CN107224975B - Preparation method of carbon monoxide methanation catalyst without reduction activation - Google Patents

Preparation method of carbon monoxide methanation catalyst without reduction activation Download PDF

Info

Publication number
CN107224975B
CN107224975B CN201610173030.1A CN201610173030A CN107224975B CN 107224975 B CN107224975 B CN 107224975B CN 201610173030 A CN201610173030 A CN 201610173030A CN 107224975 B CN107224975 B CN 107224975B
Authority
CN
China
Prior art keywords
roasting
organic solvent
preparation
catalyst
drying
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
CN201610173030.1A
Other languages
Chinese (zh)
Other versions
CN107224975A (en
Inventor
黄先亮
徐本刚
吴学其
张�杰
吴�琳
朱艳芳
王金利
蔡进
魏士新
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.)
China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
Original Assignee
China Petroleum and Chemical Corp
China Petrochemical Corp
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 China Petroleum and Chemical Corp, China Petrochemical Corp filed Critical China Petroleum and Chemical Corp
Priority to CN201610173030.1A priority Critical patent/CN107224975B/en
Publication of CN107224975A publication Critical patent/CN107224975A/en
Application granted granted Critical
Publication of CN107224975B publication Critical patent/CN107224975B/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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides

Abstract

The invention discloses a preparation method of a carbon monoxide methanation catalyst without reduction and activation, which belongs to the technical field of catalysis and is characterized in that the preparation method of the carbon monoxide methanation catalyst without reduction and activation is characterized in that Al is contained3+,Ni2+Adding the mixed nitrate solution and an alkaline precipitator into water in a concurrent flow manner, and maintaining the pH = 7-8 of the solution; after the neutralization process is finished, the obtained product and aliphatic hydroxy acid are uniformly dispersed in a volatile organic solvent through aging, washing, filtering, drying and roasting in an inert atmosphere, then the organic solvent is removed through drying and roasting in an oxygen-free condition, and the rest solid is formed through sheet beating.

