CN103464134B - Carbon dioxide decomposition prepares the catalyst of carbon monoxide and method for making and application - Google Patents
Carbon dioxide decomposition prepares the catalyst of carbon monoxide and method for making and application Download PDFInfo
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- CN103464134B CN103464134B CN201310392872.2A CN201310392872A CN103464134B CN 103464134 B CN103464134 B CN 103464134B CN 201310392872 A CN201310392872 A CN 201310392872A CN 103464134 B CN103464134 B CN 103464134B
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Abstract
The catalyst that carbon dioxide decomposition prepares carbon monoxide to adulterate the composite metal oxide obtained to cerium zirconium sosoloid with Mg, Ca, and its chemical composition general formula is expressed as: Ce
0.8-xzr
0.2m
xo
2-x, the wherein molar fraction of x=0.02-0.1, M to be doping metals Mg or Ca, x be doping metals.The present invention has high activity, high thermal stability, the advantage that the life-span is long.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method and application, relate to a kind of thermochemical cycles reaction carbon dioxide decomposition specifically and prepare CO catalyst and preparation method and application.
Technical background
A large amount of consumption of fossil energy result in a large amount of discharges of CO2.As the topmost greenhouse gases of one, CO2 is also a kind of carbon, oxygen resource of cheapness, and its chemical utilization has attracted the concern of more and more researcher.Utilize the heat chemistry CO that high temperature solar thermal energy carries out
2decomposition Cycle reaction can obtain CO, effectively can also realize the efficient cascade utilization of solar heat thus realize the green syt of organic chemicals, therefore and gradually becoming the focus of research at present.The reaction principle of this circular response is: (1400-1600 DEG C) carries out the thermal reduction reaction of higher valence metal oxide first at relatively high temperatures, discharges O
2; Then CO is carried out at a lower temperature with the oxide of reduction-state
2decomposition reaction, generates CO and higher valence metal oxide, and high oxide enters first step reaction realization response circulation again.
MO
x→ MO
x-y+ y/2 O
2(thermal reduction reaction)
MO
x-y+ y CO
2→ MO
x+ y CO (CO
2decomposition reaction)
CO
2→ CO+1/2 O
2(overall reaction)
In such course of reaction, reaction institute calorific requirement can be provided by solar energy, and the metal oxide used can constantly recycle.Product C O is a kind of important platform chemicals, and may be used for synthetic liquid fuel and various chemicals, tool has been widely used.Thus, this reaction is significant to the dependence aspect of fossil energy for minimizing CO2 emission, promotion carbon cycle and minimizing.At present, for CO
2the oxidation-reduction system of high-temperature decomposition reaction mainly contains ZnO/Zn, Fe
3o
4/ FeO and CeO
2/ Ce
2o
3deng.The subject matter that these redox systems exist has: ZnO/Zn easily distils, and must carry out quenching, to prevent it again oxidized in course of reaction to thermal reduction product Zn steam; Fe
3o
4the fusing point of/FeO is lower, and thermal reduction high temperature very easily makes material sintering deactivation; CeO
2/ Ce
2o
3thermal reduction rate lower, and then cause CO output lower, and reaction temperature is also higher.Therefore, the CO of new high reaction activity is studied
2decomposing material has certain necessity and realistic meaning.
CeO
2be a kind of metal oxide that can be used for thermal chemical reaction, and certain stability can be kept in longer circular response.But, CeO
2thermal reduction temperature higher, easily because sintering causes reactivity to decline in course of reaction.Research finds: with another metal (mainly Zr) to CeO
2carry out doping and can reduce reaction temperature, improve reactivity simultaneously.In addition, the third metal of bibliographical information (Y, La and Ga) is had to adulterate the atomic arrangement can upset in solid solution to cerium zirconium sosoloid, and then produce mobility (the Journal of Catalysis of oxygen vacancies, raising oxygen atom, 1997,171,160-168).These materials also can improve the thermochemical cycles reactivity worth (The Journal of Physical Chemistry C, 2012,116,13516-13523) of cerium zirconium sosoloid.Meanwhile, the diffusion path of material oxygen atom in circular response that grain diameter is less is also shorter, is thus conducive to the reaction rate and the CeO that improve two-step reaction
2utilization rate.But under template existent condition, the height surface of preparing with common coprecipitation, small-particulate materials do not have high-temperature thermal stability, be easy to cave in, thus make material inactive in the structure of the material under high temperature of thermal chemical reaction.
Summary of the invention
For the shortcoming of prior art, the object of this invention is to provide a kind of high activity, high thermal stability, carbon dioxide pyrolytic CO catalyst that the life-span is long and its preparation method and application.
The present invention adulterates to cerium zirconium sosoloid with Mg, Ca, obtains the material with high thermal stability and oxygen atom flow rate.Meanwhile, make template by adding P123 in coprecipitation process, then obtain the material with high-ratio surface and high thermal stability in conjunction with follow-up hydrothermal treatment process.This material can improve CO output and circular response stability simultaneously.
Catalyst of the present invention to adulterate the composite metal oxide obtained to cerium zirconium sosoloid with Mg, Ca, and its chemical composition general formula is expressed as: Ce
0.8-xzr
0.2m
xo
2-x, the wherein molar fraction of x=0.02-0.1, M to be doping metals Mg or Ca, x be doping metals.
The preparation method of catalyst of the present invention comprises the steps:
Method one: catalyst adopts coprecipitation preparation, all metallic elements are all dissolved in deionized water with the form of nitrate, mixed aqueous solution is made into by catalyst proportion of composing, co-precipitation is carried out with the alkali of 0.5-1.5 mol/L concentration and mixed aqueous solution at 50-80 DEG C, precipitation process needs fully to stir, maintenance pH value of solution is 8-12, continue after precipitation to stir aging 2-6h at 50-80 DEG C, precipitate with deionized water is fully washed, then dry at 80-120 DEG C, at 600-800 DEG C, roasting 2-4h, obtains catalyst.
Method two: catalyst adopts hydro-thermal method preparation, the nitrate of P123 and all metallic elements is dissolved in deionized water, mixed aqueous solution is made into by catalyst proportion of composing, wherein every 0.01 mol cerous nitrate uses 0.5-2 g P123 to make template, co-precipitation is carried out with the alkali of 0.5-1.5 mol/L concentration and mixed aqueous solution at 50-80 DEG C, precipitation process needs fully to stir, maintenance pH value of solution is 8-12, continue after precipitation to stir aging 2-6 h at 50-80 DEG C, precipitate with deionized water is fully washed, washing postprecipitation is distributed in deionized water, hydrothermal treatment consists 12-24 h at 120-160 DEG C, after hydro-thermal reaction terminates, naturally cool to room temperature at ambient temperature, resulting materials is dry at 80-120 DEG C after suction filtration, roasting 4-8h at 500-800 DEG C, obtain catalyst.
Alkali in method one described above and method two is NaOH, KOH or NH
3h
2o.
Catalyst application of the present invention is in fixed bed reactors, and concrete course of reaction is: catalyst is warming up in an ar atmosphere 1200-1400 DEG C and carries out thermal reduction reaction, and the reaction time is 40-60 min; Be cooled to 800-1100 DEG C under an ar atmosphere afterwards; CO is passed at 800-1100 DEG C
2carry out CO
2decomposition reaction, the reaction time is 40-60 min; In Ar gas, be warming up to 1200-1400 DEG C more afterwards, two-step reaction constantly circulates and carries out under such variations in temperature condition, and two-step reaction carries out all at ambient pressure.
O in product of the present invention
2detect with CO gas analyzer.
The present invention compared with prior art tool has the following advantages:
1) this catalyst has higher heat endurance and oxygen atom flow rate faster, can show reaction rate, higher CO output and circular response stability preferably faster in thermochemical reaction process.
2) this catalyst also has higher specific area simultaneously, can realize CO at a lower temperature
2decomposition Cycle is reacted.Significantly can reduce CO like this
2decomposition temperature, contributes to the energy conversion efficiency improving reaction and the requirement reduced reactor structure material.Thus, this catalyst has good application prospect.
3) because this catalyst has above characteristics, thus also other oxidation-reduction reactions are likely applied to, as: two step reforming reactions of Thermochemical Generation of Hydrogen from Water reaction, three-way catalyst, methane-water and chemical looping combustion etc.
4) method for preparing catalyst is relatively simple, easily operate, and catalyst performance repeatability is relatively good, is easy to realize industry and amplifies.
Detailed description of the invention
Embodiment 1. is by following metallic atom molar ratio mixed aqueous solution: each element of Ce0.78Zr0.2Mg0.02(is all dissolved in the middle of deionized water with the form of nitrate and forms mixed aqueous solution), NaOH is made into 1 mol/L precipitant solution.At 80 DEG C, two solution carry out co-precipitation, precipitation process needs fully to stir, keep pH=10, aging 2 h under 80 DEG C of stirring conditions, precipitate with deionized water is fully washed, dry and 800 DEG C of roasting 2h at 80 DEG C, obtain this metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Ce): n (Zr): n (Mg)=0.78:0.2:0.02, it is fully ground.The carbon dioxide decomposition circular response of catalyst of the present invention carries out on fixed bed reactors.Concrete course of reaction is: catalyst is warming up in an ar atmosphere 1400 DEG C and carries out thermal reduction reaction, and the reaction time is 60 min; Be cooled to 1100 DEG C under an ar atmosphere afterwards; CO is passed at 1100 DEG C
2carry out CO
2decomposition reaction, the reaction time is 60 min; 1400 DEG C are warming up to again afterwards in Ar gas.Two-step reaction constantly circulates and carries out under such variations in temperature condition, and two-step reaction carries out all at ambient pressure.O in product
2detect with CO gas analyzer, in twice circular response carried out, acquired results is as follows:
Embodiment 2. is by following metallic atom molar ratio mixed aqueous solution: each element of Ce0.7Zr0.2Mg0.1(is all dissolved in the middle of deionized water with the form of nitrate and forms mixed aqueous solution), potassium hydroxide is made into 0.5 mol/L precipitant solution.At 60 DEG C, two solution carry out co-precipitation, precipitation process needs fully to stir, keeping pH=8, aging 6 h under 60 DEG C of stirring conditions, precipitating through fully washing by deionized water, dry and 700 DEG C of roasting 4 h at 100 DEG C, obtain this metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Ce): n (Zr): n (Mg)=0.7:0.2:0.1, it is fully ground.The carbon dioxide decomposition circular response of catalyst of the present invention carries out on fixed bed reactors.Concrete course of reaction is: catalyst is warming up in an ar atmosphere 1400 DEG C and carries out thermal reduction reaction, and the reaction time is 40 min; Be cooled to 800 DEG C under an ar atmosphere afterwards; CO is passed at 800 DEG C
2carry out CO
2decomposition reaction, the reaction time is 40 min; 1400 DEG C are warming up to again afterwards in Ar gas.Two-step reaction constantly circulates and carries out under such variations in temperature condition, and two-step reaction carries out all at ambient pressure.O in product
2detect with CO gas analyzer, in twice circular response carried out, acquired results is as follows:
Embodiment 3. is by following metallic atom molar ratio mixed aqueous solution: each element of Ce0.75Zr0.2Ca0.05(is all dissolved in the middle of deionized water with the form of nitrate and forms mixed aqueous solution), ammoniacal liquor is made into 1.5 mol/L precipitant solution.At 50 DEG C, two solution carry out co-precipitation, precipitation process needs fully to stir, keep pH=12, aging 6 h under 50 DEG C of stirring conditions, precipitate with deionized water is fully washed, dry and 600 DEG C of roasting 4h at 120 DEG C, obtain this metal oxide catalyst, the metallic atom mol ratio of this catalyst is: n (Ce): n (Zr): n (Ca)=0.75:0.2:0.05, it is fully ground.Carbon dioxide pyrolysis cycles reaction condition is with example 2, and acquired results is as follows:
The nitrate of P123 and all elements is dissolved in deionized water and is made into mixed aqueous solution (0.01 mol cerous nitrate uses 0.5 g P123 to make template) by embodiment 4., and metallic atom mol ratio is Ce0.7Zr0.2Ca0.1.At 80 DEG C, carry out co-precipitation with NaOH (1 mol/L) and above-mentioned mixed aqueous solution, precipitation process needs fully to stir, and keeps pH value of solution to be 10.After precipitation under 80 DEG C of stirring conditions aging 2 h, precipitate with deionized water is fully washed.Above-mentioned precipitation is distributed in deionized water, hydrothermal treatment consists 24 h at 120 DEG C.After hydro-thermal reaction terminates, under reactor being placed room temperature condition, naturally cool to room temperature.Resulting materials is dry at 80 DEG C after suction filtration, and roasting 6h at 600 DEG C, the metallic atom mol ratio finally obtaining catalyst is: n (Ce): n (Zr): n (Ca)=0.7:0.2:0.1, it is fully ground.The carbon dioxide decomposition circular response of catalyst of the present invention carries out on fixed bed reactors.Concrete course of reaction is: catalyst is warming up in an ar atmosphere 1400 DEG C and carries out thermal reduction reaction, and the reaction time is 40 min; Be cooled to 1100 DEG C under an ar atmosphere afterwards; CO is passed at 1100 DEG C
2carry out CO
2decomposition reaction, the reaction time is 40 min; 1400 DEG C are warming up to again afterwards in Ar gas.Two-step reaction constantly circulates and carries out under such variations in temperature condition, and two-step reaction carries out all at ambient pressure.O in product
2detect with CO gas analyzer, in twice circular response carried out, acquired results is as follows:
The nitrate of P123 and all elements is dissolved in deionized water and is made into mixed aqueous solution (0.01 mol cerous nitrate uses 1g P123 to make template) by embodiment 5., and metallic atom mol ratio is Ce0.75Zr0.2Mg0.05.At 50 DEG C, carry out co-precipitation with potassium hydroxide (0.5 mol/L) and above-mentioned mixed aqueous solution, precipitation process needs fully to stir, and keeps pH value of solution to be 8.After precipitation under 50 DEG C of stirring conditions aging 6 h, precipitate with deionized water is fully washed.Above-mentioned precipitation is distributed in deionized water, hydrothermal treatment consists 18 h at 140 DEG C.After hydro-thermal reaction terminates, under reactor being placed room temperature condition, naturally cool to room temperature.Resulting materials is dry at 100 DEG C after suction filtration, and roasting 4h at 700 DEG C, the metallic atom mol ratio finally obtaining catalyst is: n (Ce): n (Zr): n (Mg)=0.75:0.2:0.05, it is fully ground.The carbon dioxide decomposition circular response of catalyst of the present invention carries out on fixed bed reactors.Concrete course of reaction is: catalyst is warming up in an ar atmosphere 1400 DEG C and carries out thermal reduction reaction, and the reaction time is 40min; Be cooled to 1000 DEG C under an ar atmosphere afterwards; CO is passed at 1000 DEG C
2carry out CO
2decomposition reaction, the reaction time is 40min; 1400 DEG C are warming up to again afterwards in Ar gas.Two-step reaction constantly circulates and carries out under such variations in temperature condition, and two-step reaction carries out all at ambient pressure.O in product
2detect with CO gas analyzer, in three circular responses carried out, acquired results is as follows:
The nitrate of P123 and all elements is dissolved in deionized water and is made into mixed aqueous solution (0.01 mol cerous nitrate uses 2 g P123 to make template) by embodiment 6., and metallic atom mol ratio is Ce0.75Zr0.2Ca0.05.At 60 DEG C, carry out co-precipitation with ammoniacal liquor (1.5 mol/L) and above-mentioned mixed aqueous solution, precipitation process needs fully to stir, and keeps pH value of solution to be 12.After precipitation under 60 DEG C of stirring conditions aging 6 h, precipitate with deionized water is fully washed.Above-mentioned precipitation is distributed in deionized water, hydrothermal treatment consists 12 h at 160 DEG C.After hydro-thermal reaction terminates, under reactor being placed room temperature condition, naturally cool to room temperature.Resulting materials is dry at 120 DEG C after suction filtration, and roasting 8 h at 500 DEG C, the metallic atom mol ratio finally obtaining catalyst is: n (Ce): n (Zr): n (Ca)=0.75:0.2:0.05, it is fully ground.Carbon dioxide pyrolysis cycles reaction condition is with example 5.Acquired results is as follows:
Embodiment 7. preparation method is equal to example 5, and the metallic atom mol ratio of catalyst is: n (Ce): n (Zr): n (Mg)=0.75:0.2:0.05.The carbon dioxide decomposition circular response of catalyst of the present invention carries out on fixed bed reactors.Concrete course of reaction is: catalyst is warming up in an ar atmosphere 1200 DEG C and carries out thermal reduction reaction, and the reaction time is 60 min; Be cooled to 1000 DEG C under an ar atmosphere afterwards; CO is passed at 1000 DEG C
2carry out CO
2decomposition reaction, the reaction time is 40 min; 1200 DEG C are warming up to again afterwards in Ar gas.Two-step reaction constantly circulates and carries out under such variations in temperature condition, and two-step reaction carries out all at ambient pressure.O in product
2detect with CO gas analyzer, in twice circular response carried out, acquired results is as follows:
Embodiment 8. preparation method is equal to example 6, and the metallic atom mol ratio of catalyst is: n (Ce): n (Zr): n (Ca)=0.75:0.2:0.05.Carbon dioxide pyrolysis cycles reaction condition is with example 7.Acquired results is as follows:
Claims (3)
1. carbon dioxide decomposition prepares a catalyst for carbon monoxide, and it is characterized in that catalyst to adulterate the composite metal oxide obtained to cerium zirconium sosoloid with Mg, Ca, its chemical composition general formula is expressed as: Ce
0.8-xzr
0.2m
xo
2-x, the wherein molar fraction of x=0.02-0.1, M to be doping metals Mg or Ca, x be doping metals;
And prepare by the following method:
Method one: catalyst adopts coprecipitation preparation, all metallic elements are all dissolved in deionized water with the form of nitrate, mixed aqueous solution is made into by catalyst proportion of composing, co-precipitation is carried out with the alkali of 0.5-1.5 mol/L concentration and mixed aqueous solution at 50-80 DEG C, precipitation process needs fully to stir, maintenance pH value of solution is 8-12, continue after precipitation to stir aging 2-6h at 50-80 DEG C, precipitate with deionized water is fully washed, then dry at 80-120 DEG C, at 600-800 DEG C, roasting 2-4h, obtains catalyst;
Method two: catalyst adopts hydro-thermal method preparation, the nitrate of P123 and all metallic elements is dissolved in deionized water, mixed aqueous solution is made into by catalyst proportion of composing, wherein every 0.01 mol cerous nitrate uses 0.5-2 g P123 to make template, co-precipitation is carried out with the alkali of 0.5-1.5 mol/L concentration and mixed aqueous solution at 50-80 DEG C, precipitation process needs fully to stir, maintenance pH value of solution is 8-12, continue after precipitation to stir aging 2-6 h at 50-80 DEG C, precipitate with deionized water is fully washed, washing postprecipitation is distributed in deionized water, hydrothermal treatment consists 12-24 h at 120-160 DEG C, after hydro-thermal reaction terminates, naturally cool to room temperature at ambient temperature, resulting materials is dry at 80-120 DEG C after suction filtration, roasting 4-8h at 500-800 DEG C, obtain catalyst.
2. a kind of carbon dioxide decomposition as claimed in claim 1 prepares the preparation method of the catalyst of carbon monoxide, it is characterized in that the alkali in described method one and method two is NaOH, KOH or NH
3h
2o.
3. a kind of carbon dioxide decomposition as claimed in claim 1 prepares the application of the catalyst of carbon monoxide, it is characterized in that catalyst application is in fixed bed reactors, concrete course of reaction is: catalyst is warming up in an ar atmosphere 1200-1400 DEG C and carries out thermal reduction reaction, and the reaction time is 40-60 min; Be cooled to 800-1100 DEG C under an ar atmosphere afterwards; CO is passed at 800-1100 DEG C
2carry out CO
2decomposition reaction, the reaction time is 40-60 min; In Ar gas, be warming up to 1200-1400 DEG C more afterwards, two-step reaction constantly circulates and carries out under such variations in temperature condition, and two-step reaction carries out all at ambient pressure.
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| CN109317130A (en) * | 2018-09-29 | 2019-02-12 | 中国科学院山西煤炭化学研究所 | One kind being used for thermochemical cycle decomposition CO2And/or H2The catalyst and preparation method of O and application |
| CN113842921B (en) * | 2021-10-27 | 2023-11-24 | 合肥神舟催化净化器股份有限公司 | Ammonia oxidation catalyst for diesel engine based on ternary metal oxide, preparation method and application |
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