CN107042113A - Cobalt gallium base catalyst and its preparation and application of the perovskite composite oxide for presoma - Google Patents

Cobalt gallium base catalyst and its preparation and application of the perovskite composite oxide for presoma Download PDF

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CN107042113A
CN107042113A CN201710270774.XA CN201710270774A CN107042113A CN 107042113 A CN107042113 A CN 107042113A CN 201710270774 A CN201710270774 A CN 201710270774A CN 107042113 A CN107042113 A CN 107042113A
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catalyst
nitrate
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carbon
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刘源
杨其磊
康娜
郭少霞
王嘉明
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Tianjin University
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Abstract

The cobalt gallium base catalyst for presoma and its preparation and application the present invention relates to perovskite composite oxide；Catalyst is that molecular formula is LaCo1‑αGaαO3；Or La, Co or Ga one or more therein are partly replaced, molecular formula is La1‑δAδCo1‑β‑γGaβBγO3；Or LaCo1‑αGaαO3、La1‑δAδCo1‑β‑γGaβBγO3It is carried on the catalyst of carrier；The present invention by citric acid complex method makes Ga ions obtain obtaining carrier loaded cobalt gallium base catalyst after catalyst, reduction into perovskite compound B, i.e., the oxide supported metal Co catalyst containing La and Ga and doped chemical is realized.The catalyst is used equally for the reaction of low-carbon alcohols processed in co hydrogenation and hydrogenation of carbon dioxide, has higher selectivity and high activity and stability to carbon atom quantity for 26 alcohols.

Description

Perovskite composite oxide for presoma cobalt gallium base catalyst and its prepare and Using
Technical field
The present invention relates to a kind of new cobalt gallium base catalyst and its system using perovskite composite oxide as presoma Standby to be respectively applied to co hydrogenation and hydrogenation of carbon dioxide preparing low-carbon mixed alcohol with application, belong to metallic catalyst should Use field.
Background technology
Low-carbon alcohols, refer to the alcohol containing two or more carbon atoms, because it is widely used in chemicals and polymer work Received much concern in industry, such as synthesize the raw material and intermediate of particular business product, and add as a kind of excellent gasoline Agent, can improve the octane number of gasoline.At present, they are mainly spread out by grain/sugar fermentation (such as ethanol and isobutanol) or oil The aquation (such as weight alcohol) of raw alkene is obtained.If can be from synthesis gas (CO+H2) low-carbon alcohols are directly made, then it can both save About grain, can make full use of the coal and natural gas resource of China's abundant again, so that the industrial consumption for alleviating China's grain is eased up Solve petroleum resources contradiction in short supply.On the other hand, greenhouse effects cause global climate environmental degradation, on carbon dioxide Emission reduction and pay attention to day by day of its comprehensive utilization by countries in the world.In the research for comprehensively utilizing, turning waste into wealth, carbon dioxide Hydrogenation directly low-carbon alcohols processed are considered as one of economical and effective method.
By co hydrogenation synthesizing low-carbon mixed alcohol, research heat both domestic and external always has been since proposing at the beginning of the last century Point.Catalyst in report is broadly divided into four classes：1st, methanol is main production in modified methanol synthesis catalyst, alcohol product Thing, and the economic value of methanol is substantially less than low-carbon alcohols；2nd, modified fischer-tropsch synthetic catalyst, mostly bimetallic concerted catalysis, Preparation method requires higher, and bimetallic is easily separated, and causes catalyst stability poor；3rd, Mo bases catalyst, has Preferable sulfur resistance, but required reaction condition is more harsh；4th, ethanol selectivity is most in Rh bases catalyst, alcohol product Height, but easily sintered in course of reaction, and it is expensive.In view of the deficiency that four class dominant catalyst performances are present above, Limit its industrial applications.Therefore, the catalyst of new catalytic activity and the CO Hydrogenation low-carbon alcohols of excellent in stability is probed into out System has important industrial application value.
