CN102247876B - Method for preparing ethylene with acetylene selective catalytic hydrogenation - Google Patents
Method for preparing ethylene with acetylene selective catalytic hydrogenation Download PDFInfo
- Publication number
- CN102247876B CN102247876B CN2010101766147A CN201010176614A CN102247876B CN 102247876 B CN102247876 B CN 102247876B CN 2010101766147 A CN2010101766147 A CN 2010101766147A CN 201010176614 A CN201010176614 A CN 201010176614A CN 102247876 B CN102247876 B CN 102247876B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetylene
- molybdenum
- mop
- hydrogenation
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing ethylene with acetylene selective catalytic hydrogenation, using molybdenum phosphide (MoP) as a catalyst. For pure phase of MoP, the selectivity of acetylene can be still steady at more than 76% under normal pressure at the temperature of 200-240 DEG C with an H2 to C2H2 ratio of 4-8 at the space velocity of 36000 h<-1> with the conversion rate of acetylene selective hydrogenation of 99.5 %; and for the supported MoP catalyst (20-35 wt% MoP/SiO2), the selectivity of acetylene is still more than 70 % with the conversion rate of acetylene selective hydrogenation of 99.8 %. Compared with traditional noble metal catalyst (e.g. palladium catalyst), the MoP catalyst has high catalytic hydrogenation activity and high selectivity, and has the advantages of simple preparation method, low cost and the like.
Description
Technical field
The present invention relates to the method for preparing ethylene with acetylene selective catalytic hydrogenation, with molybdenum phosphide catalyst, also above-mentioned catalyst is used for the method that selective catalytic hydrogenation is removed a small amount of acetylene of ethene.
Background technology
The process of industrial preparation ethene relates generally to hydrocarbon cracking ethene processed and preparing ethylene with acetylene selective catalytic hydrogenation, still contains the acetylene of trace in the ethylene gas that these processes make.The existence of trace acetylene can make that ethylene rolymerization catalyst is poisoning and inactivation makes the polymer performance variation that finally makes, therefore must be wherein before ethylene raw material gas carries out polymerisation micro-acetylene remove.From present result of study, by selective catalytic hydrogenation, acetylene optionally being hydroconverted into ethene is the most feasible and valuable method.Yet the acetylene hydrogenation reaction belongs to cascade reaction (C
2H
2→ C
2H
4→ C
2H
6), the ethene that generates in hydrogenation process very easily further hydrogenation generates ethane, thereby cause ethylene selectivity can be along with the increase of conversion of alkyne sharply to reduce, remove the Pd catalyst of ability also so (US 20090326288 even have high trace acetylene; US 20040074220; CN 1317367; CN 1657513; CN 1151908; A.Sarkany, A.Beck, L.Guczi.Appl.Catal.A, 2003,253:283; W.Huang, J.R.McCormick, J.G.Chen.J.Catal., 2007,246:40).In at present numerous research, mainly still concentrate on the research to the Pd catalyst system, and Ag, Co, Cu, Cr, alkali metal, metal oxide and lead acetate are the known auxiliary agent that can improve performance of Pd catalyst (US 7247760B2; W.Huang, W.Pyrz, J.G.Chen.Appl.Catal.A, 2007,333:254; J.H.Kang, E.W.Shin, S.H.Moon.Catal.Today, 2000,63:183; Y.Jin, A.K.Datye, J.Blackson, J.Catal., 2001,203:2001).From present achievement in research, high catalyst cost is to limit one of further key factor of using of this technology, and is still rare to the research of non-precious metal catalyst.Therefore, the selective and activity that how to reduce the catalyst cost, improves catalyst is the emphasis of this research always, develop a kind of inexpensive, catalyst that have high activity and high selectivity is also imperative.For this reason, both at home and abroad the research worker is still trying to explore selective catalytic hydrogenation and is removing the new catalyst system of Trace Acetylene in Ethylene.
Transition metal phosphide is another catalyst material with good Hydrogenation after nitride and carbide, has good hydrogen-involved reaction performance in catalytic hydrogenation reaction, obtained result (D.C.Phillips preferably in recent years in the research of the hydrodenitrogeneration of fuel oil and desulfurization, S.J.Sawhill, R.Self, M.E.Bussell.J.Catal., 2002,207:266; F.Sun, Z.Jiang, C.Li.J.Catal., 2004,228:298).This seminar has carried out the research that is used for acetonitrile gas phase hydrogenation ethylamine compounds processed take the phosphatization molybdenum as catalyst first, and has obtained a series of significant achievements.The application that molybdenum phosphide catalyst is used for other hydrogenation reaction system seldom, therefore further deeply develop the application as novel hydrogenation catalyst phosphatization molybdenum, no matter this is to the development of molybdenum phosphide catalyst or the exploitation of hydrogenation catalyst reaction, all have important academic significance and using value, the phosphatization molybdenum be yet there are no report for the research that the acetylene selective catalytic hydrogenation prepares ethene.
Summary of the invention
The object of the present invention is to provide a kind of molybdenum phosphide catalyst that uses to prepare the method for ethene at the acetylene selective catalytic hydrogenation; Method for preparing catalyst is simple, the catalyst cost is low, acetylene hydrogenation is active high, still keeps higher ethylene selectivity in high conversion of alkyne situation.
For achieving the above object, technical solution of the present invention realizes by following steps:
A kind of method of preparing ethylene with acetylene selective catalytic hydrogenation is take the phosphatization molybdenum as catalyst.
Molybdenum phosphorus mol ratio 0.9-1.1 in described phosphatization molybdenum.
Reaction pressure is normal pressure, and reaction temperature is 200～240 ℃, H
2/ C
2H
2Mol ratio=4～8, air speed are 33,000～38,000h
-1
Described molybdenum phosphide catalyst is pure phase phosphatization molybdenum or with SiO
2Support type phosphatization molybdenum for carrier.
Described SiO
2In the support type molybdenum phosphide catalyst, the weight percentage of phosphatization molybdenum is 20～35wt%.
Pure phase MoP prepares by the high-temperature hydrogen temperature programmed reduction, and support type phosphatization molybdenum is that active component Mo, P raw material are loaded on SiO by wet infusion process
2On carrier, then make by the high-temperature hydrogen temperature programmed reduction.
In technique scheme, in the precursor of pure phase MoP, the molar ratio example of molybdenum, phosphorus is 0.90～1.10.Be 200～240 ℃, H in normal pressure, reaction temperature
2/ C
2H
2=4～8 o'clock, in the situation that conversion of alkyne reaches 99.5%, selectively still the keeping more than 76% of ethene.
The molybdenum of support type MoP catalyst, phosphorus ingredient proportion are that 1, MoP load capacity is 20～35wt%.Be 200～240 ℃, H in normal pressure, reaction temperature
2/ C
2H
2=4～8 o'clock, in the situation that conversion of alkyne reaches 99.8% ethylene selectivity that still can keep more than 70%.
Catalyst composition of the present invention raw material used is: molybdenum element is selected from ammonium molybdate or molybdenum trioxide.P elements is selected from ammonium phosphate salt.
The preparation method of catalyst involved in the present invention is: mix after at first the molybdate compound of certain mol proportion and ammonium phosphate salt being dissolved in distilled water, with the liquid evaporate to dryness, 120 ℃ of dryings 10～24 hours were in 450～650 ℃ of roastings 2～8 hours.Then, the phosphatization molybdenum presoma after roasting is carried out the multi-stage procedure heating reduction under nitrogen atmosphere.Reducing condition is: rises to 250～400 ℃ take heating rate as 2～10 ℃/min from room temperature, take heating rate as 0.5～2 ℃/min, rises to 550～900 ℃ from 250～400 ℃, and outlet temperature insulation 2～4 hours.After reaction finished, under room temperature, the passivating gas take oxygen concentration as 0.5～1.5% carried out passivation to product, obtains pure phase MoP catalyst.
The preparation process of support type phosphatization molybdenum and pure phase phosphatization molybdenum is similar, and different is, is after 1 molybdate compound and ammonium phosphate salt dissolving mix, to be immersed in SiO with mol ratio
2On carrier.
Compare with known technology, the present invention has the following advantages:
This method is used for preparing ethylene with acetylene selective catalytic hydrogenation with base metal MoP catalyst, at high reaction velocity (36,000h
-1) time, for MoP and MoP/SiO
2Catalyst acetylene hydrogenation conversion ratio and hydrogenation products ethylene selectivity can reach respectively more than 99% and 70%.With traditional noble metal catalyst relatively (as palladium catalyst), molybdenum phosphide catalyst has preparation method simple, cheap and catalytic hydrogenation activity and selective advantages of higher.
For pure phase phosphatization molybdenum, at high reaction velocity (36,000h
-1), in wide range of reaction temperature (200～240 ℃), shown good acetylene catalytic hydrogenation activity, still can keep high ethylene selectivity under high conversion ratio.For with SiO
2Be the support type molybdenum phosphide catalyst of carrier, have the selective of higher acetylene catalytic hydrogenation activity and product ethene, can be at lower H
2/ C
2H
2Obtain high catalytic hydrogenation activity and selective under mol ratio.With traditional noble metal catalyst relatively (as palladium catalyst), molybdenum phosphide catalyst has preparation method simple, cheap and catalytic hydrogenation activity and selective advantages of higher.
Under described operating condition, use described catalyst can obtain higher than 99.5% conversion of alkyne with higher than 70% ethylene selectivity.
The specific embodiment
The present invention carries out selective catalytic hydrogenation with above-mentioned catalyst, and key step is: with a certain amount of MoP or MoP/SiO
2Catalyst is packed in fixed bed reactors, in the High Purity Hydrogen air-flow of 100mL/min under 600 ℃ with catalyst pretreatment 1h; After pretreatment finishes, naturally cool to the reaction temperature of setting, according to certain H
2/ C
2H
2Than passing into reactor feed gas.At normal pressure, 200～240 ℃, H
2/ C
2H
2=4～8, air speed is 33,000～38,000h
-1Lower investigation acetylene Catalytic Hydrogenation Properties.
In order to further illustrate the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1
Take molybdenum phosphorus mol ratio as the 1 pure phase phosphatization molybdenum that makes as catalyst, the acetylene hydrogenation reaction is carried out in micro fixed-bed reactor.Unstripped gas forms: the Ar gaseous mixture of the acetylene of 1.0vol% and 99.0vol%, reaction condition is: 0.10g catalyst, 200 ℃ of temperature, normal pressure, H
2/ C
2H
2=8, feed gas flow rates 60mL/min, air speed 36,000h
-1Product analysis adopts Agilent gas-chromatography, hydrogen flame detector.
Embodiment 2
With embodiment 1, the pure phase phosphatization molybdenum take molybdenum phosphorus mol ratio as 0.9 is as catalyst, and reaction result is listed in table 1.
Embodiment 3
With embodiment 1, the pure phase phosphatization molybdenum take molybdenum phosphorus mol ratio as 0.95 is as catalyst, and reaction result is listed in table 1.
Embodiment 4
With embodiment 1, the pure phase phosphatization molybdenum take molybdenum phosphorus mol ratio as 1.05 is as catalyst, and reaction result is listed in table 1.
Embodiment 5
With embodiment 1, the pure phase phosphatization molybdenum take molybdenum phosphorus mol ratio as 1.10 is as catalyst, and reaction result is listed in table 1.
Embodiment 6
With embodiment 1, be to investigate the acetylene hydrogenation activity under 200 ℃ in reaction temperature, reaction result is listed in table 1.
Embodiment 7
With embodiment 1, be to investigate the acetylene hydrogenation activity under 220 ℃ in reaction temperature, reaction result is listed in table 1.
Embodiment 8
With embodiment 1, be to investigate the acetylene hydrogenation activity under 240 ℃ in reaction temperature, reaction result is listed in table 1.
Embodiment 9
With embodiment 7, at H
2/ C
2H
2Investigate acetylene hydrogenation=8 times active, reaction result is listed in table 1.
Embodiment 10
With embodiment 7, at H
2/ C
2H
2Investigate acetylene hydrogenation=6 times active, reaction result is listed in table 1.
Embodiment 11
With embodiment 7, at H
2/ C
2H
2Investigate acetylene hydrogenation=4 times active, reaction result is listed in table 1.
Embodiment 12
With embodiment 1, with mesopore SiO
2For carrier, make that molybdenum phosphorus mol ratio is 1, MoP mass loading amount is that 15% support type phosphatization molybdenum is catalyst, at 220 ℃ of reaction temperatures, H
2/ C
2H
2=6, lower investigation acetylene hydrogenation is active, and reaction result is listed in table 1.
Embodiment 13
With embodiment 12, the acetylene hydrogenation of investigating MoP mass loading amount and be 20% MoP catalyst is active, and reaction result is listed in table 1.
Embodiment 14
With embodiment 12, the acetylene hydrogenation of investigating MoP mass loading amount and be 25% MoP catalyst is active, and reaction result is listed in table 1.
Embodiment 15
With embodiment 12, the acetylene hydrogenation of investigating MoP mass loading amount and be 30% MoP catalyst is active, and reaction result is listed in table 1.
Embodiment 16
With embodiment 12, the acetylene hydrogenation of investigating MoP mass loading amount and be 35% MoP catalyst is active, and reaction result is listed in table 1.
