CN1401430A - Catalyst for producing ethene by oxidizing ethane with carbon dioxide, and preparing process thereof - Google Patents
Catalyst for producing ethene by oxidizing ethane with carbon dioxide, and preparing process thereof Download PDFInfo
- Publication number
- CN1401430A CN1401430A CN02131334A CN02131334A CN1401430A CN 1401430 A CN1401430 A CN 1401430A CN 02131334 A CN02131334 A CN 02131334A CN 02131334 A CN02131334 A CN 02131334A CN 1401430 A CN1401430 A CN 1401430A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- carbon dioxide
- reaction
- cobalt
- barium carbonate
- 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.)
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Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 12
- 239000001569 carbon dioxide Substances 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 6
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 9
- 206010013786 Dry skin Diseases 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RUFJMLKBWUXJMX-UHFFFAOYSA-N barium;carbonic acid Chemical compound [Ba].OC(O)=O RUFJMLKBWUXJMX-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst for preparing ethene (C2H4) by oxidizing ethane by CO2 and dehydrogenating C2H6 is prepared through preparing the precursor from aqueous solution of cobalt nitrate and barium carbonate, drying, calcining at 600-750 deg.C, pressing and screening. Its advantages are high selectivity for C2H4 (97.6-6.4%), high C2H4 yield (80.3-6.4%), high mechanical strength and low reaction temp.
Description
Technical field
The present invention relates to a kind of production ethene (C
2H
4) Catalysts and its preparation method, particularly be used for the Catalysts and its preparation method of producing ethene by oxidizing ethane with carbon dioxide.
Be used for carbonic acid gas (CO
2) ethyl oxide (C
2H
6) generation ethene (C
2H
4) Catalysts and its preparation method.
Background technology
C
2H
4It is important basic chemical industry raw material.At present, to C
2H
4Demand increase day by day.C
2H
6With CO
2Prepared in reaction C
2H
4With traditional C
2H
6The high-temperature vapor cracking prepares C
2H
4Process is compared, and has unique advantages, and is low as temperature of reaction, catalyst carbon deposition is few, C
2H
4Selectivity is high.Therefore, carrying out the development of this reaction new catalyst and the exploitation of technological process has great importance.
In recent years, domestic and international investigator is to CO
2Oxidation C
2H
6Become city C
2H
4Catalyzer has carried out significant research.People such as Krylov go up report at " Catal.Today, 1995,24:371 ", with 1.5%K-5.5%Cr-17%Mn/SiO
2During for catalyzer, at 830 ℃, reactant gases air speed 3600h
-1, CO in the reactant gases
2/ C
2H
6Under=1.5/1 the condition, obtain C
2H
6Transformation efficiency be 82.6%, CO
2Transformation efficiency be 52.3%, C
2H
4Selectivity be 76.8% result.People such as Wang exist: " Catal.Lett., 1999,629 " go up report, when with 5CrO
3/ 6SO
4 2--SiO
2During for catalyzer, at 650 ℃, reactant gases air speed 3600h
-1, CO in the reactant gases
2/ C
2H
6/ N
2Under=1/5/4 the condition, obtain C
2H
6Transformation efficiency be 67.2%, CO
2Transformation efficiency be 21.9%, C
2H
4Selectivity be 81.8% result.People such as Xu go up report at " Catal.Lett., 1999,62:185 ", when being catalyzer with 9Fe-9Mn/Si-2, and at 800 ℃, reactant gases air speed 1000h
-1, CO in the reactant gases
2/ C
2H
6Under /=1 the condition, obtain C
2H
6Transformation efficiency be 68.6%, CO
2Transformation efficiency be 39.1%, C
2H
4Selectivity be 92.3% result.
The catalyzer of above bibliographical information respectively has characteristics, but the temperature of reaction during catalyzer performance greater catalytic performance is generally higher, and has CO on the catalyzer of low temperature active
2And C
2H
6Transformation efficiency lower again.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method that is used for producing ethene by oxidizing ethane with carbon dioxide, the catalyzer that is provided can carry out CO under than low reaction temperatures (650~730 ℃)
2Oxidation C
2H
6Dehydrogenation system C
2H
4Reaction, and obtaining higher C
2H
4In the time of selectivity and yield, C
2H
6Transformation efficiency and CO
2Transformation efficiency is also higher; And preparation technology is simple.
The purpose of this invention is to provide that following technical scheme realizes:
A kind of catalyzer that is used for producing ethene by oxidizing ethane with carbon dioxide, this catalyzer are the cobalt/cobalt oxide that barium carbonate supports, and wherein the CoO content range is 1~30wt%, and molecular formula is expressed as Co/BaCO
3
Above-mentioned Preparation of catalysts method provided by the present invention comprises the steps:
(1) cobalt nitrate hexahydrate is dissolved in the deionized water, being made into concentration is 2.6 * 10
-5Mol/mL~7.9 * 10
-4The cobalt nitrate solution of mol/mL;
(2) a certain amount of cobalt nitrate solution is joined barium carbonate (BaCO
3) go in the powder, make the pulpous state precursor;
(3) with the catalyzer precursor 90~120 ℃ of dryings 7~10 hours, then 600~750 ℃ of following roastings 8~12 hours;
(4) compression moulding after the roasting, screening 20~40 orders promptly make described granules of catalyst.
Catalyst performance evaluation is to carry out on high pressure, continuous flow fixed bed reactor.The reaction gas proportioning is CO
2/ C
2H
6/ N
2=10: 10~8: 1, air speed 1800~2400ml/ (g.cat) .h
-1, pressure 0.1MPa, temperature of reaction is generally between 650~730 ℃.On such catalyzer, carry out CO
2Oxidation C
2H
6Dehydrogenation prepares C
2H
4Reaction obtains C
2H
4Selectivity is 97.6~6.4%, C
2H
4Yield is 80.3~6.4%, C
2H
6Transformation efficiency is 99.6~29.3%, CO
2Transformation efficiency be 88.6~7.6%.
Catalyzer physical strength provided by the present invention is good, and the preparation method is simple.Because the Co of high oxidation state still can stable existence in reaction in the catalyzer, so catalyzer has than the high CO of most of catalyzer that has reported
2Oxidation C
2H
6Generate C
2H
4Performance, and temperature of reaction is lower.
Embodiment
Used barium carbonate (the BaCO of preparation catalyzer
3) powder is commercially available barium carbonate (BaCO
3) powder, Red Star chemical plant, Beijing produces, analytical pure; Xiao Suangu (Co (NO
3)
26H
2O is that Beijing dicyclo chemical reagent factory produces analytical pure.
The invention will be further described by embodiment below:
Embodiment 1
Is concentration 2.6 * 10
-510mL Xiao Suangu (Co (the NO of mol/mL
3)
26H
2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO
3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 90 ℃ of dryings 10 hours, and made the cobalt/cobalt oxide catalyzer that catalyzer carbonic acid barium supports in 8 hours 750 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 1wt%.Then, catalyzer compression moulding, the screening 20 purpose particles standby.On prepared catalyzer, carry out CO
2Oxidation C
2H
6Generate C
2H
4Reaction.In the reaction gas proportioning is CH
4/ O
2/ N
2=10/10/1, air speed 2000ml/ (g.cat) .h
-1, pressure 0.1MPa, temperature of reaction is to carry out under 730 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 96.7%, and carbon dioxide conversion is 83.8%, and ethylene selectivity is 83.0%, and yield of ethene is 80.3%.
Embodiment 2
Is concentration 1.3 * 10
-410mL Xiao Suangu (Co (the NO of mol/mL
3)
26H
2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO
3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 120 ℃ of dryings 7 hours, and made the cobalt/cobalt oxide catalyzer that barium carbonate supports in 9 hours 700 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 5wt%.Then, catalyzer compression moulding, the screening 20 purpose particles standby.On prepared catalyzer, carry out CO
2Oxidation C
2H
6Generate C
2H
4Reaction.In the reaction gas proportioning is CH
4/ O
2/ N
2=10/9/1, air speed 1800ml/ (g.cat) .h
-1, pressure 0.1MPa, temperature of reaction is to carry out under 700 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 89.7%, and carbon dioxide conversion is 83.1%, and ethylene selectivity is 66.8%, yield of ethene 60.0%.
Embodiment 3
Is concentration 2.6 * 10
-410mL Xiao Suangu (Co (the NO of mol/mL
3)
26H
2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO
3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 110 ℃ of dryings 8 hours, and made the cobalt/cobalt oxide catalyzer that barium carbonate supports in 10 hours 650 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 10wt%.Then, catalyzer is at 200Kg/cm
2Pressure compression moulding, the screening 30 purpose particles standby.On prepared catalyzer, carry out CO
2Oxidation C
2H
6Generate C
2H
4Reaction.In the reaction gas proportioning is CH
4/ O
2/ N
2=10/10/1, air speed 2200ml/ (g.cat) .h
-1, pressure 0.1MPa, temperature of reaction is to carry out under 670 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 83.8%, and carbon dioxide conversion is 74.1%, and ethylene selectivity is 45.8%, and yield of ethene is 38.4%.
Embodiment 4
Is concentration 7.8 * 10
-510mL Xiao Suangu (Co (the NO of mol/mL
3)
26H
2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO
3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 100 ℃ of dryings 9 hours, and made the cobalt/cobalt oxide catalyzer that barium carbonate supports in 12 hours 600 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 3wt%.Then, catalyzer compression moulding, the screening 40 purpose particles standby.On prepared catalyzer, carry out CO
2Oxidation C
2H
6Generate C
2H
4Reaction.In the reaction gas proportioning is CH
4/ O
2/ N
2=10/10/1, air speed 2400ml/ (g.cat) .h
-1, pressure 0.1MPa, temperature of reaction is to carry out under 650 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 66.3%, and carbon dioxide conversion is 52.3%, and ethylene selectivity is 93.4%, and yield of ethene is 62.0%.
Embodiment 5
Is concentration 7.8 * 10
-410mL Xiao Suangu (Co (the NO of mol/mL
3)
26H
2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO
3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 100 ℃ of dryings 10 hours, and made the cobalt/cobalt oxide catalyzer that barium carbonate supports in 11 hours 600 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 30wt%.Then, catalyzer compression moulding, the screening 30 purpose particles standby.On prepared catalyzer, carry out CO
2Oxidation C
2H
6Dehydrogenation prepares C
2H
4Reaction.In the reaction gas proportioning is CH
4/ O
2/ N
2=10/10/1, air speed 2400ml/ (g.cat) .h
-1, pressure 0.1MPa, temperature of reaction is to carry out under 730 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 94.1%, and carbon dioxide conversion is 88.2%, and ethylene selectivity is 34.7%, and yield of ethene is 32.8%.
Claims (2)
1. catalyzer that is used for producing ethene by oxidizing ethane with carbon dioxide, it is characterized in that: this catalyzer is the cobalt/cobalt oxide that barium carbonate supports, and wherein CoO content is 1~30wt%, and molecular formula is expressed as Co/BaCO
3
2. one kind prepares the method that is used for the catalyzer of producing ethene by oxidizing ethane with carbon dioxide as claimed in claim 1, it is characterized in that this method carries out as follows:
(1) cobalt nitrate hexahydrate is dissolved in the deionized water, being made into concentration is 2.6 * 10
-5Mol/mL~7.9 * 10
-4The cobalt nitrate solution of mol/mL;
(2) a certain amount of cobalt nitrate solution is joined in the barium carbonate powder go, make the precursor of pulpous state;
(3) with the catalyzer precursor 90~120 ℃ of dryings 7~10 hours, then 600~750 ℃ of following roastings 8~12 hours;
(4) compression moulding after the roasting, screening 20~40 orders promptly make described catalyst prod.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN02131334A CN1132691C (en) | 2002-09-29 | 2002-09-29 | Catalyst for producing ethene by oxidizing ethane with carbon dioxide, and preparing process thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN02131334A CN1132691C (en) | 2002-09-29 | 2002-09-29 | Catalyst for producing ethene by oxidizing ethane with carbon dioxide, and preparing process thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1401430A true CN1401430A (en) | 2003-03-12 |
CN1132691C CN1132691C (en) | 2003-12-31 |
Family
ID=4746653
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN02131334A Expired - Fee Related CN1132691C (en) | 2002-09-29 | 2002-09-29 | Catalyst for producing ethene by oxidizing ethane with carbon dioxide, and preparing process thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1132691C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2025660A3 (en) * | 2007-08-14 | 2009-03-04 | Rohm and Haas Company | Processes for producing ethylene and carbon monoxide mixtures from ethane |
-
2002
- 2002-09-29 CN CN02131334A patent/CN1132691C/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2025660A3 (en) * | 2007-08-14 | 2009-03-04 | Rohm and Haas Company | Processes for producing ethylene and carbon monoxide mixtures from ethane |
US7906699B2 (en) | 2007-08-14 | 2011-03-15 | Rohm And Haas Company | Processes for producing ethylene and carbon monoxide mixtures from ethane |
Also Published As
Publication number | Publication date |
---|---|
CN1132691C (en) | 2003-12-31 |
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