CN101607206B - Method for increasing the activity of copper-based catalyst in water-gas shift reaction - Google Patents
Method for increasing the activity of copper-based catalyst in water-gas shift reaction Download PDFInfo
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- CN101607206B CN101607206B CN2009100548852A CN200910054885A CN101607206B CN 101607206 B CN101607206 B CN 101607206B CN 2009100548852 A CN2009100548852 A CN 2009100548852A CN 200910054885 A CN200910054885 A CN 200910054885A CN 101607206 B CN101607206 B CN 101607206B
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to the inorganic chemical industry technical field, in particular to a method for increasing the activity of copper-based catalyst in water-gas shift reaction, comprising the following steps: after the reduction of the copper-based catalyst or reducing the copper-based catalyst for a period of time, lowering the temperature of catalyst bed to less than 100 DEG C under a water-bearing gas atmosphere and keeping temperature for a period of time, and then heating the temperature of catalyst bed to more than 100 DEG C to reach the aim of increasing the activity of catalyst. The reactivation process can be processed in in-situ reactions. The invention has a good application prospect in fuel cell system.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, is about the active method of a kind of raising copper-based catalysts of novelty, is specifically related to the copper based water gas converting catalyst, and the application in fuel cell system.
Background technology
Catalyst must just can have catalytic activity through proper process before being used for a certain reaction.For example for oxidation reaction, maybe presoma be carried out calcination process and obtain being in the active component of oxidation state; For hydrogenation reaction, active component then is through the metallic state component after the reduction.To be used for the copper-based catalysts of water gas shift reaction, it needs the catalyst that just can obtain having catalytic activity through following process usually before being used for reaction: (one) adopts coprecipitation method to obtain precipitating presoma particularly; (2) be converted into corresponding metal oxide through the deposition presoma after washing, the oven dry through calcination process; (3) under reducing atmosphere, be reactive metal copper with copper oxide reduction.Technological parameter in the above processing procedure all can have influence on the reactivity of catalyst.Form under the constant situation in catalyst elements, be devoted to improve the active effort of copper-based catalysts and all be basically in the preparation process parameters Optimization and carry out, and do not see proposition at present as yet except above-mentioned these other activation methods operating process.
Summary of the invention
The objective of the invention is to propose a kind of active method of water gas shift reaction that improves copper-based catalysts.
The present invention has broken through the idea that traditional activation process of thinking copper-based catalysts is promptly accomplished after reduction is handled, creatively proposed a kind of economic environmental protection, and can under the online condition of gentleness, carry out the method for activation act.This method can further increase the catalytic active site of participating in reaction, thereby reaches activating catalyst and improve active purpose, and can obviously not change the structural behaviour of original catalyst, has very high using value.
The active method of this raising copper-based catalysts of proposition of the present invention can through the modulation to reaction bed temperature, reach the purpose of activating catalyst under environment amenable moisture atmosphere.The implementation process that this method is more detailed can be described as catalyst through after the restoring operation; Perhaps catalyst is through restoring operation and after reacting a period of time (as 40～80 minutes); Under moisture activation phenomenon; The temperature of beds is reduced to below 100 ℃; Handle a period of time (as 40～80 minutes), the temperature of the time of concrete processing when handling, the flow velocity of handling the water content of atmosphere and handling atmosphere are confirmed; More than the temperature to 100 ℃ of beds of raising then, can realize activation process to catalyst.Such activation act can be carried out repeatedly, for example 1～6 time.
Copper-based catalysts among the present invention mainly is to be active component with Cu, is the catalyst of dispersible carrier with magnesia and alumina composite oxide, can also add zinc oxide, cerium oxide etc. in the carrier, is mainly used in water gas shift reaction.
Among the present invention, used activation phenomenon is by CO, CO
2, H
2, N
2, one or more and H in the gas such as Ar
2O forms and contains water mixed gas, and water content is 24～30%, and the flow velocity of mist is 20000～40000h
-1
The active method of the raising copper-based catalysts of this novelty further specifically explains through the activity change of catalyst in water gas shift reaction.Activity of such catalysts representes that with the CO conversion ratio CO conversion ratio is high more, and catalyst activity is high more, shows that promptly activation effect is good more.
The specific embodiment
Preparation of Catalyst embodiment 1～4:
With 6 gram Cu (NO
3)
23H
2O, 4.4 gram Zn (NO
3)
26H
2O, 28 gram Al (NO
3)
39H
2O and 19 gram Mg (NO
3)
26H
2The water-soluble mixed solution that is made into metal ion of O, 22 gram Na
2CO
3The water-soluble precipitant solution that obtains.60 ℃ of water-baths, stirring drip metal ion and precipitant solution simultaneously and make both co-precipitation admixed together.Drip and finish ageing 2 hours.The deposition that obtains thus also need be washed to remove foreign ion, 120 ℃ of dried over night, respectively 450,500,600 and 700 ℃ of following roastings 4 hours, can obtain catalyst embodiment 1～4 respectively then.
Preparation of Catalyst embodiment 5:
With 3 gram Cu (NO
3)
23H
2O, 17 gram Al (NO
3)
39H
2O and 12 gram Mg (NO
3)
26H
2The water-soluble mixed solution that is made into metal ion of O, 12 gram Na
2CO
3The water-soluble precipitant solution that obtains.60 ℃ of water-baths, stirring drip metal ion and precipitant solution simultaneously and make both co-precipitation admixed together.Drip and finish ageing 2 hours.The deposition that obtains thus also need be washed to remove foreign ion, 120 ℃ of dried over night, 600 ℃ of following roastings 4 hours, can obtain catalyst embodiment 5 then.
Preparation of Catalyst embodiment 6:
With 8 gram Cu (NO
3)
23H
2O, 6.4 gram Zn (NO
3)
26H
2O, 5.4 gram Al (NO
3)
39H
2The water-soluble mixed solution that is made into metal ion of O, 8 gram Na
2CO
3The water-soluble precipitant solution that obtains.70 ℃ of water-baths, stirring drip metal ion and precipitant solution simultaneously and make both co-precipitation admixed together.Drip and finish ageing 1 hour.The deposition that obtains thus also need be washed to remove foreign ion, 120 ℃ of dried over night, 450 ℃ of following roastings 4 hours, can obtain catalyst embodiment 6 then.
Preparation of Catalyst embodiment 7:
With 10 gram Cu (NO
3)
23H
2O, 6 gram Zn (NO
3)
26H
2O and 11 gram Al (NO
3)
39H
2The water-soluble mixed solution that is made into metal ion of O, 11 gram Na
2CO
3The water-soluble precipitant solution that obtains.70 ℃ of water-baths, stirring drip metal ion and precipitant solution simultaneously and make both co-precipitation admixed together.Drip and finish ageing 1 hour.The deposition that obtains thus also need be washed to remove foreign ion, 120 ℃ of dried over night, 450 ℃ of following roastings 4 hours, can obtain catalyst embodiment 7 then.
Improve the activation embodiment 1 of catalyst activity:
With catalyst embodiment 1 at 15%CO/N
2Be warming up to 300 ℃ of reduction in the gaseous mixture, keep being cooled to 150 ℃ after 1 hour, change atmosphere into 11%CO, 26%H then
2O and 63%N
2Reaction atmosphere, gas flow rate is 30000h
-1, evaluate catalysts is the activity 150 ℃ the time in binary reformation atmosphere.CO conversion ratio on the catalyst after the fresh reduction is designated as 1C.At 11%CO, 26%H
2O and 63%N
2Atmosphere in react 40～80 minutes after; Stop temperature control, cool off (about 8～15 minutes) beds fast to room temperature, and kept 40～80 minutes; To guarantee that beds is immersed in the condensed water fully; Being warming up to subsequently more than 100 ℃, is that 150 ℃ (about 18～25 minutes) are promptly accomplished activation act one time in this example, and catalyst is designated as 2C through the CO conversion ratio after activation act.Catalyst is designated as 3C through the CO conversion ratio after twice activation act, and the rest may be inferred.When catalyst embodiment 1 is respectively 150 ℃ and 200 ℃ in reaction temperature, after the fresh reduction and as shown in Figure 1 through the active result after the activation act.Visible by Fig. 1, through after the activation act, the CO conversion ratio can improve 14%～50% and do not wait under binary reformation atmosphere.
Improve the activation embodiment 2 of catalyst activity:
Catalyst embodiment 1～7 is fresh reduction back and as shown in Figure 2 through the active result after the above-mentioned activation act when reaction temperature is 250 ℃.Active result investigates in true quaternary reformation atmosphere, and reaction atmosphere consists of 26%H
2O, 27%H
2, 11%CO, 7%CO
2, 29%N
2, gas flow rate is 30000h
-1, other active investigation conditions are seen the activation embodiment 1 that improves catalyst activity.1C representes the CO conversion ratio after the fresh reduction of catalyst, and nC representes that catalyst is through the CO conversion ratio after (n-1) inferior activation act.Visible by Fig. 2, except that catalyst embodiment 5, after the activated operation of other catalyst, the CO conversion ratio can improve 3%～30% and do not wait under quaternary reformation atmosphere.
Structural behaviour parameter after catalyst embodiment 2～4 fresh reduction backs and the process activation act is shown in table 1.
Structural behaviour parameter after table 1 catalyst embodiment 2～4 reduction backs and the process activation act
Claims (3)
1. method that improves activity of copper-based catalyst in water-gas shift reaction is characterized in that concrete steps are following:
Catalyst is through after the restoring operation, and perhaps catalyst is through after restoring operation and reacting a period of time, under moisture activation phenomenon, the temperature of beds is reduced to below 100 ℃ handles, and the concrete time of handling is 40-80 minute; More than the temperature to 100 ℃ of beds of raising then, can realize activation process to catalyst.
2. method according to claim 1 is characterized in that said activation phenomenon is moisture gaseous mixture, and moisture is by CO, CO
2, H
2, N
2Drive with the atmosphere of one or more compositions in the Ar gas, the water content in the gaseous mixture is 24～30%.
3. method according to claim 2, the flow velocity that it is characterized in that moisture gaseous mixture is 20000～40000h
-1
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| CN2009100548852A CN101607206B (en) | 2009-07-16 | 2009-07-16 | Method for increasing the activity of copper-based catalyst in water-gas shift reaction |
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| CN101607206B true CN101607206B (en) | 2012-05-30 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335201A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Reduction process of copper-containing catalyst |
| US6627572B1 (en) * | 2002-03-22 | 2003-09-30 | Sud-Chemie Inc. | Water gas shift catalyst |
| CN1467029A (en) * | 2003-06-02 | 2004-01-14 | 厦门中坤化学有限公司 | Method for preparing load-type catalyst of modified cupric oxide |
-
2009
- 2009-07-16 CN CN2009100548852A patent/CN101607206B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335201A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Reduction process of copper-containing catalyst |
| US6627572B1 (en) * | 2002-03-22 | 2003-09-30 | Sud-Chemie Inc. | Water gas shift catalyst |
| CN1467029A (en) * | 2003-06-02 | 2004-01-14 | 厦门中坤化学有限公司 | Method for preparing load-type catalyst of modified cupric oxide |
Non-Patent Citations (2)
| Title |
|---|
| Pingjun Guo,et al..Cu/ZnO/Al2O3 water-gas shift catalysts for practical fuel cell applications: the performance in shut-down/start-up operation.《International Journal of Hydrogen Energy》.2009,(第34期),2361-2368. * |
| 杨意泉.改进型甲醇合成催化剂NC208的低氢活化过程.《厦门大学学报(自然科学版)》.1998,第37卷(第5期),722-726. * |
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