By the catalyst of hydrogenation of carbon dioxide synthesis of low-carbon alcohol, it is rarely reported at present, its Patent CN201310117025.5, it is main to use Cu-Zn-Cr catalyst, and primary product is methanol.And add on carbon dioxide The catalyst report of hydrogen methanol is more, mainly Cu bases catalyst.Such as patent CN201110006073.8, its catalyst master It is Cu, Zr to want metal component；Patent CN201210066240.2, its catalyst key component be Cu oxides, Zn oxides and Multi-functional complex carrier Ti oxides, Al oxides；Patent CN201510381119.2, its catalyst main metal component is： Cu、Zn、Al、Zr.Product reported above is mainly methanol.Because the economic value of low-carbon alcohols is far above methanol.Therefore, probe into Go out a kind of CO of new excellent performance2The catalyst system of Hydrogenation low-carbon alcohols has important application value.
The content of the invention
It is an object of the invention to provide the cobalt gallium base catalyst that a kind of new perovskite composite oxide is presoma And its prepare and apply.Described catalyst can be used for co hydrogenation preparing low-carbon mixed alcohol, can be used for carbon dioxide and add Hydrogen preparing low-carbon mixed alcohol, with higher selectivity, activity and stability, with C in alcohol product2+Based on alcohol.
Technical scheme is as follows：
A kind of cobalt gallium base catalyst, molecular formula is LaCo1-αGaαO3, wherein α span is 0.1~0.99.
A kind of cobalt gallium base catalyst, it is characterized in that La or Co or Ga one or more are partly replaced, molecular formula is La1-δ AδCo1-β-γGaβBγO3.Wherein A is Y, Ce, K, Sr, Cs, Ca, Na or Ba one or more of；B is Rh, In, Mn, Cu, Ru, Ni Or Fe is one or more of；δ, β, γ span are respectively 0~0.3,0.1~0.99,0~0.3, δ it is different with γ when be 0.
A kind of cobalt gallium base catalyst, it is characterized in that LaCo1-αGaαO3Or La1-δAδCo1-β-γGaβBγO3It is carried on carrier, group As LaCo1-αGaαO3/ carrier or La1-δAδCo1-β-γGaβBγO3/ carrier.Wherein described carrier is SiO2、ZrO2、TiO2、 CeO2、Al2O3、Y-ZrO2、CexTi1-xO2、 CexZr1-xO2In one or more combination；LaCo1-αGaαO3Or La1-δAδ Co1-β-γGaβBγO3Mass fraction span in the catalyst is 5~40.
The preparation method of the catalyst of the present invention, its key step is as follows：
The preparation of catalyst
Catalyst composition is LaCo1-αGaαO3Preparation method：According to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and second The mol ratio of glycol is 1：(0.1~0.99)：(0.99~0.1)：(0.5~3.0)：The proportions mixing of (0.1~5.0) Saline solution；Salting liquid is put in into the stirring of 60~100 DEG C of water-baths to be evaporated, product dries 6 in 80~200 DEG C of drying bakers~ 24h, dried product exhibited is warming up to 250~500 DEG C of 1~6h of roasting with 2~10 DEG C/min, is continuously heating to 600~900 DEG C of roastings 3~10h is burnt, it is LaCo to obtain catalyst composition1-αGaαO3, with perovskite composite oxide structure, α span is 0.1~0.99.
Catalyst composition is La1-δAδCo1-β-γGaβBγO3Preparation method：According to lanthanum nitrate, substitution La or Co or Ga members Plain one or more of nitrate, cobalt nitrate, gallium nitrate, the mol ratio of citric acid and ethylene glycol are (0~1)：(0~0.3)： (0.1~0.99)：(0.99~0.1)：(0.5~3.0)：The proportions mixed-salt aqueous solution of (0.1~5.0)；By salting liquid Be put in the stirring of 60-100 DEG C of water-bath to be evaporated, product dries 6~24h in 80~200 DEG C of drying bakers, dried product exhibited with 2~ 10 DEG C/min is warming up to 250~500 DEG C of 1~6h of roasting, is continuously heating to 600~900 DEG C of 3~10h of roasting, obtains catalyst group As La1-δAδCo1-β-γGaβBγO3, with perovskite composite oxide structure.Wherein δ, β, γ span are respectively 0 ~0.3,0.1~0.99,0~0.3, δ it is different with γ when be 0.
Catalyst composition is LaCo1-αGaαO3/ carrier or La1-δAδCo1-β-γGaβBγO3The preparation method of/carrier：According to nitre Sour lanthanum, substitution La or the one or more of nitrate of Co or Ga elements, cobalt nitrate, gallium nitrate, mole of citric acid and ethylene glycol Than for (0~1)：(0~0.3)：(0.1~0.99)：(0.99~0.1)：(0.5~3.0)：The proportions of (0.1~5.0) Mixed-salt aqueous solution, according to LaCo1-αGaαO3Or La1-δAδCo1-β-γGaβBγO3Mass fraction 5~40% in the catalyst Ratio is by carrier impregnation in salting liquid.1~48h of aging, product in 60~110 DEG C of dry 6~24h, desciccate with 2~ 10 DEG C/min is warming up to 250~500 DEG C of 1~6h of roasting, is continuously heating to 600~900 DEG C of 3~10h of roasting, obtains carrier loaded Catalyst, its structure be LaCo1-αGaαO3/ carrier or La1-δAδCo1-β-γGaβBγO3/ carrier.Wherein described carrier is SiO2、 ZrO2、 TiO2、CeO2、Al2O3、Y-ZrO2、CexTi1-xO2、CexZr1-xO2In one or more combination；LaCo1-αGaαO3Or La1-δAδCo1-β-γGaβBγO3Mass fraction span in the catalyst is 5~40.
The reduction of catalyst
It is LaCo by the composition of preparation1-αGaαO3Or La1-δAδCo1-β-γGaβBγO3Or LaCo1-αGaαO3/ carrier or La1-δAδ Co1-β-γGaβBγO3The catalyst of/carrier is placed in reactor, and volume space velocity is passed through into reactor for 300~3000mL/ (gcatH) reduction reaction gas, is then reduced to catalyst, and wherein heating rate is 2~20 DEG C/min；Temperature is 500 ~900 DEG C；Recovery time is 0.1~6h, the cobalt gallium base catalyst after being reduced.
The reduction reaction gas is one or more gaseous mixtures in hydrogen, carbon monoxide, methane, or anti-in above-mentioned reduction One or more inert gases in nitrogen, argon gas, helium should be added in gas, with reproducibility reaction gas collectively as also Primordial Qi, The volume fraction of inert gas is 1~99% wherein in gaseous mixture.
Catalyst prepares the application of low-carbon alcohols in co hydrogenation
Catalyst composition is LaCo1-αGaαO3Or La1-δAδCo1-β-γGaβBγO3Or LaCo1-αGaαO3/ carrier or La1-δAδ Co1-β-γGaβBγO3/ carrier is used for the application that co hydrogenation prepares low-carbon alcohols, and the catalyst after reduction is added into reactor In, under conditions of temperature is 200~350 DEG C and pressure is 1~10MPa, into reactor using volume space velocity as 500~ 30000mL/(gcatH) hydrogen and carbon monoxide being passed through, are made low carbon mixed alcohol.Described hydrogen and carbon monoxide mole ratios For (1~4)：Contain the carbon dioxide with carbon monoxide mole ratios 0~20% in 1, and gaseous mixture.
Catalyst prepares the application of low-carbon alcohols in hydrogenation of carbon dioxide
Catalyst composition is LaCo1-αGaαO3Or La1-δAδCo1-β-γGaβBγO3Or LaCo1-αGaαO3/ carrier or La1-δAδ Co1-β-γGaβBγO3/ carrier is used for the application that hydrogenation of carbon dioxide prepares low-carbon alcohols, and the catalyst after reduction is added into reactor In, under conditions of temperature is 200~350 DEG C and pressure is 1~10MPa, into reactor using volume space velocity as 500~ 30000mL/(gcatH) hydrogen and carbon dioxide being passed through, are made low carbon mixed alcohol.Described hydrogen and carbon dioxide mol ratio For (1~6)：Contain the carbon monoxide with carbon dioxide mol ratio 0~20% in 1, and gaseous mixture.
The beneficial effects of the invention are as follows Ga ions is entered perovskite compound B (to improve by citric acid complex method Mixed-salt aqueous solution can also be impregnated on common vector by decentralization) obtain obtaining carrier loaded cobalt after catalyst, reduction Gallium base catalyst, i.e., oxide supported metal Co catalyst containing La and Ga and doped chemical is realized.Perovskite structure Middle each component it is dispersed and interaction, by perovskite composite oxides reduce during be conducive to Co and containing La and Ga And the interaction between the oxide and carrier of doped chemical, and cobalt and the oxidation containing La and Ga and doped chemical The decentralization of the components such as thing is high, stability is good.The catalyst is used equally for system in co hydrogenation and hydrogenation of carbon dioxide The reaction of low-carbon alcohols, has higher selectivity and high activity to carbon atom quantity for 2-6 alcohols (especially ethanol) And stability.
La is generated after catalyst reduction4Ga2O9, this is extremely important to catalyst.Exist after reduction and during the course of the reaction Metallic cobalt (Co) and La4Ga2O9, the interaction both this is the key reason that catalyst has premium properties.
Brief description of the drawings
Fig. 1 is catalyst (1) prepared in example 1, the X of catalyst (2) and reacted catalyst (3) after reduction X ray diffraction (XRD) figure；
Fig. 2 is the transmission of the catalyst (B) after (A) and 200h stability tests after catalyst reduction described in example 1 Electronic Speculum (TEM) figure；Wherein, A' and B' are respectively A and B partial enlarged drawing；
In figure：(A') 0.205nm represents Co [111] crystal face, and 0.778nm represents La4Ga2O9[011] crystal face.
(B') 0.177nm represents Co [200] crystal face, and 0.304nm represents La4Ga2O9[131] crystal face.
Fig. 3 be catalyst in embodiment 1 temperature be 310 DEG C, pressure be that 3MPa, air speed are 3000mL/ (gcatH) Under the conditions of co hydrogenation low-carbon alcohols stability test curve；
In figure：(A) ■ represents CO conversion ratio；▲ represent the selectivity of alcohols；▼ represents the selectivity of hydro carbons；● represent CO2Selectivity.(B) it is methanol/ethanol propyl alcohol and the column distribution map of butanol.
Embodiment
1st, the specific preparation process of catalyst
A, the salting liquid of configuration is evaporated in the stirring of 80 DEG C of water-baths, product is in 120 DEG C of dry 12h, and dried product exhibited is with 2 DEG C/min be warming up to 450 DEG C roasting 3h, be continuously heating to 700 DEG C roasting 5h, obtain catalyst.
B, the mass ratio according to carrier in perovskite and concrete case, carrier in concrete case is impregnated into by mixing salt solution On.Aging 24h is placed, 120 DEG C of dry 12h, dried product exhibited is warming up to 450 DEG C of roasting 3h with 2 DEG C/min, is continuously heating to 700 DEG C of roasting 5h, obtain catalyst.
C, the salting liquid of configuration is evaporated in the stirring of 60 DEG C of water-baths, product is in 80 DEG C of dry 6h, and dried product exhibited is with 2 DEG C/min be warming up to 250 DEG C roasting 1h, be continuously heating to 600 DEG C roasting 3h, obtain catalyst.
D, the salting liquid of configuration is evaporated in the stirring of 100 DEG C of water-baths, product in 200 DEG C of dry 24h, dried product exhibited with 10 DEG C/min is warming up to 500 DEG C of roasting 6h, is continuously heating to 900 DEG C of roasting 10h, obtains catalyst.
E, the mass ratio according to carrier in perovskite and concrete case, carrier in concrete case is impregnated into by mixing salt solution On.Aging 1h is placed, 60 DEG C of dry 6h, dried product exhibited is warming up to 250 DEG C of roasting 1h with 2 DEG C/min, is continuously heating to 600 DEG C roasting 3h, obtain catalyst.
F, the mass ratio according to carrier in perovskite and concrete case, carrier in concrete case is impregnated into by mixing salt solution On.Aging 48h is placed, 110 DEG C of dry 24h, dried product exhibited is warming up to 500 DEG C of roasting 6h with 10 DEG C/min, is continuously heating to 900 DEG C of roasting 10h, obtain catalyst.
2nd, the specific reduction process of catalyst
A, the catalyst that will be prepared in above-mentioned steps 1, are added in reactor, into reactor using volume space velocity as 300mL/(gcatH) it is passed through H2, 800 DEG C of reduction 3h are warming up to by 5 DEG C/min of heating rate.
B, the catalyst that will be prepared in above-mentioned steps 1, are added in reactor, into reactor using volume space velocity as 300mL/(gcatH) it is passed through H2, 500 DEG C of reduction 0.1h are warming up to by 2 DEG C/min of heating rate.
C, the catalyst that will be prepared in above-mentioned steps 1, are added in reactor, into reactor using volume space velocity as 3000mL/(gcatH) it is passed through H2, 900 DEG C of reduction 6h are warming up to by 20 DEG C/min of heating rate.
D, the catalyst that will be prepared in above-mentioned steps 1, are added in reactor, into reactor using volume space velocity as 300mL/(gcatH) carbon monoxide is passed through, 800 DEG C of reduction 3h are warming up to by 5 DEG C/min of heating rate.
E, the catalyst that will be prepared in above-mentioned steps 1, are added in reactor, into reactor using volume space velocity as 300mL/(gcatH) methane is passed through, 800 DEG C of reduction 3h are warming up to by 5 DEG C/min of heating rate.
3rd, application of the catalyst in co hydrogenation prepares low-carbon alcohols
A, step 2 is reduced after catalyst, be added in reactor, in the bar that temperature is 310 DEG C and pressure is 3MPa Under part, into reactor using volume space velocity as 3900mL/ (gcatH) it is 2 to be passed through mol ratio:1 carbon monoxide and hydrogen is made Low carbon mixed alcohol.
B, step 2 is reduced after catalyst, be added in reactor, in the bar that temperature is 200 DEG C and pressure is 1MPa Under part, into reactor using volume space velocity as 500mL/ (gcatH) it is 1 to be passed through mol ratio:1 carbon monoxide and hydrogen is made low Carbon mixed alcohol.
C, step 2 is reduced after catalyst, be added in reactor, in the bar that temperature is 350 DEG C and pressure is 10MPa Under part, into reactor using volume space velocity as 30000mL/ (gcatH) it is 4 to be passed through mol ratio:1 carbon monoxide and hydrogen is made Low carbon mixed alcohol.
D, step 2 is reduced after catalyst, be added in reactor, in the bar that temperature is 310 DEG C and pressure is 3MPa Under part, into reactor using volume space velocity as 3900mL/ (gcatH) it is 2 to be passed through mol ratio:0.4:1 carbon monoxide, titanium dioxide Low carbon mixed alcohol is made in carbon and hydrogen.
CO conversion ratios, each selectivity of product and alcohols yield are shown in Table 1 on catalyst in all specific implementation cases.
4th, application of the catalyst in hydrogenation of carbon dioxide prepares low-carbon alcohols
A, step 2 is reduced after catalyst, be added in reactor, in the bar that temperature is 310 DEG C and pressure is 3MPa Under part, into reactor using volume space velocity as 3900mL/ (gcatH) it is 3 to be passed through mol ratio:1 carbon dioxide and hydrogen is made Low carbon mixed alcohol.
B, step 2 is reduced after catalyst, be added in reactor, in the bar that temperature is 200 DEG C and pressure is 1MPa Under part, into reactor using volume space velocity as 500mL/ (gcatH) it is 1 to be passed through mol ratio:1 carbon dioxide and hydrogen is made low Carbon mixed alcohol.
C, step 2 is reduced after catalyst, be added in reactor, in the bar that temperature is 350 DEG C and pressure is 10MPa Under part, into reactor using volume space velocity as 30000mL/ (gcatH) it is 4 to be passed through mol ratio:1 carbon dioxide and hydrogen is made Low carbon mixed alcohol.
D, step 2 is reduced after catalyst, be added in reactor, in the bar that temperature is 310 DEG C and pressure is 3MPa Under part, into reactor using volume space velocity as 3900mL/ (gcatH) it is 3 to be passed through mol ratio:0.6:1 carbon dioxide, an oxidation Low carbon mixed alcohol is made in carbon and hydrogen.
CO on catalyst in all specific implementation cases2Conversion ratio, each selectivity of product and alcohols yield are shown in Table 2.
In order to sketch conveniently, above-mentioned selection concrete technology condition, example below of the present invention is quoted in each above-mentioned step A B C D E F, write a Chinese character in simplified form correspond to respectively 1A 2A 3A 4A 1B 2B 3B 4B 1C 2C 3C 4C 1D 2D 3D 4D 1E\2E\1F。
【Embodiment 1】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1A0.65Ga0.35O3；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4A.As shown in Figure 1, 2, 3.Prepared catalyst (1) in Fig. 1, catalyst (2) after reduction and reacted is urged X-ray diffraction (XRD) figure of agent (3)；Fig. 2 be described in catalyst reduction after urging after (A) and 200h stability tests Transmission electron microscope (TEM) figure of agent (B)；(A) 0.205nm represents Co [111] crystal face, and 0.778nm represents La4Ga2O9's [011] crystal face.(B) 0.177nm represents Co [200] crystal face, and 0.304nm represents La4Ga2O9[131] crystal face.Urging in Fig. 3 Agent temperature be 310 DEG C, pressure be that 3MPa, air speed are 3000mL/ (gcatH) the co hydrogenation low-carbon under conditions of The stability test curve of alcohol.
【Embodiment 2】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst La is obtained through step 1A0.9Y0.1Co0.65Ga0.35O3；Through step 2A reduces to obtain Co/Y-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 3】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst La is obtained through step 1A0.9Ce0.1Co0.65Ga0.35O3.Through step 2A reduces to obtain Co/Ce-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 4】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst La is obtained through step 1A0.9K0.1Co0.65Ga0.35O3；Through step 2A reduces to obtain Co/K-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 5】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst La is obtained through step 1A0.9Sr0.1Co0.65Ga0.35O3；Through step 2A reduces to obtain Co/Sr-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 6】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst La is obtained through step 1A0.9Cs0.1Co0.65Ga0.35O3；Through step 2A reduces to obtain Co/Cs-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 7】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst La is obtained through step 1A0.9Ca0.1Co0.65Ga0.35O3；Through step 2A reduces to obtain Co/Ca-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 8】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；Catalyst LaMn is obtained through step 1A0.1Co0.60Ga0.30O3；Through step 2A Reduce to obtain Co/Mn-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide adds Hydrogen prepares the test condition 4A of low-carbon alcohols.
【Embodiment 9】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst LaRh is obtained through step 1A0.05Co0.60Ga0.35O3；Through step 2A reduces to obtain Co/Rh-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 10】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；Catalyst LaIn is obtained through step 1A0.1Co0.60Ga0.30O3；Through step 2A Reduce to obtain Co/In-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide adds Hydrogen prepares the test condition 4A of low-carbon alcohols.
【Embodiment 11】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；Catalyst LaCu is obtained through step 1A0.1Co0.60Ga0.30O3；Through step 2A Reduce to obtain Co/Cu-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide adds Hydrogen prepares the test condition 4A of low-carbon alcohols.
【Embodiment 12】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst LaRu is obtained through step 1A0.1Co0.60Ga0.30O3；Through step 2A Reduce to obtain Co/Ru-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide adds Hydrogen prepares the test condition 4A of low-carbon alcohols.
【Embodiment 13】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；Catalyst LaNi is obtained through step 1A0.1Co0.60Ga0.30O3；Through step 2A Reduce to obtain Co/Ni-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide adds Hydrogen prepares the test condition 4A of low-carbon alcohols.
【Embodiment 14】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；Catalyst LaFe is obtained through step 1A0.1Co0.60Ga0.30O3；Through step 2A Reduce to obtain Co/Fe-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide adds Hydrogen prepares the test condition 4A of low-carbon alcohols.
【Embodiment 15】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst La is obtained through step 1A0.9Na0.1Co0.65Ga0.35O3；Through step 2A reduces to obtain Co/Na-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 16】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；Catalyst La is obtained through step 1A0.9Ba0.1Co0.65Ga0.35O3；Through step 2A reduces to obtain Co/Ba-La2O3-La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 17】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio mixing salt solution is impregnated into TiO for 30%2 On carrier；TiO is obtained through step 1B2The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares low-carbon alcohols Test condition 4A.
【Embodiment 18】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and support C eO2Mass ratio mixing salt solution is impregnated into CeO for 30%2 On carrier；CeO is obtained through step 1B2The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares low-carbon alcohols Test condition 4A.
【Embodiment 19】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio mixing salt solution is impregnated into for 30% Al2O3On carrier；Al is obtained through step 1B2O3The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares low-carbon alcohols Test condition 4A.
【Embodiment 20】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio mixing salt solution is impregnated into for 30% Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The LaCo supported0.65Ga0.35O3Catalyst；Co/ is reduced to obtain through step 2A La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide system The test condition 4A of standby low-carbon alcohols.
【Embodiment 21】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio mixing salt solution is soaked for 30% Stain is to Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The LaCo supported0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/La2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 22】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio mixing salt solution is soaked for 30% Stain is to Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The LaCo supported0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/La2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 23】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The La supported0.9Y0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Y-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 24】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The La supported0.9Y0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Y-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 25】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The La supported0.9Y0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Y-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 26】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The La supported0.9Y0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Y-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 27】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The La supported0.9Y0.1Co0.65Ga0.35O3Catalyst；Through step 2A Reduce to obtain Co/Y-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 28】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The La supported0.9Y0.1Co0.65Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Y-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols. Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 29】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The La supported0.9Y0.1Co0.65Ga0.35O3 Catalyst；Co/Y-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 30】
Mol ratio according to lanthanum nitrate, yttrium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The La supported0.9Y0.1Co0.65Ga0.35O3 Catalyst；Co/Y-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 31】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The La supported0.9Ce0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ce-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 32】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The La supported0.9Ce0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ce-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 33】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The La supported0.9Ce0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ce-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 34】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The La supported0.9Ce0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ce-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 35】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The La supported0.9Ce0.1Co0.65Ga0.35O3Catalyst；Through step 2A Reduce to obtain Co/Ce-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 36】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The La supported0.9Ce0.1Co0.65Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Ce-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition of low-carbon alcohols 3A.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 37】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2Support La0.9Ce0.1Co0.65Ga0.35O3Catalyst；Co/Ce-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Ti0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 38】
Mol ratio according to lanthanum nitrate, cerous nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2Support La0.9Ce0.1Co0.65Ga0.35O3Catalyst；Co/Ce-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Zr0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 39】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The La supported0.9K0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/K-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 40】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The La supported0.9K0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/K-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 41】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The La supported0.9K0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/K-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 42】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The La supported0.9K0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/K-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 43】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The La supported0.9K0.1Co0.65Ga0.35O3Catalyst；Through step 2A Reduce to obtain Co/K-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 44】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The La supported0.9K0.1Co0.65Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/K-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols. Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 45】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The La supported0.9K0.1Co0.65Ga0.35O3 Catalyst；Co/K-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 46】
Mol ratio according to lanthanum nitrate, potassium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The La supported0.9K0.1Co0.65Ga0.35O3 Catalyst；Co/K-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 47】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The La supported0.9Sr0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Sr-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 48】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The La supported0.9Sr0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Sr-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 49】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The La supported0.9Sr0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Sr-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 50】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The La supported0.9Sr0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Sr-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 51】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The La supported0.9Sr0.1Co0.65Ga0.35O3Catalyst；Through step 2A Reduce to obtain Co/Sr-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 52】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The La supported0.9Sr0.1Co0.65Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Sr-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition of low-carbon alcohols 3A.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 53】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2Support La0.9Sr0.1Co0.65Ga0.35O3Catalyst；Co/Sr-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Ti0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 54】
