and component D is silicon oxide;
the preparation method of the catalyst for preparing chlorine by hydrogen chloride oxidation comprises the following steps:
a) nitrate or chloride containing the component B is prepared into an aqueous solution with the concentration of 1 mol/L;
b) b, adding the dried component A into the aqueous solution obtained in the step a according to the mass ratio of the nitrate or chloride of the component A to the nitrate or chloride of the component B of 8-10:1, and adjusting the dried component A to be neutral by using ammonia water under stirring;
c) adding the component C into the solution obtained in the step b according to the mass ratio of the component C to the component A of 1:10, heating, stirring and refluxing for 8 hours, adjusting to alkalescence by using ammonia water, continuously stirring for 2 hours, filtering, washing and drying to obtain a solid material;
d) and c) uniformly mixing the solid material obtained in the step c) with the component D, granulating, pressing and forming to obtain a catalyst precursor, and roasting at the temperature of 500 ℃ for 12 hours to obtain the catalyst for preparing chlorine by oxidizing hydrogen chloride.
CN201811588792.3A 2018-12-25 2018-12-25 Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof Active CN109675582B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811588792.3A CN109675582B (en) 2018-12-25 2018-12-25 Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811588792.3A CN109675582B (en) 2018-12-25 2018-12-25 Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109675582A CN109675582A (en) 2019-04-26
CN109675582B true CN109675582B (en) 2021-11-23

Family

ID=66189315

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811588792.3A Active CN109675582B (en) 2018-12-25 2018-12-25 Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109675582B (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069616C (en) * 1997-12-19 2001-08-15 化学工业部天津化工研究院 Method for preparing zirconium oxide-aluminum oxide composite and its use
AU2001286831A1 (en) * 2000-08-25 2002-03-04 Apyron Technologies, Inc. Adsorbent and/or catalyst compounds promoted with halide ions and methods of making and using thereof
DE102007033113A1 (en) * 2007-07-13 2009-01-15 Bayer Technology Services Gmbh Stable, high activity hydrogen chloride oxidation catalyst, for producing chlorine, comprises active component supported on carrier based on uranium compound
JP5642706B2 (en) * 2008-12-30 2014-12-17 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Ruthenium and nickel containing catalysts for hydrogen chloride oxidation.
CN104923239A (en) * 2015-05-29 2015-09-23 华东理工大学 Copper-based catalyst for preparing chlorine gas by catalyzing and oxidizing hydrogen chloride as well as preparation method and application thereof
CN107952436B (en) * 2016-10-14 2019-12-10 中国石油化工股份有限公司 Copper-zirconium-based catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method and application thereof
CN106861707B (en) * 2017-02-09 2019-08-27 西安近代化学研究所 A kind of preparation method of preparing chlorine by oxidizing hydrogen chloride catalyst
CN106902848B (en) * 2017-02-09 2019-06-28 西安近代化学研究所 A kind of hydrogen chloride reforming catalyst
CN108928803B (en) * 2017-05-27 2022-03-04 中国石油化工股份有限公司 Method for producing chlorine by oxidizing hydrogen chloride

Also Published As

Publication number Publication date
CN109675582A (en) 2019-04-26

Similar Documents

Publication Publication Date Title
Kato et al. Reduction of nitric oxide with ammonia on iron oxide-titanium oxide catalyst
JP5624221B2 (en) Catalyst for preparing chlorine by oxidation of hydrogen chloride and process for its preparation
CN102266784B (en) Preparation method for and application of novel load type composite metal catalyst
CN111013614B (en) Catalyst carrier and catalyst for preparing chlorine by oxidizing hydrogen chloride, and preparation method and application thereof
BR112015022805A2 (en) process for oxidation of ammonia with oxygen, and installation for oxidation of ammonia
CN101362080B (en) Active carbon loading ruthenium ammonia synthesis catalyst and preparation method thereof
CN106861707B (en) A kind of preparation method of preparing chlorine by oxidizing hydrogen chloride catalyst
CN103626240A (en) Method for preparing ruthenium trichloride with low-concentration complicated ruthenium-containing waste liquid
WO2023123753A1 (en) Method for catalytic synthesis of accelerator cbs by using ionic liquid protective agent
CN106861714B (en) A kind of catalyst of hydrogen chloride conversion preparing chlorine gas
CN103626222B (en) A kind of preparation method of micron order tin dioxide powder
CN109675582B (en) Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof
CN104549542B (en) Carrier, carbonyl sulfide hydrolysis catalyst based on carrier and preparation method of carbonyl sulfide hydrolysis catalyst
CN110721719A (en) Preparation method and application of bismuth and nitrogen co-doped carbon material
CN106560239B (en) A kind of catalyst and its preparation method and application of catalytic chlorination hydroxide
WO2018145344A1 (en) Hydrogen chloride conversion catalyst
CN109806881A (en) A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol
CN113929058B (en) Catalyst carrier for preparing chlorine by catalytic oxidation of fluorine-containing HCl gas, and preparation method and application thereof
KR100685658B1 (en) Copper ferrite catalyst and decomposition of sulfur trioxide using the same
CN106824231B (en) A kind of noble metal catalyst and preparation method thereof for acetylene hydrochlorination synthesis vinyl chloride thereof
JP5746539B2 (en) Ammonia decomposition catalyst, method for producing the catalyst, ammonia decomposition method and hydrogen production method using the catalyst
CN112675834B (en) Preparation method of uranium-based catalyst, catalyst prepared by preparation method and application of catalyst in preparation of chlorine gas by hydrogen chloride oxidation
CN101773777A (en) Method for removing hydrogen phosphide by wet catalytic air oxidation
CN106890666B (en) A kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas
CN102794187A (en) Au-Co-Cu catalyst used in synthesis of vinyl chloride by hydrochlorination of acetylene and preparation method for Au-Co-Cu catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant