CN114032076B - Process for synthesizing hydrogenated terphenyl heat conduction oil - Google Patents
Process for synthesizing hydrogenated terphenyl heat conduction oil Download PDFInfo
- Publication number
- CN114032076B CN114032076B CN202111610872.6A CN202111610872A CN114032076B CN 114032076 B CN114032076 B CN 114032076B CN 202111610872 A CN202111610872 A CN 202111610872A CN 114032076 B CN114032076 B CN 114032076B
- Authority
- CN
- China
- Prior art keywords
- carrier
- catalyst
- composite oxide
- terphenyl
- molar ratio
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a process for synthesizing hydrogenated terphenyl heat conduction oil, and belongs to the technical field of chemical synthesis. The process comprises biphenyl synthesis, distillation and hydrogenation, wherein pure benzene and a catalyst are used for high-temperature reaction in a reactor in the biphenyl synthesis process, the catalyst comprises a carrier and active components, and the active components account for 10-35% of the mass of the carrier; the carrier is modified active carbon or molecular sieve, and the active ingredient is CuMgAl, cuFeAl, cuFeZn, caMgZn composite oxide. The catalyst adopts a supported catalyst with composite metal oxide as an active component in the terphenyl synthesis stage, so that the selectivity of the terphenyl is improved, the generation of byproducts such as the terphenyl, the pentabiphenyl and the like is reduced, and finally the purity of the hydrogenated terphenyl heat-conducting oil is improved.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a process for synthesizing hydrogenated terphenyl heat conduction oil.
Background
The hydrogenated terphenyl is heat conducting oil with excellent performance, and is a mixture of partially hydrogenated terphenyl isomers obtained by partially hydrogenating mixtures of ortho, meta and para terphenyl in different proportions. Hydrogenated terphenyl has excellent heat stability, oxidation resistance, low vapor pressure and other characteristics.
The production process of hydrogenated terphenyl includes synthesizing terphenyl isomer, and hydrogenating terphenyl to obtain hydrogenated terphenyl product. In the biphenyl synthesis process, in addition to the terphenyl isomer, byproducts such as tetrabiphenyl, pentabiphenyl and the like are generated. In the prior art, all products obtained in the biphenyl synthesis stage are directly subjected to a hydrogenation process, and after hydrogenation, separation and purification are performed through multiple times of distillation, so that the hydrogen consumption is large, and the distillation and separation process is complex. How to improve the selectivity of generating terphenyl in the biphenyl synthesis stage and reduce the generation of byproducts, thereby improving the purity of hydrogenated terphenyl heat-conducting oil is always researched and hoped to break through.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide a process for synthesizing hydrogenated terphenyl heat conduction oil, wherein a supported catalyst with composite metal oxide as an active component is adopted as a catalyst in the terphenyl synthesis stage, so that the selectivity of terphenyl is improved, the generation of byproducts such as terphenyl, pentabiphenyl and the like is reduced, and finally the purity of the hydrogenated terphenyl heat conduction oil is improved.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
The process for synthesizing the hydrogenated terphenyl heat-conducting oil comprises biphenyl synthesis, distillation and hydrogenation, wherein pure benzene and a catalyst are used for high-temperature reaction in a reactor in the biphenyl synthesis process, the catalyst comprises a carrier and active components, and the active components account for 10% -35% of the mass of the carrier; the carrier is modified active carbon or molecular sieve, and the active ingredient is CuMgAl, cuFeAl, cuFeZn, caMgZn composite oxide.
According to the hydrogenated terphenyl heat-conducting oil synthesis process, the molar ratio of Cu to Mg to Al in the CuMgAl composite oxide is 1:0.8-1.5:2, the molar ratio of Cu to Fe to Al in the CuFeAl composite oxide is 1:0.3-1.0:1.2-2.2, the molar ratio of Cu to Fe to Zn in the CuFeZn composite oxide is 1:0.1-0.5:0.6-1.2, and the molar ratio of Ca to Mg to Zn in the CaMgZn composite oxide is 1:2.3-3.8:0.1-0.8.
The preparation process of the catalyst specifically comprises the following steps of:
(1) Weighing corresponding nitrate solution according to the molar ratio of different metals in the composite metal oxide, and preparing a metal salt solution with the concentration of 0.10-0.50 mol/L of mixed solution;
(2) Weighing sodium hydroxide or potassium hydroxide to prepare an alkali solution with the concentration of 0.8-1 mol/L;
(3) Weighing carrier modified active carbon or molecular sieve, placing in deionized water, controlling the temperature at 85-90 ℃, adopting a coprecipitation method, simultaneously dripping the solutions in the step (1) and the step (2), and adding phosphoric acid solution with mass fraction of 10+/-1% to control the pH of the system at 9-10; after the precipitation is completed, aging the reaction solution for 24-48 hours at 70-75 ℃;
(4) Filtering the reaction liquid in the step (3), washing the precipitate with deionized water, drying at 100-105 ℃, calcining at 550-600 ℃ for 1-5h in a muffle furnace, and grinding into particles below 120 meshes to obtain the catalyst.
The preparation of the modified activated carbon in the hydrogenated terphenyl heat-conducting oil synthesis process comprises the following steps: adding the mixture into phosphoric acid solution with the mass fraction of 10+/-1% into 60-80 mesh active carbon particles, and soaking for 4-6h; and then ball milling the mixed material to 100-120 meshes, filtering, washing the solid material to neutrality by deionized water, and drying to constant weight at 100-120 ℃ to obtain the modified activated carbon carrier.
In the process for synthesizing the hydrogenated terphenyl heat conduction oil, the molecular sieve carrier is ZSM-5 or ZSM-11.
The active component of the hydrogenated terphenyl heat conduction oil synthesis process is 20% -28% of the mass of the carrier; the carrier is modified active carbon, and the active ingredient is CuFeZn, caMgZn composite oxide; the mol ratio of Cu, fe and Zn in CuFeZn composite oxide is 1:0.2-0.3:0.8-1.0, and the mol ratio of Ca, mg and Zn in CaMgZn composite oxide is 1:3.0-3.3:0.5-0.8.
The active component of the hydrogenated terphenyl heat conduction oil synthesis process is 23% of the mass of the carrier; the carrier is modified active carbon, and the active ingredient is CuFeZn composite oxide; the molar ratio of Cu, fe and Zn in CuFeZn composite oxide is 1:0.25:0.9.
The beneficial effects are that:
Compared with the prior art, the catalyst adopts the composite metal oxide as the supported catalyst of the active component in the terphenyl synthesis stage, improves the selectivity of the terphenyl, reduces the generation of byproducts such as the terphenyl, the pentabiphenyl and the like, and finally improves the purity of the hydrogenated terphenyl heat-conducting oil.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
The preparation of the CuMgAl composite oxide supported catalyst specifically comprises the following steps:
(1) Weighing corresponding nitrate solution according to the molar ratio of Cu, mg and Al in the composite metal oxide of 1:1:2, and preparing a metal salt solution with the concentration of 0.10 mol/L of mixed solution;
(2) Weighing sodium hydroxide or potassium hydroxide to prepare an alkali solution with the concentration of 0.80 mol/L;
(3) The active component is 28% of the carrier mass, the carrier molecular sieve ZSM-11 is weighed and placed in deionized water, the temperature is controlled at 85 ℃, a coprecipitation method is adopted, meanwhile, the solutions in the step (1) and the step (2) are added dropwise, and the pH of the system is controlled at 9 by adding 10% phosphoric acid solution; after the precipitation is completed, aging the reaction solution for 48 hours at 70 ℃;
(4) Filtering the reaction solution in the step (3), washing the precipitate with deionized water, drying at 100 ℃, calcining at 550 ℃ for 4 hours in a muffle furnace, and grinding into 120-mesh particles to obtain the catalyst.
Mixing pure benzene and the catalyst in a reactor, wherein the dosage of the catalyst is 10 percent of the mass of the pure benzene, and then adding the mixture into an evaporator for evaporation; benzene steam is added into a tubular reactor for reaction; after the reaction, cooling was performed.
The content of the terphenyl is 83.45% by sampling chromatographic analysis.
Example 2
CuFeAl preparation of a composite oxide supported catalyst, specifically:
(1) Weighing corresponding nitrate solution according to the molar ratio of Cu, fe and Al in the composite metal oxide of 1:0.6:1.8, and preparing a metal salt solution with the concentration of 0.10 mol/L of mixed solution;
(2) Weighing sodium hydroxide or potassium hydroxide to prepare an alkali solution with the concentration of 0.80 mol/L;
(3) The active component is 20% of the carrier mass, the carrier molecular sieve ZSM-5 is weighed and placed in deionized water, the temperature is controlled at 85 ℃, a coprecipitation method is adopted, meanwhile, the solutions in the step (1) and the step (2) are added dropwise, and the pH of the system is controlled at 9 by adding 10% phosphoric acid solution; after the precipitation is completed, aging the reaction solution for 48 hours at 70 ℃;
(4) Filtering the reaction solution in the step (3), washing the precipitate with deionized water, drying at 100 ℃, calcining at 550 ℃ for 4 hours in a muffle furnace, and grinding into 120-mesh particles to obtain the catalyst.
Mixing pure benzene and the catalyst in a reactor, wherein the dosage of the catalyst is 15 percent of the mass of the pure benzene, and then adding the mixture into an evaporator for evaporation; benzene steam is added into a tubular reactor for reaction; after the reaction, cooling was performed.
The content of the terphenyl was 90.22% by sample chromatography.
Example 3
CuFeZn preparation of a composite oxide supported catalyst, specifically:
(1) Weighing corresponding nitrate solution according to the mol ratio of Cu, fe and Zn in the composite metal oxide of 1:0.25:0.9, and preparing into metal salt solution with the concentration of 0.10 mol/L of mixed solution;
(2) Weighing sodium hydroxide or potassium hydroxide to prepare an alkali solution with the concentration of 0.80 mol/L;
(3) Adding 10% phosphoric acid solution into 60-80 mesh active carbon particles, and soaking for 4h; then ball milling the mixed material to 100-120 meshes, filtering, washing the solid material to neutrality by deionized water, and drying at 120 ℃ to constant weight to obtain a modified activated carbon carrier;
(4) The active component is 23% of the carrier mass, and the modified active carbon is weighed; placing the carrier in deionized water, controlling the temperature at 85 ℃, adopting a coprecipitation method, simultaneously dripping the solutions in the step (1) and the step (2), and adding a phosphoric acid solution with the mass fraction of 10% to control the pH of the system at 9; after the precipitation is completed, aging the reaction solution for 48 hours at 70 ℃;
(5) Filtering the reaction solution in the step (4), washing the precipitate with deionized water, drying at 100 ℃, calcining at 550 ℃ for 4 hours in a muffle furnace, and grinding into 120-mesh particles to obtain the catalyst.
Mixing pure benzene and the catalyst in a reactor, wherein the dosage of the catalyst is 10 percent of the mass of the pure benzene, and then adding the mixture into an evaporator for evaporation; benzene steam is added into a tubular reactor for reaction; after the reaction, cooling was performed.
Sample chromatographic analysis shows that the content of the terphenyl is 96.31%.
Example 4
CaMgZn preparation of a composite oxide supported catalyst, specifically:
(1) Weighing corresponding nitrate solution according to the mol ratio of Cu, mg and Zn in the composite metal oxide of 1:3.0:0.6, and preparing into metal salt solution with the concentration of 0.10 mol/L of mixed solution;
(2) Weighing sodium hydroxide or potassium hydroxide to prepare an alkali solution with the concentration of 0.80 mol/L;
(3) Adding 10% phosphoric acid solution into 60-80 mesh active carbon particles, and soaking for 6h; then ball milling the mixed material to 100-120 meshes, filtering, washing the solid material to neutrality by deionized water, and drying at 120 ℃ to constant weight to obtain a modified activated carbon carrier;
(4) The active component is 25% of the carrier mass, the carrier is weighed and placed in deionized water, the temperature is controlled at 85 ℃, a coprecipitation method is adopted, meanwhile, the solutions in the step (1) and the step (2) are added dropwise, and the pH of the system is controlled at 9 by adding 10% of phosphoric acid solution; after the precipitation is completed, aging the reaction solution for 48 hours at 70 ℃;
(5) Filtering the reaction solution in the step (4), washing the precipitate with deionized water, drying at 100 ℃, calcining at 550 ℃ for 4 hours in a muffle furnace, and grinding into 120-mesh particles to obtain the catalyst.
Mixing pure benzene and the catalyst in a reactor, wherein the dosage of the catalyst is 15 percent of the mass of the pure benzene, and then adding the mixture into an evaporator for evaporation; benzene steam is added into a tubular reactor for reaction; after the reaction, cooling was performed.
The content of the terphenyl is 94.67% by sampling chromatographic analysis.
Claims (4)
1. The process for synthesizing the hydrogenated terphenyl heat-conducting oil is characterized by comprising biphenyl synthesis, distillation and hydrogenation processes, wherein pure benzene and a catalyst are used for high-temperature reaction in a reactor in the biphenyl synthesis process, the catalyst comprises a carrier and active components, and the active components are 20-28% of the mass of the carrier;
The carrier is modified activated carbon or molecular sieve, and the active ingredient is CuMgAl, cuFeAl, cuFeZn, caMgZn composite oxide;
the molar ratio of Cu, mg and Al in the CuMgAl composite oxide is 1:0.8-1.5:2, the molar ratio of Cu, fe and Al in the CuFeAl composite oxide is 1:0.3-1.0:1.2-2.2, the molar ratio of Cu, fe and Zn in the CuFeZn composite oxide is 1:0.2-0.3:0.8-1.0, and the molar ratio of Ca, mg and Zn in the CaMgZn composite oxide is 1:3.0-3.3:0.5-0.8;
the preparation process of the catalyst specifically comprises the following steps:
(1) Weighing corresponding nitrate solution according to the molar ratio of different metals in the composite metal oxide, and preparing a metal salt solution with the concentration of 0.10-0.50 mol/L of mixed solution;
(2) Weighing sodium hydroxide or potassium hydroxide to prepare an alkali solution with the concentration of 0.8-1 mol/L;
(3) Weighing carrier modified active carbon or molecular sieve, placing in deionized water, controlling the temperature at 85-90 ℃, adopting a coprecipitation method, simultaneously dripping the solutions in the step (1) and the step (2), and adding phosphoric acid solution with mass fraction of 10+/-1% to control the pH of the system at 9-10; after the precipitation is completed, aging the reaction solution for 24-48 hours at 70-75 ℃;
(4) Filtering the reaction liquid in the step (3), washing the precipitate with deionized water, drying at 100-105 ℃, calcining at 550-600 ℃ for 1-5h in a muffle furnace, and grinding into particles below 120 meshes to obtain the catalyst.
2. The process for synthesizing hydrogenated terphenyl heat transfer oil according to claim 1, wherein the modified activated carbon is prepared by: adding the mixture into phosphoric acid solution with the mass fraction of 10+/-1% into 60-80 mesh active carbon particles, and soaking for 4-6h; and then ball milling the mixed material to 100-120 meshes, filtering, washing the solid material to neutrality by deionized water, and drying to constant weight at 100-120 ℃ to obtain the modified activated carbon carrier.
3. The process for synthesizing hydrogenated terphenyl heat conductive oil according to claim 1, wherein the molecular sieve carrier is ZSM-5 or ZSM-11.
4. The process for synthesizing hydrogenated terphenyl heat transfer oil according to claim 1, wherein the active component is 23% of the mass of the carrier; the carrier is modified active carbon, and the active ingredient is CuFeZn composite oxide; the molar ratio of Cu, fe and Zn in CuFeZn composite oxide is 1:0.25:0.9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111610872.6A CN114032076B (en) | 2021-12-27 | 2021-12-27 | Process for synthesizing hydrogenated terphenyl heat conduction oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111610872.6A CN114032076B (en) | 2021-12-27 | 2021-12-27 | Process for synthesizing hydrogenated terphenyl heat conduction oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114032076A CN114032076A (en) | 2022-02-11 |
| CN114032076B true CN114032076B (en) | 2024-06-14 |
Family
ID=80141275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111610872.6A Active CN114032076B (en) | 2021-12-27 | 2021-12-27 | Process for synthesizing hydrogenated terphenyl heat conduction oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114032076B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028403A (en) * | 2011-09-30 | 2013-04-10 | 北京化工大学 | Body type copper-based ester hydrogenation catalyst and preparation method and application thereof |
| CN103804114A (en) * | 2013-12-05 | 2014-05-21 | 安徽奥瑞化工有限公司 | Method for preparing hydrogenated terphenyl |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR707431A (en) * | 1929-12-16 | 1931-07-08 | Ig Farbenindustrie Ag | Process for the production of condensation products |
| JP2011213804A (en) * | 2010-03-31 | 2011-10-27 | Sumitomo Chemical Co Ltd | Preliminary polymerization method, preliminary polymerized catalyst component for addition polymerization, and method for producing addition polymer using the same |
| CN102989521B (en) * | 2012-12-17 | 2015-03-04 | 中国科学院大连化学物理研究所 | Zirconium-containing spinel supported honeycomb monolithic catalyst for selective hydrogenation of benzene and preparation method for same |
| CN107185548B (en) * | 2017-06-07 | 2020-06-16 | 中国石油大学(华东) | Method for preparing cyclohexylbenzene by selective hydrogenation of biphenyl |
| CN109456736A (en) * | 2018-10-19 | 2019-03-12 | 江苏中能化学科技股份有限公司 | A kind of high―temperature nuclei type conduction oil |
| CN111018652A (en) * | 2019-12-15 | 2020-04-17 | 江苏曼拓化学有限公司 | Preparation method of high-purity hydrogenated terphenyl heat conduction oil |
| CN111330582A (en) * | 2020-05-06 | 2020-06-26 | 济南大学 | A kind of preparation method of copper-based catalyst and application thereof |
| CN111482177A (en) * | 2020-05-07 | 2020-08-04 | 江苏新河农用化工有限公司 | Catalyst for preparing hydrogenated terphenyl and preparation method and application thereof |
| CN112108148A (en) * | 2020-09-24 | 2020-12-22 | 华东理工大学 | Supported copper-based catalyst for hydrogen production by methanol steam reforming, and preparation method and application thereof |
| CN112442339B (en) * | 2020-11-05 | 2021-09-07 | 涉县津东经贸有限责任公司 | Preparation method for synthesizing heat conduction oil at high temperature |
| CN113636908A (en) * | 2021-08-13 | 2021-11-12 | 涉县津东经贸有限责任公司 | Terphenyl composition and preparation method thereof |
| CN113750994B (en) * | 2021-10-21 | 2023-12-26 | 西安凯立新材料股份有限公司 | Catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid and preparation method thereof |
-
2021
- 2021-12-27 CN CN202111610872.6A patent/CN114032076B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028403A (en) * | 2011-09-30 | 2013-04-10 | 北京化工大学 | Body type copper-based ester hydrogenation catalyst and preparation method and application thereof |
| CN103804114A (en) * | 2013-12-05 | 2014-05-21 | 安徽奥瑞化工有限公司 | Method for preparing hydrogenated terphenyl |
Non-Patent Citations (1)
| Title |
|---|
| 活性炭负载金属催化剂催化合成三联苯的性能研究;刘俊成等;现代化工;第43卷;188-191、196 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114032076A (en) | 2022-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6037301A (en) | Amorphous alloy catalyst containing boron, its preparation and use | |
| CN88101443A (en) | The preparation method of aromatic hydrocarbon | |
| CN105126845A (en) | Oxalate hydrogenation catalyst for producing ethanol and preparation method of catalyst | |
| CN102407121A (en) | A kind of preparation method of hydrogenation catalyst using X/Ni/Al hydrotalcite as precursor | |
| CN109503388B (en) | Method for co-producing cyclohexylamine and dicyclohexylamine and catalyst system used in method | |
| CN103664524A (en) | Method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid | |
| CN114032076B (en) | Process for synthesizing hydrogenated terphenyl heat conduction oil | |
| CN112237931B (en) | Bulk phase nickel phosphide catalyst, preparation method and application in phenol hydrodeoxygenation | |
| CN110433802B (en) | Hydrogenation catalyst, preparation method thereof and method for preparing saturated aldehyde by hydrogenation of alpha, beta-unsaturated aldehyde by using catalyst | |
| Molchanov et al. | Scientific grounds for the application of mechanochemistry to catalyst preparation | |
| CN101074187B (en) | Production of o-phenylphenol | |
| JP2023022829A (en) | Method for producing azulene compound | |
| CN102020568A (en) | Method for preparing 1,5-diaminonaphthalene and 1,8-diaminonaphthalene | |
| US6051528A (en) | Amorphous alloy catalyst containing phosphorus, its preparation and use | |
| CN101209415B (en) | Catalyst for preparing linalyl acetate by hydrogenation of dehydrogenated linalyl acetate | |
| CN109046405B (en) | Iodine supported catalyst, preparation method and preparation method of all-trans vitamin A acetate | |
| CN115893315B (en) | Preparation method of high-purity hydrogen | |
| CN101579633B (en) | Skeletal copper catalyst and preparation method thereof | |
| CN114870886A (en) | Preparation method and application of catalyst for directly preparing gasoline by carbon dioxide hydrogenation | |
| CN105085167B (en) | Two-section method process for preparing alcohol by oxalic ester hydrogenation | |
| CN115555011A (en) | Auxiliary agent for improving heavy metal pollution resistance of FCC (fluid catalytic cracking) catalyst | |
| CN107866249B (en) | Molybdenum carbide catalyst for preparing nerol and geraniol by hydrogenating citral | |
| CN103408434A (en) | Method for synthesizing aniline by directly oxidizing and aminating benzene by one step | |
| CN114570376B (en) | Catalyst for synthesizing menthone and method for synthesizing menthone | |
| CN115536487B (en) | High-purity low-carbon alkane production process and equipment |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Country or region after: China Address after: 056400 original steel mill, Dongxiang Village, Gengle Town, Shexian County, Handan City, Hebei Province Applicant after: Hebei Jindong Technology Group Co.,Ltd. Address before: 056400 original steel mill, Dongxiang Village, Gengle Town, Shexian County, Handan City, Hebei Province Applicant before: SHEXIAN JINDONG ECONOMIC AND TRADE CO.,LTD. Country or region before: China |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |