CN1241452A - Hydration-resisting and sulfur-resisting conversion catalyst and its preparation - Google Patents
Hydration-resisting and sulfur-resisting conversion catalyst and its preparation Download PDFInfo
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- CN1241452A CN1241452A CN98110348A CN98110348A CN1241452A CN 1241452 A CN1241452 A CN 1241452A CN 98110348 A CN98110348 A CN 98110348A CN 98110348 A CN98110348 A CN 98110348A CN 1241452 A CN1241452 A CN 1241452A
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The catalyst has compound of Co and Mo as active component and oxide of alkali metal as assistant, and its carrier has compound of Ti as main component and oxide of Al, Mg or other alkali earth metals as skeleton material, into which rare earth compound and/or alkali earth metal compound are added as hydration resisting assistant. During the preparation, the carrier skeleton material is first modified with hydration resisting assistant and then mixed with the compound of Ti as main component, and the carrier is finally soaked with the active component. The catalyst has excellent hydration resisting performance and structural stability.
Description
The present invention relates to a kind of CO sulfur-resistant transformation catalyst and preparation method, specifically, the present invention relates to a kind of sulfur-resistant transformation catalyst and preparation method of hydration-resisting.
At present, in the reconstruction of expanding production of China's large chemical fertilizer " coal for oil " and middle chemical fertilizer plant, major part selected for use with the coal be raw material, 4.0MPa gasification gas making, three sections sulphur-resistant conversions (middle change string is low to be become), after connect the technological process that methanation purifies.Because the low temperature shift process pressure of this flow process is higher, temperature is lower, catalyst will move under less than 20 ℃ harsh conditions in the distance dew-point temperature, therefore the sulfur-resistant transformation catalyst that requires to be adapted to this technology not only will have good low temperature active, also good anti-hydration and structural stability will be arranged.And the antisulphour Low Temperature Transform Catalyst of present industrial extensive use, how with Υ-Al
2O
3Or with rare earth modified Υ-Al
2O
3Be carrier, as Chinese patent CN1003979 and U.S. Pat 4,153, the catalyst described in 580.When the carrier of this class catalyst uses, all can hydration reaction take place to some extent, cause catalyst to produce phase transformation and inactivation under above-mentioned process conditions.In the Chinese patent application 96100935.7 before us, a kind of catalyst that carrier is carried out modification with the titanium component is provided, this catalyst has higher intensity and strength stability, also have better low temperature activity and curability, but when using under above-mentioned process conditions, hydration and inactivation also can take place in catalyst to some extent.
Purpose of the present invention just provides a kind of not hydration, not phase transformation when using, has good anti-hydration, low temperature active and structural stability under above-mentioned harsh conditions catalyst.
In sulfur-resistant transformation catalyst of the present invention, used active constituent is the compound of cobalt and molybdenum, and the adding alkali metal compound is made auxiliary agent, carrier is then selected the good titanium compound of hydration-resisting performance for use, and the quality percentage composition of titanium compound in carrier preferably is controlled in 30%～80% the scope (with TiO
2Meter).
The selected titanium compound of the present invention can be titanium oxide, metatitanic acid, four titanium oxide, the red stone of titanium or anatase, also can be the mixture of any two or more material in the above-mentioned substance.
The quality percentage composition of active constituent in catalyst is MoO
35%～20%, CoO0.5%～5%; Alkali metal promoter shared quality percentage composition in catalyst is 0.1%～20% (in oxide), and alkali metal can be potassium, also can be sodium.
Though titanium compound has good hydration-resisting performance, if carrier all uses titanium compound, then the mechanical strength of carrier and catalyst is not ideal enough, thereby in the present invention, makes the skeleton material with compounds such as aluminium, magnesium, improves the intensity of catalyst.These compounds can be that the oxide or the hydroxide of aluminium hydroxide, boehmite, gibbsite, alundum (Al, zinc oxide, magnesium hydroxide, magnesium carbonate, magnesia or other alkaline-earth metal is made the skeleton material.Also can adopt in the above-claimed cpd arbitrarily two or more mixture to make the skeleton material.