Description

Preparation method of carbon monoxide methanation catalyst without reduction activation
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a carbon monoxide methanation catalyst without reduction activation.
Background
Natural gas is a highly efficient clean energy source. At present, the proportion of natural gas in world primary energy is 24.3%. Because of the shortage of natural gas resources and development amount in China, the proportion of natural gas in primary energy is only about 4 percent, which is far lower than the average level in the world. In recent years, with the successive construction and use of national-level fuel gas transportation projects such as Shanxi gas import Jing and Xiqi Dongyi, the demand of natural gas is explosively increased, the gap between supply and demand of natural gas is larger and larger, and the coal resources in China are relatively abundant.
Methanation catalysts are generally based on Al2O3Supported by a methanation catalyst such as disclosed in patent US 3933833 and highly pure gamma-Al2O3Is used as a carrier and loaded with active components of nickel oxide and cobalt oxide. The patent CN 1043639A discloses a methanation catalyst with Al2O3Is used as carrier, Ni is used as active component, and rare earth metal or alkaline earth metal is used as cocatalyst. In the methanation catalyst disclosed in patent CN1043449A, nickel is used as an active component, rare earth metal and magnesium are used as promoters, and the balance is alumina. The methanation catalysts take alumina as a carrier and an active component is nickel. The nickel being present in the general form Ni2+And the nickel with methanation performance is metallic simple substance nickel. Therefore, the catalyst is subjected to a reduction treatment before the start of the methanation reaction.
Chinese patent CN 1054269 discloses a preparation method of a methanation catalyst for preparing synthesis gas from coal, and the active components of the catalyst are nickel and Al2O3As carrier, 10% H is needed before using the catalyst2/N2And (4) carrying out reduction for 2-6 h by raising the temperature to 250-350 ℃ by a medium temperature program.
The reduction activation process of the nickel-based catalyst before use requires the consumption of H2And often takes a long time, which brings extra energy consumption and inconvenience to the catalyst using process.
Disclosure of Invention
The invention provides a preparation method of a carbon monoxide methanation catalyst without reduction activation. The methanation catalyst prepared by the method has good catalytic activity and stability.
The method is mainly characterized in that after the aliphatic hydroxy acid is introduced in the preparation process of the catalyst and is combusted in an inert atmosphere, gas generated by decomposing the aliphatic hydroxy acid has a pore-forming effect, and CO obtained by decomposition can reduce NiO into metal Ni.
The technical scheme of the invention is as follows: will contain Al3+,Ni2+Adding the mixed nitrate solution and an alkaline precipitator into water in a concurrent flow manner, and maintaining the pH = 7-8 of the solution; after the neutralization process is finished, the obtained product and aliphatic hydroxy acid are uniformly dispersed in a volatile organic solvent through aging, washing, filtering, drying and roasting in an inert atmosphere, then the organic solvent is removed through drying and roasting in an oxygen-free condition, and the rest solid is formed through sheet beating.
Generally, the total amount of Al and Ni in the nitrate solution is 1, wherein the content of Al element is 30-80%, and the content of Ni element is 20-50%.
The mixed nitrate solution also contains Mg2+、La3+、Zr4+、Ce3+And Ga3+The ratio of the total amount of the Al element to the total amount of the Al element is 0.01 to 0.2.
The alkaline precipitant used in the invention is Na2CO3、NaHCO3、K2CO3Or KHCO3An aqueous solution.
The hydroxyl polycarboxylic acid is citric acid or tartaric acid.
The ratio of the using amount of the hydroxyl polycarboxylic acid to the amount of the Al element substance in the product is 0.01-0.2.
The volatile organic solvent is ethanol, acetone or diethyl ether.
The roasting temperature in the inert atmosphere is 350-700 ℃.
The roasting temperature of the organic solvent removing method under the anaerobic condition is 200-400 ℃.
The methanation catalyst prepared by the method has good catalytic activity and stability.
Detailed Description
The present invention will be described in detail with reference to the following examples:
example 1
302.0g Al (NO) was weighed3)3·9H2O、87.8g Ni(NO3)2·3H2Dissolving O in water solution to obtain solution with total salt concentration of 1mol/L, mixing with nitrate solution and 1mol/L Na2CO3Preheating the solutions to 60 ℃, and then adding the solutions into 60 ℃ deionized water in a parallel flow manner, and maintaining the pH = 7-8; aging for 30min, washing the precipitate with deionized water, filtering to obtain filter cake, drying, and roasting at 350 deg.C; weighing 15.0 parts of citric acid, uniformly dispersing the citric acid and the filter cake in 3L of ethanol, stirring at normal temperature for 30min, heating to 60 ℃, distilling and recovering the ethanol, drying the obtained solid, roasting at 200 ℃ for 2h under an anaerobic condition, cooling to room temperature, and tabletting and forming the obtained solid to obtain the catalyst I.
Example 2
150.0g Al (NO) was weighed3)3·9H2O、43.9g Ni(NO3)2·3H2O、5.0g Mg(NO3)2·6H2Dissolving O in water solution to prepare solution with total salt concentration of 1mol/L, mixing nitrate solution and 1mol/L NaHCO3Preheating the solutions to 60 ℃, and then adding the solutions into 60 ℃ deionized water in a parallel flow manner, and maintaining the pH = 7-8; aging for 30min, washing the precipitate with deionized water, filtering to obtain filter cake, drying, and roasting at 700 deg.C; weighing 15.0 of tartaric acid, uniformly dispersing the tartaric acid and the filter cake in 3L of acetone, stirring at normal temperature for 30min, raising the temperature to 60 ℃, distilling and recovering the acetone, drying the obtained solid, roasting at 400 ℃ for 2h under an anaerobic condition, then cooling to room temperature, and tabletting and forming the obtained solid to obtain the catalyst II.
Example 3
302.0g Al (NO) was weighed3)3·9H2O、87.8g Ni(NO3)2·3H2O、5.0g Ce(NO3)3·6H2Dissolving O in water solution to obtain solution with total salt concentration of 1mol/L, mixing nitrate solution and 1mol/L K2CO3After the solutions were all preheated to 60 ℃ and added concurrentlyPutting the mixture into deionized water at 60 ℃ and maintaining the pH = 7-8; aging for 30min, washing the precipitate with deionized water, filtering to obtain filter cake, drying, and roasting at 700 deg.C; weighing 15.0 of citric acid, uniformly dispersing the citric acid and the filter cake in 3L of diethyl ether, stirring at normal temperature for 30min, raising the temperature to 60 ℃, distilling and recovering the diethyl ether, drying the obtained solid, roasting at 300 ℃ for 2h under an anaerobic condition, then reducing the temperature to 40 ℃, switching nitrogen into oxygen nitrogen with the oxygen volume percentage of 2.5%, maintaining for 30min, then reducing the temperature to room temperature, and tabletting and forming the obtained solid to obtain the catalyst III.
Example 4
302.0g Al (NO) was weighed3)3·9H2O、87.8g Ni(NO3)2·3H2O、5.0g La(NO3)3·6H2Dissolving O in water solution to obtain solution with total salt concentration of 1mol/L, mixing nitrate solution and 1mol/L KHO3Preheating the solutions to 60 ℃, and then adding the solutions into 60 ℃ deionized water in a parallel flow manner, and maintaining the pH = 7-8; aging for 30min, washing the precipitate with deionized water, filtering to obtain filter cake, drying, and roasting at 700 deg.C; weighing 15.0 parts of citric acid, uniformly dispersing the citric acid and the filter cake in 3L of ethanol, stirring at normal temperature for 30min, raising the temperature to 60 ℃, distilling and recovering the ethanol, drying the obtained solid, roasting at 350 ℃ for 2h under an anaerobic condition, cooling to room temperature, and tabletting and forming the obtained solid to obtain the catalyst IV.
Example 5
302.0g Al (NO) was weighed3)3·9H2O、87.8g Ni(NO3)2·3H2O、5.0g Zr(NO3)3·5H2Dissolving O in water solution to obtain solution with total salt concentration of 1mol/L, mixing with nitrate solution and 1mol/L Na2CO3Preheating the solutions to 60 ℃, and then adding the solutions into 60 ℃ deionized water in a parallel flow manner, and maintaining the pH = 7-8; aging for 30min, washing the precipitate with deionized water, filtering to obtain filter cake, drying, and roasting at 700 deg.C; weighing 15.0 citric acid, uniformly dispersing in 3L ethanol together with the filter cake, stirring at room temperature for 30min, heating to 60 deg.C, distilling and recovering ethanol to obtain solid, drying, and optionally adding citric acidRoasting at 350 ℃ for 2h under an oxygen condition, then cooling to 40 ℃, switching nitrogen into oxygen-nitrogen with the oxygen volume percentage content of 1%, maintaining for 30min, then cooling to room temperature, and tabletting and molding the obtained solid to obtain the catalyst V.
The methanation catalysts I, II, III, IV and V are respectively filled in a fixed bed tubular reactor, and the reaction conditions are as follows: pressure 3.0MPa, gas composition H239.12， CO 7.18，CO21.30，N2The air speed is 5000-30000 h-1After the reaction is carried out for 500 hours at the temperature of 600 ℃, the activity of the catalyst is kept good, wherein the conversion rate of CO is close to 100 percent, the selectivity of methane is close to 100 percent, the mechanical strength of the disassembled catalyst is still high, and the surface of the catalyst is not deposited with carbon.
Catalyst and process for preparing same Airspeed Total CO conversion (%) Methane selectivity (%)
Ⅰ 10000 99.3 99.5
Ⅱ 10000 99.5 99.0
Ⅲ 10000 99.8 98.9
Ⅳ 10000 99.1 99.1
Ⅴ 10000 99.7 99.3

