CN101199929A - Macroporous Pt/CeO2 catalyst for water gas shift reaction and preparing process thereof - Google Patents
Macroporous Pt/CeO2 catalyst for water gas shift reaction and preparing process thereof Download PDFInfo
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- CN101199929A CN101199929A CNA2007100601395A CN200710060139A CN101199929A CN 101199929 A CN101199929 A CN 101199929A CN A2007100601395 A CNA2007100601395 A CN A2007100601395A CN 200710060139 A CN200710060139 A CN 200710060139A CN 101199929 A CN101199929 A CN 101199929A
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Abstract
The invention discloses a macroporous Pt/CeO2 catalyst used for water-gas shifting reaction and the preparation method, belonging to the catalyst technology used for water-gas shifting reaction. The catalyst uses three-dimensionally ordered macroporous oxide CeO2 as carrier and supported platinum as active ingredient, whose mass content accounts for 0.5-5% that of the catalyst. The preparation method includes the following steps: by taking polystyrene as template and Ce solution as supported platinum, after repeated times of impregnation of the template and temperature-programmed calcinations, three-dimensionally ordered macroporous oxide CeO2 is well prepared; by impregnating the macroporous CeO2 into H2PtC16 solution, the three-dimensionally ordered macroporous Pt/CeO2 catalyst is prepared after being dried and roasted. The invention has the advantages that the preparation process is simple and practical; the catalyst prepared by the invention is of high activity, good selectivity and stability in water-gas shifting reaction.
Description
Technical field
The present invention relates to be used for the macroporous Pt/CeO of water gas shift reaction
2Catalysts and its preparation method belongs to the catalyst technology that water gas shift reaction is used.
Background technology
Water gas shift reaction is an industrial important reaction, and it can make carbon monoxide and steam reaction in the syngas for synthetic ammonia, is transformed into CO
2And H
2, therefore in synthetic ammonia, synthesizing methanol, hydrogen manufacturing and town gas industry, have a wide range of applications.In recent years, along with the development of fuel cell hydrogen producing technology, water gas shift reaction has had new application background again.It can reduce the CO in the reformation gas, increases H simultaneously
2Content, so water gas shift reaction becomes the focus of research once more.
Three-dimensional ordered macroporous oxide is because having the duct of rule arranges, and the characteristics of aperture between hundreds of nanometer to tens micron are so obtain in recent years paying close attention to aspect catalysis.Three-dimensional ordered macroporous oxide as catalyst or carrier have that pressure drop is low, the advantage of mass transfer, good heat-transfer.If it is prepared into integral catalyzer, can significantly reduce the volume of catalytic reactor, raise the efficiency.
Research at present or the water-gas shift reaction catalyst of using have:
(1) beaded catalyst
Traditional high temperature conversion catalyst is the Fe-Cr HTS catalyst, its active phase Fe
3O
4Be spinel structure, Cr
2O
3Structural promoter as main is evenly dispersed in Fe
3O
4Between the particle and suppressed Fe
3O
4Growing up of particle, the Fe-Cr HTS catalyst also is called Fe
3O
4-Cr
2O
3Spinel solid solution.This catalyst have active wide temperature range, Heat stability is good, life-span long, certain poison resistance, advantage such as cheap and easy to get arranged.Its shortcoming is that activity is lower, and energy consumption is big.Copper zinc is that low temperature conversion catalyst is industrial low change catalyzer, it has active height, inhibition side reaction ability is strong, be the low change catalyzer of topic before having most, but the shortcoming of maximum is a poor heat resistance, easily sintering takes place and inactivation, and run into the easy spontaneous combustion of air when transformationreation surpasses 280 ℃.
Except that the water-gas shift reaction catalyst of these two kinds of industrial uses, the catalyst of having reported also has following several classes.
1. M/Ce0
2Catalyst series
M/Ce0
2In M acute pyogenic infection of finger tip metal, this class catalyst be research focus.Ce0
2In cleaning catalyst for tail gases of automobiles, obtained using widely as important co-catalyst, it is significant for the transformation efficiency that improves vehicle exhaust that it stores the oxygen ability, and its high-temperature stability has also prolonged the life-span of auto-exhaust catalyst greatly.In recent years, CeO
2Also in the research of the required transformation catalyst of mobile reformation hydrogen production, obtained attention.The Gorte of U.S. Pennsylvania university etc.
[1,2]Studied CeO
2Support catalyst such as Pt, Pd, Rh, Co, Fe at CO-H
2Transformationreation dynamics in the O-Ar gas and deactivation mechanism are also pointed out CeO
2Oxygen storage capacity be the key factor that influences this type of catalyst shift activity.Fu etc.
[3]Studied the shift activity of Au-Ce (La) the Ox catalyst that adopts co-precipitation and deposition-distinct methods such as precipitation preparation, the result slightly is better than Cu-Ce (La) Ox catalyst, and its activity and H
2-TPR test result has correlation preferably.Fu etc. think the OSC and the CeO of Au-Ce (La) Ox catalyst
2Grain size relevant, and little with the grain size correlation of Au.Because have problems such as the higher and stability of cost has much room for improvement, this class catalyst is all in development.
2. composite oxides transformation catalyst
Myers etc.
[4]Transformation catalysts such as copper catalyst Cu that the V-Co composite oxides support and other composite oxide of metal have been studied.Wherein composite oxides carry the Cu catalyst and have obtained good result, can be at ingress of air below 300 ℃ and non-inactivation keeps active constant also basic after the contact of subcooling condensate, and also catalyst need not at H
2Middle prereduction.Based on the experimental result that composite oxides carry the Cu catalyst, the consumption that calculates transformation catalyst in the mobile hydrogen making system is 0.15L/kW (0.14kg/kW), and cost is $0.9/kW.But the not anti-sulphur of this catalyst is containing 43ppmH
2Complete deactivation behind the operation 40h in the reformation gas of S, conversion ratio is reduced to below 10% from 63%.
3. other carried metal type transformation catalysts
The Igarashi of SUNX company etc.
[5]Invented Pt/ZrO
2Transformation catalyst, this catalyst can (200～400 ℃) operation in wider temperature range.But, use the content of noble metal higher in this patent, Pt content is lower in 3% activity of such catalysts when following.The Aoyama of Toyota Motor Corporation etc. and Yamazaki etc. have invented Pt/TiO
2Transformation catalyst is at unstripped gas 1.8%CO-10%H
2O-88.2%N
2In, air speed is 200000h
-1The time, surpass 90% at conversion ratio more than 350 ℃,, still lower when surpassing 400 ℃ in activity below 300 ℃ near equilibrium conversion.
(2) integer catalyzer
Compare with beaded catalyst, integer catalyzer has following advantage: pressure drop is low, intensity is high, startup is fast, mechanical strength is high and Heat stability is good.Integer catalyzer is widely used in the processes such as the removing of purifying vehicle exhaust, VOC, catalytic combustion and nitric acid industry NOX tail gas clean-up at present.Characteristics such as its low pressure drop, high flux be other form catalyst can not compare.As the part of mobile hydrogen making system, because transformationreation is lower with respect to the kinetic rate of other reaction, so the volume of shift-converter is just very big, the pressure drop of this part accounts for a big chunk of whole system.Integer catalyzer is used for the existing bibliographical information of water gas shift reaction.Though integral catalyzer particularly microreactor has clear superiority, its volume is still bigger.
The volume that integral catalyzer will significantly dwindle catalytic reactor then in nanoscale scope (tens nanometers are to the hundreds of nanometer), is therefore made with large pore material in the hole wall of large pore material and aperture, raises the efficiency.On the other hand, the hole of large pore material (3DOM) is regularly arranged, and than big two to three orders of magnitude in the hole in the general beaded catalyst, so the pressure when gas passes falls little.Therefore large pore material is prepared into integral catalyzer and is used for the optimal path that hydrogen manufacturing is likely the miniaturization of solution fuel cell hydrogen source system.This is new trial and exploration, and up to the present large pore material does not appear in the newspapers as yet as catalyst for preparing hydrogen or catalyst carrier.
List of references
[1]Bunluesin?T，Gorte?R?J.and?Graham?G?W.Studies?of?the?water-gas-shiftreation?on?ceria-supported?Pt，Pd?and?Rh：implications?for?oxygen-storage?properties.Appl.Catal.B，1998，15：107-114
[2]Hilaire?S，Wang?X，Luo?T，Gorte?R?J，Wagner?J.A?comparative?study?of?water-gas-shiftreaction?over?ceria?supported?metallic?catalysts.Appl.Catal.A，2001，215：271-278
[3]Wang?X，Gorte?R?J，Wagner?J?P.Deactivation?Mechanisms?for?Pd/Ceria?during?the?Water-Gas-ShiftReaction.J.Catal.，2002，212：225-230
[4]Luo?T，Gorte?R?J.A?mechanistic?study?of?sulfur?poisoning?of?the?water-gas-shift?react?ion?over?Pd/ceria.Catal.Lett.，2003，85：139-146
[5]Wang?X，Gorte?R?J.The?effect?of?Fe?and?other?promoters?on?the?activity?of?Pd/ceria?for?the?water-gas?shiftreaction.Appl.Catal.A，2003，8543：1-6
Summary of the invention
The object of the present invention is to provide a kind of macroporous Pt/CeO that is used for water gas shift reaction
2Catalysts and its preparation method, this catalyst are used for water gas reaction and have low, the active height of pressure drop, and its preparation method process is simple.
The present invention is realized by following technical proposals, a kind of macroporous Pt/CeO that is used for water gas shift reaction
2Catalyst is characterized in that, this catalyst is 500nm～10um macropore CeO with the aperture
2Be carrier, the active component of load is a platinum on the carrier, load capacity be catalyst quality be 0.5～5%.
Above-mentioned Preparation of catalysts method is characterized in that comprising following process:
1) adopt emulsion polymerization to prepare masterplate:
With styrene is monomer, and adding quality is the sodium peroxydisulfate initator of monomer 0.1～2%, and polymerization is after 8～24 hours in 60～80 ℃ of water-baths, and it is dry more than 12 hours that polymer is put into drying box.Template 100～120 ℃ of following heat treatments, is strengthened the mechanical strength of template.
2) macropore CeO
2Preparation:
With Ce (NO
3)
36H
2O is the cerium source, add mole is that 0.2～0.4 times citric acid of cerium mole is a chelating agent, joins in the absolute ethyl alcohol, is stirred to be transparent color.The polystyrene moulding that step 1) is made is immersed in this solution, dipping 5～20min final vacuum filters, drying, repeat above-mentioned dipping one then to filter-dry run 3～4 times, heating rate with 0.1～5 ℃/min is warming up to 500～700 ℃ in the tubular type Muffle furnace then, constant temperature calcining 2～4h obtains three-dimensional ordered macroporous CeO
2
3) load active component:
Get the H that concentration is 0.03～0.1mol/L
2PtCl
6, regulating pH value is 1～5, with step 2) and the three-dimensional ordered macroporous CeO for preparing
2Incipient impregnation is at H
2PtCl
6, then 20～25 ℃ of dryings, more than 12 hours,, obtain the CeO that carrier is aperture 500nm～10um in 70～80 ℃ of dryings more then 400～600 ℃ of roastings
2, active component is Pt, its mass content is 0.5～5% Pt/CeO
2Catalyst.
The invention has the advantages that preparation process is simple, the macroporous catalyst Pt/CeO that makes
2Be used for the characteristics that water gas reaction has low, active height of pressure drop and good stable.
Description of drawings:
Fig. 1 is the embodiment of the invention 1 prepared macroporous catalyst Pt/CeO
2Stereoscan photograph.
Fig. 2 is the embodiment of the invention 1 prepared macroporous catalyst Pt/CeO
2X-ray diffractogram.
Fig. 3 is the embodiment of the invention 1 prepared catalyst Pt/CeO
2With particle Pt/CeO
2The CO conversion ratio vary with temperature curve map.
The specific embodiment
Embodiment 1:
Get 20ml styrene (for several times), be added drop-wise in 110mL deionized water and the 60mL ethanol solution, stir while dripping with the washing of 0.1mol/LNaOH and deionized water, evenly after, adding 10mL initator sodium peroxydisulfate concentration is 0.068mol/L.After stirring 24 hours under 70 ℃, put into drying box dry 12 hours.Template 110 ℃ of following heat treatments 10 minutes, is strengthened the mechanical strength of template.
Get 9.118gCe (NO
3)
36H
2O joins in the 20mL absolute ethyl alcohol, adds the 2.206g citric acid again, is stirred to be transparent color.Polystyrene moulding is flooded this solution, 5 minutes final vacuum suction filtrations, drying is 2 hours in 70 ℃ of drying boxes.Repeat above-mentioned dipping-suction filtration-dry run then 4 times, then in the tubular type Muffle furnace with 2 ℃/min temperature programming to 550 ℃, constant temperature calcining 4 hours obtains three-dimensional ordered macroporous CeO
2Carrier.
Get the H that concentration is 0.07mol/L
2PtCl
6LmL, adding absolute ethyl alcohol adjusting pH value is 1, with the macropore CeO of above-mentioned preparation
2The carrier incipient impregnation is to H
2PtCl
6In, 20 ℃ of dryings, more than 12 hours, 500 ℃ of roastings of temperature 3 hours, obtain the CeO that the carrier average pore size is 700nm in 75 ℃ of dryings then again
2, active component is Pt, its mass content is 3% Pt/CeO
2Catalyst.
With the above-mentioned catalyst screening that makes, getting granularity is 60-100 purpose catalyst 50mg, carries out performance test on the fixed bed quartz tube reactor.The quartz ampoule specification is Φ 8 * 2, and the unstripped gas air speed is 120,000mL/hg
CatUnstripped gas consists of: 3vol.%CO, 10vol.%H
2O, 87vol.%N
2Sample rises to 400 ℃ from room temperature, uses 10vol.%H
2-N
2Reduced 1 hour, then at N
2Purging drops to 200 ℃, feeds unstripped gas and reacts.Reaction temperature is from 200 ℃ to 400 ℃, and every intensification is a reflecting point for 50 ℃, each temperature spot reaction 1 hour.Adopt the on-line analysis of SP-2100 type gas-chromatography, the TDX-502 post, TCD detects.The CO conversion ratio reached 90% when catalyst test the results are shown in 3,350 ℃ in accompanying drawing.
Embodiment 2:
Press the preparation process among the embodiment 1, change H
2PtCl
6Concentration is 0.023mol/L, and preparation Pt load capacity is 1% a catalyst of catalyst quality.Carry out the water gas shift reaction performance test with this catalyst, test condition is with embodiment 1.Its result is, activity of such catalysts is a little less than activity of such catalysts among the embodiment 1, and the CO conversion ratio reaches 80% in the time of 350 ℃.
Embodiment 3:
Press the preparation process among the embodiment 1, change H
2PtCl
6Concentration is 0.12mol/L, and preparation Pt load capacity is 5% a catalyst of catalyst quality.Carry out the water gas shift reaction performance test with this catalyst, test condition is with embodiment 1.Its result is, activity of such catalysts is starkly lower than activity of such catalysts among the embodiment 1, and conversion ratio reaches 60% in the time of 350 ℃.
Embodiment 4:
Press the preparation process among the embodiment 1, the sintering temperature of catalyst carrier is 500 ℃.Carry out the water gas shift reaction performance test with this catalyst, test condition is with embodiment 1.Its result is, activity of such catalysts is lower than activity of such catalysts among the embodiment 1, and conversion ratio reaches 70% in the time of 350 ℃.
Embodiment 5:
Press the preparation process among the embodiment 1, the sintering temperature of catalyst carrier is 600 ℃.Carry out the water gas shift reaction performance test with this catalyst, test condition is with embodiment 1.Its result is, activity of such catalysts is a little more than activity of such catalysts among the embodiment 1, and conversion ratio reaches equilibrium conversion in the time of 350 ℃.
Comparative Examples:
Adopt particle Pt/CeO
2Catalyst (average grain diameter is 10nm) carries out the Water gas shift/WGS active testing, and experiment condition is with embodiment 1.Wherein the CO conversion ratio can only reach 60%, and as seen, activity of such catalysts of the present invention is apparently higher than granular pattern Pt/CeO
2Catalyst.
Claims (2)
1. macroporous Pt/CeO who is used for water gas shift reaction
2Catalyst is characterized in that, this catalyst is the CeO of 500nm～10um with the aperture
2Be carrier, the active component of load is a platinum on the carrier, load capacity be catalyst quality be 0.5～5%.
2. one kind prepares the described macroporous Pt/CeO2 catalyst method that is used for water gas shift reaction of claim 1, it is characterized in that comprising following process:
1) adopt emulsion polymerization to prepare masterplate:
With styrene is monomer, add quality and be 0.1～2% sodium peroxydisulfate initator of monomer mass, polymerization is after 8～24 hours in 60～80 ℃ of water-baths, and it is dry more than 12 hours that polymer is put into drying box, template 100～120 ℃ of following heat treatments, is strengthened the mechanical strength of template;
2) macropore CeO
2Preparation:
With Ce (NO
3)
36H
2O is the cerium source, add mole is that 0.2～0.4 times citric acid of cerium mole is a chelating agent, join in the absolute ethyl alcohol, be stirred to and be transparent color, the polystyrene moulding that step 1) is made is immersed in this solution, dipping 5～20min final vacuum filters, drying, repeats above-mentioned dipping-filter-dry run then 3～4 times, and the heating rate with 0.1～5 ℃/min is warming up to 500～700 ℃ in the tubular type Muffle furnace then, constant temperature calcining 2～4h obtains three-dimensional ordered macroporous CeO
2
3) load active component:
Get the H that concentration is 0.03～0.1mol/L
2PtCl
6, regulating pH value is 1～5, with step 2) and the three-dimensional ordered macroporous CeO for preparing
2Incipient impregnation is at H
2PtCl
6, then 20～25 ℃ of dryings, more than 12 hours,, obtain the CeO that the aperture is 500nm～10um in 70～80 ℃ of dryings more then 400～600 ℃ of roastings
2Be carrier, the mass content of active component Pt is 0.5～5% Pt/CeO
2Catalyst.
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| CN111565837B (en) * | 2018-02-27 | 2023-08-22 | N.E.化学株式会社 | Ternary catalyst for purifying exhaust gas, method for producing same, and integrated exhaust gas purifying catalyst |
| CN108940306A (en) * | 2018-06-25 | 2018-12-07 | 广东工业大学 | A kind of ordered porous PtCu/CeO2Catalyst and its preparation method and application |
| CN108940306B (en) * | 2018-06-25 | 2021-02-12 | 广东工业大学 | Ordered porous PtCu/CeO2Catalyst, preparation method and application thereof |
| WO2021078308A1 (en) * | 2019-10-23 | 2021-04-29 | 广东工业大学 | Three-dimensionally ordered macroporous oxygen-deficient cerium dioxide catalyst and preparation method and use therefor |
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