Embodiment 17
With embodiment 14, investigate acetylene hydrogenation active under 200 ℃ of reaction temperatures, reaction result is listed in table 1.
Embodiment 18
With embodiment 14, reaction result is listed in table 1.
Embodiment 19
With embodiment 14, investigate acetylene hydrogenation active under 240 ℃ of reaction temperatures, reaction result is listed in table 1.
Embodiment 20
With embodiment 14, at H
2/ C
2H
2Investigate acetylene hydrogenation=8 times active, reaction result is listed in table 1.
Embodiment 21
With embodiment 14, reaction result is listed in table 1.
Embodiment 22
With embodiment 14, at H
2/ C
2H
2Investigate acetylene hydrogenation=4 times active, reaction result is listed in table 1.
Table 1
As can be seen from Table 1, pure phase MoP catalyst is at high reaction velocity (33,000～38,000h
-1), in wide range of reaction temperature (200-240 ℃) have high acetylene catalytic hydrogenation activity and selective, still can keep surpassing 76% hydrogenation selectivity when conversion of alkyne reaches 99.5%.Support type MoP/SiO
2Catalyst can keep high acetylene catalytic hydrogenation activity and selective equally in high reaction velocity and wide range of reaction temperature; Simultaneously, has higher low temperature acetylene hydrogenation activity and selectivity, at low H
2/ C
2H
2Has higher acetylene catalytic hydrogenation conversion ratio and selective during mol ratio.
Claims (3)
1. the method for a preparing ethylene with acetylene selective catalytic hydrogenation, is characterized in that: take the phosphatization molybdenum as catalyst;
Reaction pressure is normal pressure, and reaction temperature is 200～240 ℃, H
2/ C
2H
2Mol ratio=4～8, air speed are 33,000～38,000h
-1
Described molybdenum phosphide catalyst is pure phase phosphatization molybdenum or with mesopore SiO
2Support type phosphatization molybdenum for carrier.
2. it is characterized in that in accordance with the method for claim 1: molybdenum phosphorus mol ratio 0.9-1.1 in described phosphatization molybdenum.
3. it is characterized in that in accordance with the method for claim 1: described mesopore SiO
2In the support type molybdenum phosphide catalyst, the weight percentage of phosphatization molybdenum is 20～35wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101766147A CN102247876B (en) | 2010-05-19 | 2010-05-19 | Method for preparing ethylene with acetylene selective catalytic hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101766147A CN102247876B (en) | 2010-05-19 | 2010-05-19 | Method for preparing ethylene with acetylene selective catalytic hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102247876A CN102247876A (en) | 2011-11-23 |
| CN102247876B true CN102247876B (en) | 2013-06-26 |
Family
ID=44975655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101766147A Active CN102247876B (en) | 2010-05-19 | 2010-05-19 | Method for preparing ethylene with acetylene selective catalytic hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102247876B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9327265B2 (en) | 2012-08-21 | 2016-05-03 | Uop Llc | Production of aromatics from a methane conversion process |
| US8933275B2 (en) | 2012-08-21 | 2015-01-13 | Uop Llc | Production of oxygenates from a methane conversion process |
| US9434663B2 (en) | 2012-08-21 | 2016-09-06 | Uop Llc | Glycols removal and methane conversion process using a supersonic flow reactor |
| US9656229B2 (en) | 2012-08-21 | 2017-05-23 | Uop Llc | Methane conversion apparatus and process using a supersonic flow reactor |
| US20140058156A1 (en) * | 2012-08-21 | 2014-02-27 | Uop Llc | Process of energy management from a methane conversion process |
| US8937186B2 (en) | 2012-08-21 | 2015-01-20 | Uop Llc | Acids removal and methane conversion process using a supersonic flow reactor |
| US9023255B2 (en) | 2012-08-21 | 2015-05-05 | Uop Llc | Production of nitrogen compounds from a methane conversion process |
| US9205398B2 (en) | 2012-08-21 | 2015-12-08 | Uop Llc | Production of butanediol from a methane conversion process |
| US9308513B2 (en) | 2012-08-21 | 2016-04-12 | Uop Llc | Production of vinyl chloride from a methane conversion process |
| US9689615B2 (en) | 2012-08-21 | 2017-06-27 | Uop Llc | Steady state high temperature reactor |
| US8927769B2 (en) | 2012-08-21 | 2015-01-06 | Uop Llc | Production of acrylic acid from a methane conversion process |
| US9370757B2 (en) | 2012-08-21 | 2016-06-21 | Uop Llc | Pyrolytic reactor |
| US9707530B2 (en) | 2012-08-21 | 2017-07-18 | Uop Llc | Methane conversion apparatus and process using a supersonic flow reactor |