Claims (8)

1. A preparation method of a carbon monoxide methanation catalyst without reduction activation is characterized in that Al is contained3+,Ni2+Adding the mixed nitrate solution and an alkaline precipitator into water in a concurrent flow manner, and maintaining the pH = 7-8 of the solution; after the neutralization process is finished, aging, washing, filtering, drying, roasting in an inert atmosphere, uniformly dispersing the obtained product and aliphatic hydroxy acid in a volatile organic solvent, drying, roasting under an oxygen-free condition to remove the organic solvent, and tabletting and forming the residual solid;
the total amount of Al and Ni in the nitrate solution is 1, wherein the content of Al element is 30-80%, and the content of Ni element is 20-50%;
the roasting temperature under the anaerobic condition for removing the organic solvent is 200-400 ℃.
2. The method of claim 1, wherein the mixed nitrate solution further comprises Mg2+、La3+、Zr4+、Ce3+And Ga3+The ratio of the total amount of the Al element to the total amount of the Al element is 0.01 to 0.2.
3. Preparation of the catalyst according to claim 1The method is characterized in that the alkaline precipitant is Na2CO3、NaHCO3、K2CO3Or KHCO3An aqueous solution.
4. The method of claim 1, wherein the aliphatic hydroxy acid is a hydroxy polycarboxylic acid.
5. The method for preparing the catalyst according to claim 4, wherein the hydroxy polycarboxylic acid is citric acid or tartaric acid.
6. The method for preparing a catalyst according to claim 4 or 5, wherein the ratio of the amount of the hydroxy polycarboxylic acid to the amount of the Al element in the product is 0.01 to 0.2.
7. The method for preparing the catalyst according to claim 1, wherein the volatile organic solvent is ethanol, acetone or diethyl ether.
8. The method for preparing the catalyst according to claim 1, wherein the calcination temperature is 350 ℃ to 700 ℃ in an inert atmosphere.
CN201610173030.1A 2016-03-24 2016-03-24 Preparation method of carbon monoxide methanation catalyst without reduction activation Active CN107224975B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610173030.1A CN107224975B (en) 2016-03-24 2016-03-24 Preparation method of carbon monoxide methanation catalyst without reduction activation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610173030.1A CN107224975B (en) 2016-03-24 2016-03-24 Preparation method of carbon monoxide methanation catalyst without reduction activation

Publications (2)

Publication Number Publication Date
CN107224975A CN107224975A (en) 2017-10-03
CN107224975B true CN107224975B (en) 2020-04-14

Family

ID=59932619

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610173030.1A Active CN107224975B (en) 2016-03-24 2016-03-24 Preparation method of carbon monoxide methanation catalyst without reduction activation

Country Status (1)

Country Link
CN (1) CN107224975B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103480375A (en) * 2013-09-29 2014-01-01 福州大学 Carbon monoxide methanating catalyst and preparation method thereof
CN104275185A (en) * 2013-07-12 2015-01-14 中国石油化工股份有限公司 Preparation method of copper-based hydrogenation catalyst without reduction activation
CN105797785A (en) * 2016-04-15 2016-07-27 西安向阳航天材料股份有限公司 Pre-reduction type high-temperature methanation catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104275185A (en) * 2013-07-12 2015-01-14 中国石油化工股份有限公司 Preparation method of copper-based hydrogenation catalyst without reduction activation
CN103480375A (en) * 2013-09-29 2014-01-01 福州大学 Carbon monoxide methanating catalyst and preparation method thereof
CN105797785A (en) * 2016-04-15 2016-07-27 西安向阳航天材料股份有限公司 Pre-reduction type high-temperature methanation catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN107224975A (en) 2017-10-03

Similar Documents

Publication Publication Date Title
CN101920201B (en) Method for preparing cobalt-based Fischer-Tropsch synthesis catalyst
CN110975938A (en) Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
CN110152663A (en) It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application
CN114702434A (en) Continuous synthesis method of tetramethyl piperidinol
CN105944719B (en) It is a kind of for catalyst of crotonaldehyde selective hydrogenation crotyl alcohol preparation and preparation method thereof
CN109851473B (en) Method for preparing 1,3-propylene glycol by hydrogenolysis of glycerol solution
CN107224975B (en) Preparation method of carbon monoxide methanation catalyst without reduction activation
CN105727972B (en) A kind of method for preparing catalyst for synthesizing gas by reforming methane with co 2
CN114160143B (en) CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof
CN107224980B (en) Preparation method of carbon dioxide methanation catalyst without reduction activation
CN102911693A (en) Fischer-Tropsch synthesis method by employing mixed catalyst
CN115837275A (en) Perovskite type high-entropy oxide and preparation method and application thereof
CN112275304B (en) Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof
CN102441388B (en) Preparation method for cobalt-base Fischer Tropsch synthetic catalyst with high stability
CN114054023B (en) Preparation method and application of alloy monoatomic catalyst
CN113145127A (en) Cu catalyst for hydrogen production by methanol steam reforming and preparation method and application thereof
CN113398918A (en) Catalyst for synthesizing methyl mercaptan and preparation and application methods thereof
KR101988370B1 (en) Catalysts for methanation of carbon dioxide and the manufacturing method of the same
CN107020102B (en) A kind of nickel-chrome acid Mg catalyst and preparation method thereof and the application in ethyl alcohol is prepared in glycerol
CN105727977B (en) A kind of synthesis gas methanation substitutes the method for preparing catalyst of natural gas
CN114192142B (en) Catalyst for dinonyl phenol hydrogenation and preparation method thereof
CN105642305B (en) A kind of method for preparing catalyst for hydrogen production from methane vapor reforming
CN107486210A (en) A kind of catalyst for acetic acid one-step method ethanol and preparation method thereof
CN105727974B (en) A kind of method for preparing catalyst for synthesis gas methanation
CN105727969B (en) A kind of preparation method of synthesis gas methanation 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
CP01 Change in the name or title of a patent holder

Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699

Patentee after: China Petroleum & Chemical Corp.

Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd.

Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699

Patentee before: China Petroleum & Chemical Corp.

Patentee before: Nanhua Group Research Institute

CP01 Change in the name or title of a patent holder