CN104689829A - Ferric hydroxide loaded rhodium-based catalyst and preparation and application thereof - Google Patents

Ferric hydroxide loaded rhodium-based catalyst and preparation and application thereof Download PDF

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Publication number
CN104689829A
CN104689829A CN201310670592.3A CN201310670592A CN104689829A CN 104689829 A CN104689829 A CN 104689829A CN 201310670592 A CN201310670592 A CN 201310670592A CN 104689829 A CN104689829 A CN 104689829A
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catalyst
preparation
water
application
rhodium
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关红玲
王晓东
林坚
李林
张涛
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • 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

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Abstract

The invention relates to a loading type small grain-size rhodium (Rh)-based catalyst and preparation and application thereof. Specifically, the rhodium-based catalyst is prepared by adopting a coprecipitation method, precious metal Rh is highly dispersed on a ferric hydroxide carrier, the grain size of the Rh is less than 1nm, wherein Rh accounts for 0.2-5% of the catalyst in total mass. The catalyst disclosed by the invention adopts the elimination of trace CO in reformed hydrogen source such as fuel batteries as the application background, is suitable for water-vapor conversion and CO selected oxidizing reaction in a rich-hydrogen atmosphere, is capable of achieving water-vapor conversion reaction under 300 DEG C with the CO conversion rate being higher than 98%, and capable of completely converting the trace CO into CO2 in the rich-hydrogen atmosphere under the room temperature condition.