When preparation catalyst of the present invention, key is the preparation of carrier.During the preparation carrier, earlier the carrier framework material is carried out modification with the hydration-resisting auxiliary agent, soon the skeleton material mixes with the hydration-resisting auxiliary agent, roasting is decomposed and pulverizing, to improve the anti-hydration and the structural stability of carrier component; Then that the carrier framework material after the modification and hydration-resisting performance is good novel carriers component be the compound of titanium do mix, extrusion, roasting, make catalyst carrier; According to a conventional method the compound and the alkali metal compound of active constituent molybdenum, cobalt is mixed with co-impregnated solution again, impregnated carrier and roasting, decomposition make the sulfur-resistant transformation catalyst of hydration-resisting.
In the preparation process, the carrier framework material can be selected the oxide or the hydroxide of aluminium hydroxide, boehmite, gibbsite, alundum (Al, zinc oxide, magnesium hydroxide, magnesium carbonate, magnesia or other alkaline-earth metal, also can select any two or more mixture in the above-claimed cpd; The hydration-resisting auxiliary agent can be selected rare earth compound and/or alkaline earth metal compound, as the nitrate or the sulfate of the nitrate of the nitrate of lanthanum or oxide, cerium or oxide, alkali-metal nitrate or sulfate, alkaline-earth metal, also can be two or more mixture arbitrarily in the above-claimed cpd; The compound of titanium can the selective oxidation titanium, metatitanic acid, four titanium oxide, the red stone of titanium or anatase or its mixture.
In the catalyst carrier, make the hydration-resisting auxiliary agent if add rare earth compound, then its quality percentage composition is 0.01%～10% (in oxide); Make the hydration-resisting auxiliary agent if add alkaline earth compound, then its quality percentage composition is 10%～20% (in oxide); Titanium compound is the main component of carrier, and its quality percentage composition is preferably in titanium dioxide in 30%～80% the scope.
Carrier framework material and titanium compound are done when mixing, can add peptizing agent mixes, peptizing agent can be the liquid glue solvent, as the nitrate aqueous solution of nitric acid, alkaline-earth metal, alkali-metal nitrate aqueous solution, alkali-metal sulfate solution or its solution of two or more mixture arbitrarily; Peptizing agent also can be the peptizing agent of solid, as the oxide of alkaline-earth metal, the hydroxide of alkaline-earth metal or the sulfate of alkaline-earth metal.
Adopt sulfur-resistant transformation catalyst of the present invention when the distance dew point uses under less than 20 ℃ harsh conditions, not hydration of catalyst, not phase transformation has anti-hydration and structural stability preferably, and industrial low change catalyzer C
25-2-02, when QCS-02, EB-04 etc. use in same process conditions, all undergo phase transition (seeing accompanying drawing 1).In addition, the technology that the present invention prepares catalyst is simple, can significantly reduce manufacturing cost.
Further specify the present invention below in conjunction with drawings and Examples, but scope of the present invention is not limited to following examples of implementation.
Fig. 1 is the thing phase change figure before and after the catalyst CT-4 hydrothermal treatment consists of the present invention, among the figure, and a: before the hydrothermal treatment consists; B: after the hydrothermal treatment consists.
Fig. 2 is the thing phase change figure before and after several common used in industry catalyst hydrothermal treatment consists, among the figure, and the fresh sample of a:EB-4; The fresh sample of b:QCS-02; C:C
25-2-02Fresh sample; After the d:EB-4 hydrothermal treatment consists; After the e:QCS-02 hydrothermal treatment consists; F:C
25-2-02After the hydrothermal treatment consists.
Fig. 3 is the thing phase spectrogram of each catalyst of the present invention after hydrothermal treatment consists, among the figure, after the a:CT-1 hydrothermal treatment consists; After the b:CT-2 hydrothermal treatment consists; After the c:CT-3 hydrothermal treatment consists; After the d:CT-4 hydrothermal treatment consists.
Embodiment 1 Preparation of catalysts
Catalyst CT-1:
Get La
2O
310 gram wiring solution-formings are with MgCO
3100 grams mix, and 700 ℃ of following roastings 2 hours, pulverize; Add 400 gram titanium hydroxides, add again that 10% nitric acid is mediated, extrusion, and, make catalyst carrier in 500 ℃ of following roastings.Ammonium molybdate 55 grams, cobalt nitrate 5.0 grams and potash 50 grams are mixed with co-impregnated solution; Get the above-mentioned carrier of 50 grams,, and, make catalyst CT-1 in 400 ℃ of following roastings decomposition with this co-impregnated solution dipping.
Catalyst CT-2:
The preparation method is with catalyst CT-1, and different is to replace La with zinc nitrate aqueous solution
2O
3The aqueous solution and MgCO
3Mix, the catalyst of last gained is CT-2.
Catalyst CT-3:
The preparation method is with catalyst CT-2, and different is with Al (OH)
3MgCO among the replaced C T-2
3, the catalyst that makes at last is CT-3.
Catalyst CT-4:
The preparation method is with catalyst CT-3, and different is to replace zinc nitrate aqueous solution to mix with magnesium nitrate aqueous solution, and the catalyst that makes at last is CT-4.
Catalyst CT-5:
The preparation method is with catalyst CT-1, and different is with 400 gram titanium hydroxides among 200 gram titanium hydroxides and the 300 gram metatitanic acid replaced C T-1, makes the nitric acid of 10% among the peptizing agent replaced C T-1 with 20 gram potassium nitrate, and the catalyst of gained is CT-5 at last.The performance test of embodiment 2 catalyst
On former granularity pressurization evaluating apparatus, be medium with hydrogen and water vapour, at 18 ℃～20 ℃ of distance dew points (pressure 4.0Mpa, 220 ℃～222 ℃ of temperature, air speed 2000h
-1, water/gas 0.7) condition under, to catalyst of the present invention and industrial catalyst hydrothermal treatment consists 72 hours, detect its thing phase change, the results are shown in accompanying drawing 1, accompanying drawing 2 and accompanying drawing 3.As can be seen, catalyst of the present invention (CT-4) is after hydrothermal treatment consists from accompanying drawing 1 and accompanying drawing 2, and thing does not change mutually basically, and the hydration peak that occurs yet useless does not form algeldrate after showing hydrothermal treatment consists, and industrial catalyst C
25-2-02, QCS-02 and EB-4 be all having occurred hydration peak (peak between 10 °～20 ° is the hydration peak) after the hydrothermal treatment consists, shows that hydration has taken place these catalyst; As can be seen, hydration does not all take place in each catalyst CT-1, CT-2 of the present invention, CT-3, CT-4 after hydrothermal treatment consists from accompanying drawing 3, forms the hydration peak.
Then, measure each catalyst of the present invention and industrial catalyst C
25-2-02Fresh sample, boiling test sample and the intensity of hydrothermal treatment consists test sample, data see Table-1.From the table-1 data as can be seen, each catalyst of the present invention is not only than industrial catalyst C
25-2-02Have better initial strength, and strength retention ratio is also high after poach and hydrothermal treatment consists, shows that catalyst of the present invention has good strength stability.The field investigation of embodiment 3 catalyst
Under the following conditions, catalyst CT-4 of the present invention is carried out Simulation evaluation, the results are shown in Table-2.
Appreciation condition: the loadings of catalyst is 50ml, with α-Al
2O
3Bead by 1: 1 dilution proportion extremely
100ml
Conditions of vulcanization: pressure 1.5MPa; 260 ℃ of temperature; Air speed 1000h
-1 Cure time 20 hours
The intensity of table-1 catalyst of the present invention and industrial catalyst and stability contrast thereof
The simulation operation test of table-2 catalyst CT-4 of the present invention
| Pressure (Mpa) | Air speed (h -1) | Water/gas | Inlet temperature (℃) | CO% (percent by volume) | CO interconversion rate (%) | |
| Inlet | Outlet | |||||
| ?1.5 | ?1000 | ?1.0 | ?260.6 | ?5.89 | ?0.47 | ?91.58 |
| ?3.8 | ?3000 | ?0.76 | ?260.0 | ?5.49 | ?0.36 | ?93.11 |
| ?3.8 | ?2000 | ?0.76 | ?260.1 | ?5.41 | ?0.27 | ?94.75 |
| ?3.8 | ?2000 | ?0.63 | ?260.0 | ?5.41 | ?0.30 | ?94.16 |
| ?3.8 | ?2000 | ?0.63 | ?220 | ?5.20 | ?0.34 | ?93.14 |
| ?3.8 | ?2000 | ?0.63 | ?215 | ?5.29 | ?0.30 | ?94.04 |
| ?3.8 | ?2000 | ?0.63 | ?210 | ?5.16 | ?0.28 | ?94.31 |
| ?3.8 | ?2000 | ?0.63 | ?210 | ?3.77 | ?0.20 | ?94.51 |
| ?3.8 | ?2000 | ?0.63 | ?210 | ?1.67 | ?0.10 | ?94.52 |
| ?3.8 | ?2000 | ?0.63 | ?205 | ?3.44 | ?0.21 | ?93.69 |
Claims (16)
1. the sulfur-resistant transformation catalyst of a hydration-resisting, its active constituent is the compound of cobalt and molybdenum, it is characterized in that adding in the catalyst alkali metal compound and make auxiliary agent, and the main component of catalyst carrier is the compound of titanium, and titanium compound quality percentage composition counts 30%～80% with titanium dioxide.
2. the described catalyst of claim 1 is characterized in that the titanium compound in the catalyst carrier can be titanium oxide, metatitanic acid, four titanium oxide, the red stone of titanium or anatase, also can above-mentioned substance in two or more mixture arbitrarily.
3. the described catalyst of claim 1 is characterized in that active constituent molybdenum, cobalt and the alkali metal promoter quality percentage composition in catalyst is respectively 5%～20%, 0.5%～5% and 0.1%～20% in oxide.
4. the described catalyst of claim 1, it is characterized in that catalyst carrier makes the skeleton material with the oxide or the hydroxide of aluminium hydroxide, boehmite, gibbsite, alundum (Al, zinc oxide, magnesium hydroxide, magnesium carbonate, magnesia or other alkaline-earth metal, also can make the skeleton material with any two or more mixture in the above-claimed cpd.
5. the described catalyst of claim 4 is characterized in that adding rare earth compound in the skeleton material of catalyst carrier and/or alkaline earth metal compound is made the hydration-resisting auxiliary agent.
6. the described catalyst of claim 5, the nitrate, cerium oxide, alkali-metal nitrate, alkali-metal sulfate, the nitrate of alkaline-earth metal or the sulfate of alkaline-earth metal that it is characterized in that added hydration-resisting auxiliary agent is a lanthanum in the carrier nitrate, lanthana, cerium also can be two or more mixtures arbitrarily in the above-claimed cpd.
7. the described catalyst of claim 5 is characterized in that added rare earth compound quality percentage composition is 0.01%～10% (in oxide) in the carrier.
8. the described catalyst of claim 5 is characterized in that added alkaline earth compound quality percentage composition is 10%～20% (in oxide) in the carrier.
9. method for preparing the hydration-resisting sulfur-resistant transformation catalyst is characterized in that:
A. the carrier framework material is carried out modification with the hydration-resisting auxiliary agent;
B. with the compound of the main component titanium of carrier framework material after the modification and carrier, extrusion, roasting
Burn, make the carrier of catalyst;
C. compound and the alkali metal compound with activity of such catalysts component molybdenum, cobalt is mixed with co-impregnated solution,
Impregnated carrier and roasting, decomposition make the sulfur-resistant transformation catalyst of hydration-resisting.
10. the described method of claim 9, when it is characterized in that the compound of main component titanium of carrier framework material and carrier, adding peptizing agent mixes, peptizing agent can be the nitrate aqueous solution of nitric acid, alkaline-earth metal, alkali-metal nitrate aqueous solution, alkali-metal sulfate solution or its solution of two or more mixture arbitrarily, also can be the oxide of alkaline-earth metal, the hydroxide of alkaline-earth metal or the sulfate of alkaline-earth metal.
11. claim 9 or 10 described methods, the skeleton material that it is characterized in that catalyst carrier can be the oxide or the hydroxide of aluminium hydroxide, boehmite, gibbsite, alundum (Al, magnesium hydroxide, magnesium carbonate, magnesia or other alkaline-earth metal, also can be any two or more mixture in the above-claimed cpd.
12. claim 9 or 10 described methods, it is characterized in that the nitrate that added hydration-resisting auxiliary agent is a lanthanum in the carrier, the nitrate of cerium, alkali-metal nitrate, alkali-metal sulfate, the nitrate of alkaline-earth metal or the sulfate of alkaline-earth metal, also can be any two or more mixture in the above-claimed cpd.
13. claim 9 or 10 described methods, the carrier component titanium compound of its feature carried catalyst can be titanium oxide, metatitanic acid, four titanium oxide, the red stone of titanium or anatase, also can above-mentioned substance in two or more mixture arbitrarily.
14. claim 9 or 10 described methods is characterized in that the quality percentage composition of active constituent molybdenum, cobalt and alkali metal promoter in the catalyst is respectively 5%～20%, 0.5%～5% and 0.1%～20% in oxide.
15. the described method of claim 12 is characterized in that added rare earth compound quality percentage composition is 0.01%～10% (in oxide).
16. the described method of claim 12 is characterized in that added alkaline earth compound quality percentage composition is 10%～20% (in oxide).
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110348A CN1087192C (en) | 1998-07-15 | 1998-07-15 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
| ZA9904562A ZA994562B (en) | 1998-07-15 | 1999-07-15 | Anti-hydrating and sulfur-resistant catalyst for Co-shift process and preparation method therof. |
| CZ0253199A CZ297807B6 (en) | 1998-07-15 | 1999-07-15 | Catalyst for conversion carbon monooxide with steam and process for preparing thereof |
| AU40129/99A AU747821B2 (en) | 1998-07-15 | 1999-07-15 | Anti-hydrating and sulfur-resistant catalyst for CO-shift process and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110348A CN1087192C (en) | 1998-07-15 | 1998-07-15 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1241452A true CN1241452A (en) | 2000-01-19 |
| CN1087192C CN1087192C (en) | 2002-07-10 |
Family
ID=5220404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110348A Expired - Fee Related CN1087192C (en) | 1998-07-15 | 1998-07-15 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1087192C (en) |
| AU (1) | AU747821B2 (en) |
| CZ (1) | CZ297807B6 (en) |
| ZA (1) | ZA994562B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151574A (en) * | 2011-02-16 | 2011-08-17 | 山东齐鲁科力化工研究院有限公司 | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
| CN105478131A (en) * | 2014-10-09 | 2016-04-13 | 中国石油化工股份有限公司 | CO medium-high-pressure low-temperature sulfur-tolerant pre-shift catalyst and preparation method thereof |
| CN106552637A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Cobalt molybdenum system low temperature sulfur tolerant shift catalyst and preparation method |
| CN108940298A (en) * | 2017-05-29 | 2018-12-07 | 镇江瑞德新材料科技研发有限公司 | Cobalt molybdenum system CO sulfur-resistant transformation catalyst and preparation method thereof |
| CN110237852A (en) * | 2018-03-09 | 2019-09-17 | 国家能源投资集团有限责任公司 | The modified sulfur-resistant transformation catalyst and preparation method thereof of the titanium compound of sulphate-containing ion |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
| CN115518661A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst, preparation method and application |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201109376D0 (en) * | 2011-06-06 | 2011-07-20 | Johnson Matthey Plc | Water-gas shift catalyst |
| CN103480358A (en) * | 2013-10-11 | 2014-01-01 | 神华集团有限责任公司 | High temperature and sulfur resistant methanation catalyst and preparation method thereof |
| CN114177912B (en) * | 2020-09-14 | 2024-02-13 | 中国石油化工股份有限公司 | Perovskite sulfur-resistant shift catalyst and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4153580A (en) * | 1977-12-09 | 1979-05-08 | United Catalysts Inc. | CO conversion catalyst |
| CN1003979B (en) * | 1987-11-14 | 1989-04-26 | 湖北省化学研究所 | Sulfur resistant carbon monoxide transformation catalyst and its prepn |
| JPH08176034A (en) * | 1994-12-22 | 1996-07-09 | Cosmo Sogo Kenkyusho:Kk | Synthesis of methanol |
| CN1067917C (en) * | 1996-01-11 | 2001-07-04 | 中国石化齐鲁石油化工公司 | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
-
1998
- 1998-07-15 CN CN98110348A patent/CN1087192C/en not_active Expired - Fee Related
-
1999
- 1999-07-15 CZ CZ0253199A patent/CZ297807B6/en not_active IP Right Cessation
- 1999-07-15 AU AU40129/99A patent/AU747821B2/en not_active Ceased
- 1999-07-15 ZA ZA9904562A patent/ZA994562B/en unknown
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151574A (en) * | 2011-02-16 | 2011-08-17 | 山东齐鲁科力化工研究院有限公司 | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
| CN102151574B (en) * | 2011-02-16 | 2015-06-17 | 山东齐鲁科力化工研究院有限公司 | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
| CN105478131A (en) * | 2014-10-09 | 2016-04-13 | 中国石油化工股份有限公司 | CO medium-high-pressure low-temperature sulfur-tolerant pre-shift catalyst and preparation method thereof |
| CN105478131B (en) * | 2014-10-09 | 2018-09-21 | 中国石油化工股份有限公司 | CO mesohigh low temperature resistant to sulfur pre-transform catalyst and preparation method thereof |
| CN106552637A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Cobalt molybdenum system low temperature sulfur tolerant shift catalyst and preparation method |
| CN106552637B (en) * | 2015-09-30 | 2019-03-29 | 中国石油化工股份有限公司 | Cobalt molybdenum system low temperature sulfur tolerant shift catalyst and preparation method |
| CN108940298A (en) * | 2017-05-29 | 2018-12-07 | 镇江瑞德新材料科技研发有限公司 | Cobalt molybdenum system CO sulfur-resistant transformation catalyst and preparation method thereof |
| CN110237852A (en) * | 2018-03-09 | 2019-09-17 | 国家能源投资集团有限责任公司 | The modified sulfur-resistant transformation catalyst and preparation method thereof of the titanium compound of sulphate-containing ion |
| CN110237852B (en) * | 2018-03-09 | 2022-04-15 | 国家能源投资集团有限责任公司 | Sulfate ion-containing titanium compound modified sulfur-tolerant shift catalyst and preparation method thereof |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
| CN115518661A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst, preparation method and application |
| CN115518661B (en) * | 2021-06-25 | 2023-12-05 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1087192C (en) | 2002-07-10 |
| CZ253199A3 (en) | 2000-02-16 |
| AU4012999A (en) | 2000-02-10 |
| CZ297807B6 (en) | 2007-04-04 |
| AU747821B2 (en) | 2002-05-23 |
| ZA994562B (en) | 2000-01-18 |
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Owner name: CHINA PETROCHEMICAL CORPORATION Free format text: FORMER OWNER: SINOPEC QILU PETRO-CHEMICAL CORP. Effective date: 20071228 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20071228 Address after: Linzi Zibo District, Shandong province Sinopec Qilu Branch of science and technology Patentee after: China Petrochemical Group Corp. Address before: 124 mailbox, Zibo City, Shandong Province Patentee before: Qilu Petrochemical Company of China Petrochemical Corp. |
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| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20020710 Termination date: 20130715 |