CN1966143A - Ferric oxide carried palladium catalyst and its preparation method and application - Google Patents
Ferric oxide carried palladium catalyst and its preparation method and application Download PDFInfo
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- CN1966143A CN1966143A CN 200510125520 CN200510125520A CN1966143A CN 1966143 A CN1966143 A CN 1966143A CN 200510125520 CN200510125520 CN 200510125520 CN 200510125520 A CN200510125520 A CN 200510125520A CN 1966143 A CN1966143 A CN 1966143A
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- catalyst
- palladium
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- ferric oxide
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Abstract
The invention relates to a ferric oxide palladium catalyst, wherein said catalyst is palladium catalyst loaded on ferric oxide, while the palladium mass percentage is 0.1-20% of carrier; and it is prepared by deposit method; said catalyst is multifunctional one, which has better low-temperature oxidize activity on CO, H2, CO+H2 and methane, and eliminates CO+H2 at room temperature, while it has high catalysis activity on steam.
Description
Invention field
The present invention relates to a kind of ferric oxide carried palladium catalyst and its production and application.
Background technology
Noble metal catalyst is because its catalytic activity that can not be substituted and selectivity are occupied extremely important status in oil refining, petrochemical industry and organic synthesis.Precious metal palladium has excellent catalytic performance, palladium catalyst in petro chemical industry application in addition surpass platinum catalyst.For example, the catalytic reforming in the petroleum refining, the isomerization reaction of alkane, aromatic hydrocarbons, dehydrogenation reaction, the selective hydrogenation reaction during alkene is produced, the production of Organic Chemicals such as acetaldehyde, vinyl acetate, methyl methacrylate all be unable to do without palladium catalyst.One of in addition, as in the reactions such as hydrogenation, oxidative dehydrogenation, hydrocrack, coupling, hydroesterification, one-carbon chemical and purifying vehicle exhaust, palladium is good catalyst in all kinds of organic chemical reactionses, or the important component of catalyst.
Up to now, the method for palladium catalyst preparation has infusion process, metal ion vapor deposition process, solvated metal atom impregnation method, ion-exchange, sol-gel process etc., and coprecipitation is more rare.Palladium catalyst will be dispersed on the suitable carrier and use, at different reactions, the maximum carrier of research is active carbon, alundum (Al, molecular sieve and zeolite, pottery, silica gel etc. at present, and the technology of preparing of palladium base catalytic membrane new material also is one of research emphasis.Up to the present, Shang Weijian uses the report of iron oxide as the carried palladium catalyst carrier.
The elimination of micro CO has extremely important meaning for environmental protection and industrial production as aspects such as gas purification, safety guarantee, and catalytic oxidation is a kind of simple and effective way.For example, industrial urea synthesis, owing to contain a spot of hydrogen usually in the CO 2 raw material gas, it is not consumed in building-up process, if accumulation too much, might cause blast, and such incident once had generation.But, the oxidation of the carbon monoxide of trace meeting strong inhibition hydrogen in the CO 2 raw material gas, the reaction temperature that only is improved largely usually just can reach the elimination fully of hydrogen.Equally, H
2The rich hydrogen unstripped gas of fuel cell wherein often contains the CO of trace greatly from methyl alcohol, the conversion of reformation G﹠W steam, can poison the Pt electrode, reduces fuel cell performance.Simultaneously, submarine is under water during operation, battery and engine can produce a spot of CO in the course of the work, for blast and the personnel that avoid causing poison, are necessary to seek a kind of catalyst of realizing CO complete oxidation and selective oxidation under alap temperature.
In recent years, the optimization utilization of natural gas more and more is subject to people's attention.One of important use of natural gas (main component is a methane) is to can be used as clean energy resource and be widely used.Because the imperfect combustion of methane causes a small amount of discharge of methane in atmosphere, cause greenhouse effects (be carbon dioxide 20 times).Catalytic combustion is a kind of effective technology that suppresses discharge of methane.Research realizes the completing combustion of methane under alap temperature, have important scientific meaning and practical value, also is the problem of a very challenging property.Precious metal palladium, platinum, rhodium are widely studied as the catalyst of methane low-temperature burning, and wherein palladium is considered to the active best catalyst of methane catalytic combustion, Al always
2O
3Also because its huge surface area and cheap price and as the carrier of palladium, but because Pd/Al
2O
3Catalyst is active relatively poor below 350 ℃, and initiation temperature is lower.Therefore be necessary to develop catalyst, make the initiation temperature of methane complete oxidation and the final temperature of eliminating drop to enough low with better activity.
In recent years, because the potential application aspect Proton Exchange Membrane Fuel Cells, the steam transformationreation is subjected to showing great attention to of people again.In addition, have simultaneously and contain a certain amount of water owing to contain CO usually in the environmental pollution gas, the steam transformationreation can consume CO, so this reaction pair environmental protection is also significant; Meanwhile, the product H of transformationreation
2Still NO efficiently
xReducing agent.Support gold, the application of platinum catalyst in the steam transformationreation and all be subjected to paying close attention to widely and research, the application of exclusive palladium catalyst in the steam transformationreation seldom.
Summary of the invention
The purpose of this invention is to provide a kind of ferric oxide carried palladium catalyst and its production and application.
Catalyst of the present invention is characterized in that catalyst carrier is an iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier.
Catalyst of the present invention is characterized in that catalyst adopts the coprecipitation preparation, and detailed process is: under the normal temperature, with Fe (NO
3)
3Solution and (NH
4)
2PdCl
4Or H
2PdCl
4Solution mixes, stir down and dropwise join in the precipitant solution, form co-precipitation, dispersed with stirring, leave standstill, filter, washing, room temperature to 100 ℃ drying, 300～800 ℃ of roastings are that 1%～100% hydrogen is 100～500 ℃ of reduction down with volumn concentration.
In the process of preparation catalyst, used precipitating reagent is selected from NaOH, Na
2CO
3, Li
2CO
3, KOH or K
2CO
3
Catalyst is a multifunction catalyst, can be applied to following aspect:
Catalyst of the present invention is to CO and H
2All have very high oxidation activity, can under being lower than room temperature, eliminate the CO and the H of individualism in the air respectively
2
Catalyst of the present invention is to CO+H
2Gaseous mixture has very high oxidation activity, can be lower than under the room temperature condition airborne CO+H
2The gaseous mixture cooxidation.
Catalyst of the present invention is to CH
4Have lower initiation temperature and very high total oxygen activity, can be with airborne CH under 350 ℃ of conditions
4Total oxygenization.
Catalyst of the present invention, transformationreation has very high catalytic activity to steam, CO is transformed reach equilibrium conversion.
This catalyst can be eliminated airborne CO.
A kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier, it is characterized in that this catalyst under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During the ml/g-catalyst, eliminate in the air 0.01～5% CO for-20～50 ℃.
This catalyst can be eliminated airborne H
2
A kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier, it is characterized in that catalyst under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During ml/g-cat, eliminate in the air 0.01～5% H for-20～20 ℃
2
This catalyst can be eliminated airborne CO+H
2Gaseous mixture.
A kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, it is characterized in that catalyst under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During ml/g-cat, eliminate CO and H under the aerobic conditions simultaneously for-10～60 ℃
2CO in the gaseous mixture and H
2, CO accounts for 0.01～5% of cumulative volume, H
2Account for 0.01～5%% of cumulative volume, oxygen accounts for 1～5% of cumulative volume.
This catalyst can be eliminated airborne CH
4
A kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier, it is characterized in that catalyst under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During ml/g-cat, eliminate in the air 0.01～5% CH for 350～450 ℃
4
This catalyst can the catalyzed aqueous vapour transformationreation.
A kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier, it is characterized in that catalyst can be under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During ml/g-cat, 250～350 ℃ make that the CO conversion ratio reaches equilibrium conversion in the steam transformationreation.
Compared with the prior art, the substantial characteristics that have of the present invention are:
1. catalyst prepares with coprecipitation, can obtain the less nanometer palladium particle of yardstick relatively uniformly of high dispersive.
2. this catalyst is a multifunction catalyst, to CO, H
2, CO+H
2Gaseous mixture and CH
4The elimination of gas can both show good catalytic activity, and the steam transformationreation is also had catalytic activity preferably.
3. as single-metal reforming catalyst, this catalyst can be realized the CO+H under the room temperature condition
2The cooxidation of gaseous mixture is that any other single-metal reforming catalyst is irrealizable.
4. the existence of steam can not reduce this catalyst to CO, H
2, CO+H
2Gaseous mixture and CH
4The catalytic activity of reaction such as complete oxidation.
5. compare with Au catalyst, under to the suitable situation of CO oxidation activity, this catalyst life is longer.
6. this catalyst and existing honeycomb support combine the catalyst that preparation shape, big I are regulated as required easily.
The specific embodiment
Embodiment 1:
Fe (NO with 1M
3)
3The H of solution 10ml and 0.29M
2PdCl
4Solution 0.05ml mixes, and dropwise joins the NaCO of 30ml (wt) 10% under the strong agitation
3In the solution, form co-precipitation, regulating pH value is 8, continues to stir 2h, leaves standstill 2.5h, filters, with the distilled water washing, place under the room temperature and made the catalyst air dry in 24 hours, 400 ℃ of roastings 5 hours, 200 ℃ of pure hydrogen reductase 12s hour, catalyst cat 1.
Embodiment 2:
Fe (NO with 1M
3)
3The H of solution 10ml 0.29M
2PdCl
4Solution 0.2ml mixes, place a conical flask, dropwise add the NaOH solution 20ml of 1M under the strong agitation, form co-precipitation, regulating pH value is 7.5, continue to stir 2h, leave standstill 2.5h, filter, wash with distilled water, place under the room temperature and made the catalyst air dry in 24 hours, 500 ℃ of roastings 5 hours, 200 ℃ of 50%H
2Reductase 12 hour, catalyst cat 2.
Embodiment 3:
Fe (NO with 1M
3)
3(the NH of solution 10ml and 0.35M
4)
2PdCl
4Solution 0.2ml mixes, and places a conical flask, dropwise adds the K of 1M under the strong agitation
2CO
3Solution 30ml forms co-precipitation, and regulating pH value is 8, continues to stir 2h, leaves standstill 2.5h, filter, and with the distilled water washing, 50 ℃ of dryings 4 hours, 600 ℃ of roastings 5 hours, 300 ℃ of 10%H
2Reductase 12 hour, catalyst cat 3.
Embodiment 4:
Fe (NO with 1M
3)
3(the NH of solution 5ml and 0.35M
4)
2PdCl
4Solution mixes, and places a conical flask, dropwise adds the KOH solution 15ml of 1M under the strong agitation, forms co-precipitation, regulating pH value is 9, continues to stir 2h, leaves standstill 2.5h, filters, with distilled water washing, 80 ℃ dry 4 hours down, 500 ℃ of roastings 5 hours, 200 ℃ of 10%H
2Reductase 12 hour, catalyst cat 4.
Embodiment 5:
Consist of CO:1.0% at unstripped gas; O
2: 5.0%; N
2Balance (percent by volume), gas volume air speed are 2.0 * 10
4h
-1Situation under, use cat 1 to reach remaining CO amount＜10ppm in the tail gas at 40 ℃.
Embodiment 6:
Consist of CO:1.0% at unstripped gas; O
2: 5.0%; N
2Balance (percent by volume), gas volume air speed are 2.0 * 10
4h
-1Situation under, use cat 3 to reach remaining CO amount＜10ppm in the tail gas at-20 ℃.
Embodiment 7:
Consist of H at unstripped gas
2: 1.0%; O
2: 5.0%; N
2Balance (percent by volume), gas volume air speed are 2.0 * 10
4h
-1Situation under, use cat 1 to reach remaining H in the tail gas at 10 ℃
2Amount＜5ppm.
Embodiment 8:
Consist of H at unstripped gas
2: 2.0%; O
2: 5.0%; N
2Balance (percent by volume), gas volume air speed are 2.0 * 10
4h
-1Situation under, use cat 4 to reach remaining H in the tail gas at-10 ℃
2Amount＜5ppm.
Embodiment 9:
Consist of CO:1.0% at unstripped gas; H
2: 1.0%; O
2: 1.0%; N
2Balance (percent by volume), gas volume air speed are 1.0 * 10
4h
-1Situation under, use cat 1 to reach remaining CO amount＜10ppm in the tail gas, remaining H at 50 ℃
2Amount＜5ppm.
Embodiment 10:
Consist of CO:1.0% at unstripped gas; H
2: 2.0%; O
2: 2.0%; N
2Balance (percent by volume), gas volume air speed are 1.0 * 10
4h
-1Situation under, use cat 3 to reach remaining CO amount＜10ppm in the tail gas, remaining H at 0 ℃
2Amount＜5ppm.
Embodiment 11:
Consist of CH at unstripped gas
4: 1.0%; O
2: 5.0%; N
2Balance (percent by volume), gas volume air speed are 2.0 * 10
4h
-1Situation under, use cat 2 to reach remaining CH in the tail gas at 400 ℃
4Amount＜10ppm.
Embodiment 12:
Consist of CH at unstripped gas
4: 1.0%; O
2: 5.0%; N
2Balance (percent by volume), gas volume air speed are 2.0 * 10
4h
-1Situation under, use cat 4 to reach remaining CH in the tail gas at 350 ℃
4Amount＜10ppm.
Embodiment 13:
Consist of CO:5.0% at unstripped gas, N
2Dilution (percent by volume), water flowing steam under the oxygen free condition, the gas volume air speed is 2.0 * 10
4h
-1Situation under, use cat 3 to reach equilibrium conversion at 250 ℃ of CO conversion ratios.
Claims (8)
1, a kind of ferric oxide carried palladium catalyst is characterized in that catalyst carrier is an iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier.
2, as the said Preparation of catalysts method of claim 1, it is characterized in that catalyst adopts the coprecipitation preparation, detailed process is: under the normal temperature, with Fe (NO
3)
3Solution and (NH
4)
2PdCl
4Or H
2PdCl
4Solution mixes, stir down and dropwise join in the precipitant solution, form co-precipitation, dispersed with stirring, leave standstill, filter, washing, room temperature to 100 ℃ drying, 300～800 ℃ of roastings are that 1%～100% hydrogen is 100～500 ℃ of reduction down with volumn concentration.
3,, it is characterized in that precipitating reagent is selected from NaOH, Na as the said method of claim 1
2CO
3, Li
2CO
3, KOH or K
2CO
3
4, a kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier, it is characterized in that this catalyst under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During the ml/g-catalyst, eliminate in the air 0.01～5% CO for-20～50 ℃.
5, a kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier, it is characterized in that catalyst under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During ml/g-cat, eliminate in the air 0.01～5% H for-20～20 ℃
2
6, a kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, it is characterized in that catalyst under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During ml/g-cat, eliminate CO and H under the aerobic conditions simultaneously for-10～60 ℃
2CO in the gaseous mixture and H
2, CO accounts for 0.01～5% of cumulative volume, H
2Account for 0.01～5%% of cumulative volume, oxygen accounts for 1～5% of cumulative volume.
7, a kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier, it is characterized in that catalyst under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During ml/g-cat, eliminate in the air 0.01～5% CH for 350～450 ℃
4
8, a kind of application of ferric oxide carried palladium catalyst, the carrier of this catalyst are iron oxide, and active component is a palladium, and palladium quality percentage composition is 0.1%～20% of a carrier, it is characterized in that catalyst can be under normal pressure, gas space velocity is 5.0 * 10
3～3.0 * 10
4h
-1During ml/g-cat, 250～350 ℃ make that the CO conversion ratio reaches equilibrium conversion in the steam transformationreation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510125520 CN1966143A (en) | 2005-11-17 | 2005-11-17 | Ferric oxide carried palladium catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510125520 CN1966143A (en) | 2005-11-17 | 2005-11-17 | Ferric oxide carried palladium catalyst and its preparation method and application |
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| Publication Number | Publication Date |
|---|---|
| CN1966143A true CN1966143A (en) | 2007-05-23 |
Family
ID=38075225
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|---|---|---|---|
| CN 200510125520 Pending CN1966143A (en) | 2005-11-17 | 2005-11-17 | Ferric oxide carried palladium catalyst and its preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111306A (en) * | 2013-02-07 | 2013-05-22 | 浙江工业大学 | Magnetic load type nanometer palladium/iron grain catalyst and preparation method and application thereof |
| CN103521243A (en) * | 2013-09-24 | 2014-01-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Palladium oxide composite oxide catalyst as well as preparation method and application thereof |
| CN104010699A (en) * | 2011-11-07 | 2014-08-27 | 庄信万丰股份有限公司 | Apparatus for the treatment of air |
| CN108126708A (en) * | 2017-12-08 | 2018-06-08 | 中国科学院兰州化学物理研究所 | A kind of CO room-temperature catalytic oxidation catalysts |
| CN114618521A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing methyl propionate by using supported bimetallic core-shell structure catalyst |
-
2005
- 2005-11-17 CN CN 200510125520 patent/CN1966143A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104010699A (en) * | 2011-11-07 | 2014-08-27 | 庄信万丰股份有限公司 | Apparatus for the treatment of air |
| CN104010699B (en) * | 2011-11-07 | 2016-10-26 | 英美铂业营销有限公司 | Air-treatment equipment |
| CN103111306A (en) * | 2013-02-07 | 2013-05-22 | 浙江工业大学 | Magnetic load type nanometer palladium/iron grain catalyst and preparation method and application thereof |
| CN103521243A (en) * | 2013-09-24 | 2014-01-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Palladium oxide composite oxide catalyst as well as preparation method and application thereof |
| CN108126708A (en) * | 2017-12-08 | 2018-06-08 | 中国科学院兰州化学物理研究所 | A kind of CO room-temperature catalytic oxidation catalysts |
| CN108126708B (en) * | 2017-12-08 | 2020-11-10 | 中国科学院兰州化学物理研究所 | CO normal temperature catalytic oxidation catalyst |
| CN114618521A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing methyl propionate by using supported bimetallic core-shell structure catalyst |
| CN114618521B (en) * | 2020-12-11 | 2023-05-09 | 中国科学院大连化学物理研究所 | Method for preparing methyl propionate by using supported bimetallic core-shell catalyst |
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