Description

A kind of rhodium base catalyst of iron hydroxide load and Synthesis and applications thereof
Technical field
The present invention relates to the catalyst based and Synthesis and applications of a kind of small particle diameter (average grain diameter is 1nm) rhodium (Rh), specifically a kind of iron hydroxide load Rh catalyst by trace amounts of CO in the reaction elimination reformed gas hydrogen source of CO oxidation (PROX) in water-gas shift (WGS) and hydrogen rich gas atmosphere and Synthesis and applications thereof.
Background technology
Hydrogen Energy is generally acknowledged clean energy resource, shows one's talent as low-carbon (LC) and the zero carbon energy.In recent years, China and the U.S., Japan, Canada, European Union etc. have all formulated Hydrogen Energy development plan, and achieve many-sided progress, be expected in the near future become Hydrogen Technology and apply one of leading country, also by the internationally recognized country realizing hydrogen energy automobile and hydrogen fuel cell industrialization for most possibly taking the lead in.
Fuel cell technology has the advantages such as efficiency is high, environmental pollution is little, is a kind of eco-friendly energy utilization technology.In various fuel cell technology, Proton Exchange Membrane Fuel Cells (PEMFC) has low emission, starts the feature convenient, specific power is large, condition of work is gentle, becomes the most competitive dynamic origin.And fuel hydrogen wherein used generally adopts steam reforming, the technical limit spacing such as partial oxidation and thermal reforming of the hydrocarbon such as methyl alcohol, natural gas.The hydrogen source prepared thus is unavoidably containing a small amount of CO gas (2 ~ 10%), and the CO of trace seriously can poison electrode catalyst of fuel cell, reduces battery operated efficiency, therefore needs CO concentration to be reduced to 50 ~ below 100ppm, battery efficiency is declined.The method of elimination CO general at present first removes most of CO (CO content reaches 0.5 ~ 2%) through high/low temperature water gas shift reation (WGS), and then in hydrogen rich gas atmosphere, CO Selective Oxidation (PROX) eliminates residual CO again.
According to the difference of catalyst activity component, catalyst mainly comprises that Cu-is catalyst based, Au-is catalyst based and platinum metal catalysts.Although the catalyst based price advantage of Cu is obvious, water repelling property is poor, and stability declines when system closing reboot operation; Au-is catalyst based well-known with its good low-temperature catalytic activity, but Au catalyst also constrains its practical application to features such as preparation condition are responsive, Conservation environment is harsh.Compared with Au, Cu catalyst, platinum-group noble metals catalyst activity becomes because of its good activity and stability the water-gas shift and CO selective oxidation catalyst that have actual application prospect most.
But because Precious Metals Resources is deficient, price becomes a key factor of the practical process of restriction noble metal catalyst.Therefore, the decentralization improving noble metal catalyst is just necessary to improve its atom utilization ratio very much.Existing many research finds that the catalyst such as Pt, Ir of sub-nano-scale show greater activity, but then less to the research of support type small particle diameter Rh catalyst preparing and application thereof.
As everyone knows, rhodium (Rh) is the noble metal homogeneous catalysis agent of most extensive use, late 1960s, has first occurred synthesizing acetic acid by methanol low-pressure carbonylation using rhodium complex catalysts.In heterogeneous catalysis system, rhodium also has excellent catalytic performance, and from 1974, automobile exhaust gas purifying noble metal catalyst (based on platinum, being aided with palladium, rhodium) large-scale popularization was applied, and develops into the maximum noble metal catalyst of consumption very soon.1975, the reported first such as the Wilson of Union Carbide Corporation on load type rhodium catalyst can from synthesis gas (CO+H 2) produce the C2 such as ethanol, acetaldehyde oxygenatedchemicals after, synthesis gas oxygenatedchemicals has started new climax in the whole world.The Dalian Chemistry and Physics Institute has carried out a large amount of screening operations for the loading of Noble Metal Rhodium and rhodium catalyst auxiliary agent subsequently, develops the catalyst of a series of low rhodium carrying capacity and high selectivity, simultaneously the scale pilot scale of completion rate 300,000 tons/year.In recent ten years, along with the fast development of hydrogen source efficiency utilization and fuel cell technology, CO selective oxidation and water gas shift reation obtain more and more extensive and deep concern and research, and Au, Pt become catalyst of greatest concern due to its higher catalytic activity.And due to some reasons, the research of Rh in CO selective oxidation and water gas shift reation is not a lot.
The high price that scarce resource causes is the main factor affecting rhodium catalyst heavy industrialization.The defects such as the particle diameter in addition caused due to the limitation of traditional preparation methods is excessive, Cl ion is poisoning, complicated process of preparation, cycle are long make the activity of some rhodium catalysts not high enough, and therefore the application of rhodium catalyst also receives certain restriction.But, along with discovery and the development of various catalyst preparing new technology, be also far from terminating to the preparation research of rhodium catalyst, but invent and be a kind ofly applied to the load type rhodium catalyst that trace amounts of CO in hydrogen source eliminates there is not been reported so far efficiently, eco-friendly.
Summary of the invention
The object of this invention is to provide a kind of small particle diameter rhodium base catalyst of iron compound load, this catalyst has CO selective oxidation catalytic activity in higher water-gas shift and hydrogen rich gas atmosphere, can be used for the elimination of CO in reformed gas hydrogen source.
The invention is characterized in: CO selective oxidation catalyst in a kind of water-gas shift and hydrogen rich gas atmosphere, catalyst is formed with iron hydroxide and noble metal Rh double activated component, and Rh content is 0.2 ~ 5% of catalyst gross mass.Noble metal Rh is highly dispersed on iron hydroxide.
Catalyst of the present invention adopts coprecipitation preparation, it is characterized in that: by the soluble ferric iron salt that mixes through ultrasonic disperse and Rh presoma glycol water, add in the strong base solution in rapid stirring and carry out co-precipitation, dispersed with stirring, leave standstill, filter, wash, be drying to obtain product
Described Rh precursor is radium chloride (RhCl 33H 2o); Molysite is ferric nitrate (Fe (NO 3) 39H 2o); Highly basic is NaOH.
Required precipitation and aging temperature preferably 70 ~ 80 DEG C; The PH of solution preferably 8 ~ 9; The baking temperature of described catalyst preferably 60 ~ 80 DEG C, drying time is 12h preferably.
Need activation process before described catalyst application, condition is 1 ~ 100vol%H at 100 ~ 500 DEG C 2reduction 0.5 ~ 2h in/He, gas flow rate is 20 ~ 100ml/min.
Described catalyst can be used for CO selective oxidation in hydrogen rich gas atmosphere, will consist of 0.5 ~ 3vol%CO, 0.5 ~ 3vol%O 2, 20 ~ 40vol%H 2, all the other are the rich hydrogen unstripped gas of He, with air speed 1x10 4~ 1x10 5ml g cat -1h -1air speed pass into and be equipped with in the fixed bed reactors of catalyst, measure the CO selective oxidation of catalyst in 20 ~ 140 DEG C of temperature under normal pressure active.
Described catalyst can be used for CO water gas shift reation.0.5 ~ 5vol%CO will be consisted of, 1 ~ 10vol%H 2o, all the other are the unstripped gas of He, with air speed 1x10 4~ 1x10 5ml g cat -1h -1pass into and be equipped with in the fixed bed reactors of catalyst, measure catalyst CO water gas shift reation in 150 ~ 300 DEG C of temperature under normal pressure active.
Compared with the prior art, the substantive distinguishing features that the present invention has is:
1. the catalyst spent glycol aqueous solution is the coprecipitation preparation of solvent, can obtain high dispersive, relatively uniform, that size is less nanometer rhodium particle (see Fig. 1), be conducive to improving catalyst activity, thus improve the utilization rate of active component rhodium.
2. catalyst preparation process is simple, and manufacturing cycle is short, does not need roasting, and horsepower requirements is low, avoids because of roasting discharge HCl, NO xdeng dusty gas, cause environmental pollution.
3. (40%H in hydrogen rich gas atmosphere 2), catalyst shows higher CO catalytic oxidation activity (data result see legend 2), can realize CO conversion ratio reach 100%. in room temperature
4. catalyst shows higher water-gas shift activity (data result see legend 3), and 300 DEG C time, CO conversion ratio reaches 98%.
Accompanying drawing explanation
Fig. 1 is the iron hydroxide of different rhodium content and the XRD figure of rhodium bicomponent catalyst.
Fig. 2 is prepared Rh/Fe (OH) xthe high-resolution-ration transmission electric-lens figure of catalyst.
Fig. 3 is the comparison diagram that under the hydrogen rich gas atmosphere of the embodiment of the present invention 1,2,3,4 Kaolinite Preparation of Catalyst, CO selects CO conversion ratio in reaction.
Fig. 4 is the comparison diagram of CO conversion ratio in the water gas shift reation of the embodiment of the present invention 1,3 Kaolinite Preparation of Catalyst.
Fig. 5 is the comparison diagram that under the hydrogen rich gas atmosphere of the embodiment of the present invention 4,5 and comparative example Kaolinite Preparation of Catalyst, CO selects CO conversion ratio in reaction.
Detailed description of the invention
Embodiment 1:
By the Fe (NO of 3.78g 3) 39H 2the RhCl of O and 0.1wt% 33H 2o solution 2.02g add 100ml glycol water (ethylene glycol: water=3:1) afterwards ultrasonic disperse mix, dropwise join in the NaOH solution of 100ml0.3mol/L under strong agitation, adjust ph is 8, form co-precipitation, continue at 80 DEG C to stir 3h, leave standstill 1h, filter, hot wash, places 12h and makes catalyst dry, obtain 0.2%Rh/Fe (OH) at 80 DEG C xcatalyst.
Embodiment 2:
By the Fe (NO of 3.78g 3) 39H 2the RhCl of O and 0.10wt% 33H 2o solution 9.98g add 100ml glycol water (ethylene glycol: water=3:1) afterwards ultrasonic disperse mix, dropwise join in the NaOH solution 100ml of 0.3mol/L under strong agitation, adjust ph is 8, form co-precipitation, continue at 80 DEG C to stir 3h, leave standstill 1h, filter, hot wash, places 12h and makes catalyst dry, obtain 1%Rh/Fe (OH) at 80 DEG C xcatalyst.
Embodiment 3:
By the Fe (NO of 3.78g 3) 39H 2the RhCl of O and 0.1wt% 33H 2o solution 20.01g add 100ml glycol water (ethylene glycol: water=3:1) afterwards ultrasonic disperse mix, dropwise join in the NaOH solution of 100ml0.3mol/L under strong agitation, adjust ph is 8, form co-precipitation, continue at 80 DEG C to stir 3h, leave standstill 1h, filter, hot wash, places 12h and makes catalyst dry, obtain 2%Rh/Fe (OH) at 80 DEG C xcatalyst.
Embodiment 4:
By the Fe (NO of 3.78g 3) 39H 2the RhCl of O and 0.1wt% 33H 2o solution 30.01g add 100ml glycol water (ethylene glycol: water=3:1) afterwards ultrasonic disperse mix, dropwise join in the NaOH solution of 100ml0.3mol/L under strong agitation, adjust ph is 8, form co-precipitation, continue at 80 DEG C to stir 3h, leave standstill 1h, filter, hot wash, places 12h and makes catalyst dry, obtain 3%Rh/Fe (OH) at 80 DEG C xcatalyst.
Comparative example 1:
Employing glycol water is that the coprecipitation of solvent prepares Rh/Al 2o 3catalyst.Wherein tenor is 3%.
By the Al (NO of 4.82g 3) 39H 2the RhCl of O and 0.1wt% 33H 2o solution 30.01g add 100ml glycol water (ethylene glycol: water=3:1) afterwards ultrasonic disperse mix, dropwise join in the NaOH solution of 100ml0.3mol/L under strong agitation, adjust ph is 8, forms co-precipitation, continues to stir 3h at 80 DEG C, leave standstill 1h, filter, hot wash, place 12h at 80 DEG C and make catalyst dry, 400 DEG C of roasting 4h, obtain 3%Rh/Al 2o 3catalyst.
Comparative example 2:
Employing water is that the coprecipitation of solvent prepares Rh/Fe (OH) xcatalyst.Wherein tenor is 3%.
By the Fe (NO of 3.78g 3) 39H 2the RhCl of O and 0.1wt% 33H 2o solution 30.01g adds 100ml deionized water for stirring and mixes, dropwise join in the NaOH solution of 100ml0.3mol/L under strong agitation, adjust ph is 8, form co-precipitation, continue at 80 DEG C to stir 3h, leave standstill 1h, filter, hot wash, places 12h and makes catalyst dry, obtain 3%Rh/Fe (OH) at 80 DEG C x-H 2o catalyst.
For evaluating the catalytic performance of prepared catalyst, micro anti-evaluation device is adopted to carry out CO Selective Oxidation active testing in water-gas shift and hydrogen rich gas atmosphere to catalyst.Test condition is: adopt tube furnace and fixed bed reactors, catalyst amount is 100mg, and gas volume consists of 2%CO+10%H 2o+He (WGS) or 1%CO+1%O 2+ 40%H 2+ He(PROX), total flow is 30ml/min (STP), and mass space velocity is 1.8x10 4ml g cat -1h -1, test procatalyst is in advance at 10vol%H 2the lower 300 DEG C of reduction 0.5h of/He atmosphere, catalyst CO water gas shift reation activity (WGS) or 200 DEG C of reduction 0.5h in 150 ~ 300 DEG C of temperature are measured under normal pressure after being down to 150 DEG C, measure the CO selective oxidation activity (PROX) of catalyst in 20 ~ 140 DEG C of temperature after being down to room temperature under normal pressure, sample after each temperature spot constant temperature 20min to be measured.By chromatogram detection reaction device exit gas composition, and calculate conversion ratio and selective.
CO conversion ratio and CO 2selective calculation method as follows:
CO Conversion(%)={([CO] in–[CO] out)/[CO] in}×100%
Wherein: [CO] infor charging CO chromatographic peak area, [CO] outfor outlet CO chromatographic peak area.
Result:
Can find out that catalyst carrier is unbodied iron hydroxide in investigated Rh content temperature range by the iron hydroxide of rhodium content different in Fig. 1 and the XRD figure of rhodium bicomponent catalyst, on active component Rh high degree of dispersion and amorphous carrier.
Rh/Fe (OH) shown in Fig. 2 xthe high-resolution-ration transmission electric-lens figure of catalyst shows on prepared catalyst active component Rh high degree of dispersion and carrier, and its average grain diameter is less than 1nm.
Under the hydrogen rich gas atmosphere being the embodiment of the present invention 1,2,3,4 Kaolinite Preparation of Catalyst by Fig. 3, the comparison diagram of CO selective oxidation temperature-programmed reaction CO conversion ratio can show that catalyst described in this patent has the activity of CO selective oxidation in very high hydrogen rich gas atmosphere, transforms completely under can realizing room temperature condition.
The comparison diagram of the water-gas shift temperature-programmed reaction CO conversion ratio of the embodiment of the present invention 1 shown in Fig. 4,3 Kaolinite Preparation of Catalysts shows catalyst described in this patent and has very high water gas shift reation activity, and 300 DEG C time, CO conversion ratio reaches 98%.
Fig. 5 is the comparison diagram of CO selective oxidation temperature-programmed reaction CO conversion ratio under the hydrogen rich gas atmosphere of the embodiment of the present invention 4 and comparative example Kaolinite Preparation of Catalyst, therefrom can find out that substituting with glycol water the Catalyst for CO selective oxidation activity that in conventional coprecipitation method, water prepares gained for solvent is significantly improved; What iron hydroxide was that the catalyst activity of carrier also prepared far above same method take aluminium oxide as the catalyst of carrier.
Catalyst of the present invention is to eliminate in reformed gas trace amounts of CO for application background, be applicable to CO Selective Oxidation in water-gas shift and hydrogen rich gas atmosphere subsequently, it can realize water gas shift reation CO conversion ratio higher than 98% at 300 DEG C, and at ambient temperature trace amounts of CO in hydrogen rich gas atmosphere can be converted into CO completely 2.