| CN105170167A (en) * | 2015-09-21 | 2015-12-23 | 北京华福工程有限公司 | Catalyst for acetylene selective hydrogenation ethylene and preparation method and application thereof |
| CN108579779B (en) * | 2018-04-28 | 2020-08-04 | 苏州大学 | Three-dimensional composite material, preparation method thereof and application of three-dimensional composite material in visible light catalytic degradation removal of water pollutants |
| CN113713840B (en) * | 2020-05-25 | 2023-07-25 | 台州学院 | Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN1764617A (en) * | 2003-03-26 | 2006-04-26 | 巴斯福股份公司 | Palladium-based catalyst for selective hydrogenation of acetylene |
| CN101658796A (en) * | 2009-09-17 | 2010-03-03 | 南开大学 | New method for preparing molybdenum phosphide by reducing molybdenum trioxide precursor |
-
2010
- 2010-05-19 CN CN2010101766147A patent/CN102247876B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1764617A (en) * | 2003-03-26 | 2006-04-26 | 巴斯福股份公司 | Palladium-based catalyst for selective hydrogenation of acetylene |
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN101658796A (en) * | 2009-09-17 | 2010-03-03 | 南开大学 | New method for preparing molybdenum phosphide by reducing molybdenum trioxide precursor |
Non-Patent Citations (1)
| Title |
|---|
| E.L.Muetterties et al.,.Catalytic Properties of Metal Phosphides. I. Qualitative Assay of Catalytic Properties.《Journal of the American Chemical Society》.1974,第96卷(第11期),第3414页左栏第1段-第3415页右栏最后1段. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102247876A (en) | 2011-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102247876B (en) | Method for preparing ethylene with acetylene selective catalytic hydrogenation | |
| CN102206130A (en) | Process for the selective hydrogenation of a carbon-containing fraction | |
| CN106111162B (en) | One type graphene-structured molybdenum sulfide catalyst and preparation method thereof | |
| CN102199067A (en) | Method for selective hydrogenation of carbon-containing distillate | |
| CN101767022B (en) | Catalyst with non-oxide as carrier and application thereof | |
| CN102614870B (en) | Vinylacetylene hydrogenation catalyst and preparation method thereof | |
| CN102745648A (en) | Preparation method of catalyst for producing synthetic gas by methane and carbon dioxide reformation | |
| CN109701588A (en) | Dehydrogenation and preparation method thereof | |
| CN106582706B (en) | Selective hydrogenation of butadiene catalyst | |
| CN107537560A (en) | Dehydrogenation, preparation method and its application method | |
| CN101940958B (en) | Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas | |
| CN115041188B (en) | Modification method of supported platinum-copper alloy catalyst and application of supported platinum-copper alloy catalyst in propylene preparation by propane dehydrogenation | |
| CN115672316B (en) | Biomass framework carbon-metal composite micro-nano structure catalytic material and preparation method and application thereof | |
| CN103846100A (en) | Pd/C-SiC catalyst for p-phthalic acid hydrorefining, preparation method and application thereof | |
| CN103127945B (en) | Method for preparing catalyst used for preparing acetaldehyde through direct dehydrogenation of ethanol and application of catalyst | |
| CN102553583B (en) | Mesoporous carbon-loaded gold nano catalyst and application thereof | |
| CN109701610A (en) | Modified dehydrogenation, preparation method and its usage | |
| CN105396582A (en) | Propane dehydrogenation propylene preparation catalyst, preparation method and applications thereof | |
| CN102908957A (en) | Method for Fischer-Tropsch synthesis | |
| CN112452340B (en) | Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof | |
| CN107970933A (en) | A kind of three selective hydrogenation catalyst of carbon, preparation method and method of hydrotreating | |
| CN101406839B (en) | Nickel catalyst for catalytic hydrogenation of dicyclopentadiene | |
| CN110508290B (en) | High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof | |
| CN101693643B (en) | Novel process for catalytic conversion of tetrachloromethane on non-hydrogen condition | |
| CN102211036A (en) | Modified molecular sieve catalyst, and precursor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191111 Address after: 215600 A 207 room A building center of Zhangjiagang Free Trade Zone, Suzhou Free Trade Zone, Jiangsu Co-patentee after: Dalian Institute of Chemical Physics, Chinese Academy of Sciences Patentee after: Zhangjiagang Institute of industrial technology, Dalian Institute of Chemical Physics, China Academy of Sciences Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |
|
| TR01 | Transfer of patent right |