Claims (8)

1. a rhodium base catalyst, is characterized in that: take iron hydroxide as carrier, and Rh content is 0.2 ~ 5%, Rh average particle size of catalyst gross mass is 1nm.
2. a preparation method for catalyst described in claim 1, it is characterized in that catalyst adopts the preparation of glycol water coprecipitation, concrete preparation process is:
By the theoretical proportions of iron and Rh, soluble iron salting liquid and Rh precursor solution are mixed, in mixed liquor, iron speciation is 1 ~ 5%, dropwise joins in precipitant solution under stirring, the volume ratio of mixed liquor and precipitant solution is 1:1, regulate solution pH value to 8 ~ 9, stirring reaction, leave standstill aging, suction filtration, washing, dry, obtain final catalyst.
3. according to the preparation method of catalyst described in claim 2, it is characterized in that: described Rh presoma is radium chloride; Described molysite is ferric nitrate (Fe (NO 3) 39H 2o), soluble iron salting liquid and Rh precursor solution solvent for use are the aqueous solution of the ethylene glycol of volumetric concentration 20 ~ 75%; Described precipitant solution is the aqueous solution of 0.1 ~ 0.5mol/L NaOH.
4. according to the preparation method of catalyst described in claim 2, it is characterized in that: required reaction and aging temperature are 20 ~ 80 DEG C, 3 ~ 5 hours reaction time, ageing time 1 ~ 3 hour.
5. according to the preparation method of catalyst described in claim 2, it is characterized in that: the baking temperature of described catalyst is 60 ~ 120 DEG C.
6. an application for catalyst described in claim 1, is characterized in that: described catalyst can be used for CO selective oxidation in hydrogen rich gas atmosphere, will consist of 0.5 ~ 3vol%CO, 0.5 ~ 3vol%O 2, 20 ~ 40vol%H 2, all the other are the rich hydrogen unstripped gas of He, with air speed 1x10 4~ 1x10 5ml g cat -1h -1pass into and be equipped with in the fixed bed reactors of catalyst, measure the CO selective oxidation of catalyst in 20 ~ 140 DEG C of temperature under normal pressure active.
7. an application for catalyst described in claim 1, is characterized in that: described catalyst can be used for water gas shift reation, will consist of 0.5 ~ 5vol%CO, 0.5 ~ 5vol%H 2o, all the other are the unstripped gas of He, with air speed 1x10 4~ 1x10 5ml g cat -1h -1pass into and be equipped with in the fixed bed reactors of catalyst, measure catalyst CO water gas shift reation in 150 ~ 300 DEG C of temperature under normal pressure active.
8. according to the application of catalyst described in claim 6 or 7, it is characterized in that: need activation process before described catalyst application, condition is 1 ~ 100vol%H at 100 ~ 500 DEG C 2reduction 0.5 ~ 2h in/He, gas flow rate is 20 ~ 100ml/min.
CN201310670592.3A 2013-12-10 2013-12-10 Ferric hydroxide loaded rhodium-based catalyst and preparation and application thereof Pending CN104689829A (en)

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Publication number Priority date Publication date Assignee Title
CN106861684A (en) * 2015-12-10 2017-06-20 中国科学院大连化学物理研究所 A kind of titania oxide supported sub- nanometer rhodium catalyst and its preparation and application
CN107863544A (en) * 2017-09-29 2018-03-30 武汉市能智达科技有限公司 The minimizing technology and its removal device and fuel cell unit of a kind of carbon monoxide
CN115069242A (en) * 2022-05-05 2022-09-20 有研工程技术研究院有限公司 Catalyst for hydrogen production by oxidation and reforming of ethanol and preparation and activation methods thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106861684A (en) * 2015-12-10 2017-06-20 中国科学院大连化学物理研究所 A kind of titania oxide supported sub- nanometer rhodium catalyst and its preparation and application
CN106861684B (en) * 2015-12-10 2019-07-12 中国科学院大连化学物理研究所 A kind of titania oxide supported sub-nanometer rhodium catalyst and its preparation and application
CN107863544A (en) * 2017-09-29 2018-03-30 武汉市能智达科技有限公司 The minimizing technology and its removal device and fuel cell unit of a kind of carbon monoxide
CN115069242A (en) * 2022-05-05 2022-09-20 有研工程技术研究院有限公司 Catalyst for hydrogen production by oxidation and reforming of ethanol and preparation and activation methods thereof

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