Mol ratio according to lanthanum nitrate, strontium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2Support La0.9Sr0.1Co0.65Ga0.35O3Catalyst；Co/Sr-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Zr0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 55】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The La supported0.9Cs0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Cs-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 56】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The La supported0.9Cs0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Cs-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 57】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The La supported0.9Cs0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Cs-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 58】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The La supported0.9Cs0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Cs-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 59】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The La supported0.9Cs0.1Co0.65Ga0.35O3Catalyst；Through step 2A Reduce to obtain Co/Cs-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 60】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The La supported0.9Cs0.1Co0.65Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Cs-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition of low-carbon alcohols 3A.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 61】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2Support La0.9Cs0.1Co0.65Ga0.35O3Catalyst；Co/Cs-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Zr0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 62】
Mol ratio according to lanthanum nitrate, cesium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2Support La0.9Cs0.1Co0.65Ga0.35O3Catalyst；Co/Cs-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Ti0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 63】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The La supported0.9Ca0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ca-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 64】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The La supported0.9Ca0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ca-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 65】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The La supported0.9Ca0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ca-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 66】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The La supported0.9Ca0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ca-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 67】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The La supported0.9Ca0.1Co0.65Ga0.35O3Catalyst；Through step 2A Reduce to obtain Co/Ca-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 68】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The La supported0.9Ca0.1Co0.65Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Ca-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition of low-carbon alcohols 3A.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 69】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2Support La0.9Ca0.1Co0.65Ga0.35O3Catalyst；Co/Ca-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Ti0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 70】
Mol ratio according to lanthanum nitrate, calcium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2Support La0.9Ca0.1Co0.65Ga0.35O3Catalyst；Co/Ca-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Zr0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 71】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The LaMn supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Mn-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 72】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The LaMn supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Mn-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 73】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The LaMn supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Mn-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 74】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The LaMn supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Mn-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 75】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The LaMn supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A also It is former to obtain Co/Mn-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 76】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The LaMn supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A reduces to obtain Co/Mn-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols. Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 77】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The LaMn supported0.1Co0.60Ga0.30O3 Catalyst；Co/Mn-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 78】
Mol ratio according to lanthanum nitrate, manganese nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The LaMn supported0.1Co0.60Ga0.30O3 Catalyst；Co/Mn-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 79】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The LaRh supported0.05Co0.60Ga0.35O3Catalyst；Reduced through step 2A Obtain Co/Rh-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 80】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The LaRh supported0.05Co0.60Ga0.35O3Catalyst；Reduced through step 2A Obtain Co/Rh-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 81】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The LaRh supported0.05Co0.60Ga0.35O3Catalyst；Reduced through step 2A Obtain Co/Rh-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 82】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The LaRh supported0.05Co0.60Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Rh-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 83】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The LaRh supported0.05Co0.60Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Rh-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 84】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The LaRh supported0.05Co0.60Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Rh-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition of low-carbon alcohols 3A.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 85】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The LaRh supported0.05Co0.60Ga0.35O3 Catalyst；Co/Rh-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 86】
Mol ratio according to lanthanum nitrate, rhodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The LaRh supported0.05Co0.60Ga0.35O3 Catalyst；Co/Rh-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 87】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The LaIn supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/In-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 88】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The LaIn supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/In-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 89】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The LaIn supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/In-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 90】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The LaIn supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/In-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 91】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The LaIn supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A also It is former to obtain Co/In-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 92】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The LaIn supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A reduces to obtain Co/In-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols. Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 93】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The LaIn supported0.1Co0.60Ga0.30O3 Catalyst；Co/In-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low The test condition 3A of carbon alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 94】
Mol ratio according to lanthanum nitrate, indium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The LaIn supported0.1Co0.60Ga0.30O3 Catalyst；Co/In-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low The test condition 3A of carbon alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 95】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The LaCu supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Cu-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 96】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The LaCu supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Cu-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 97】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The LaCu supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Cu-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 98】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The LaCu supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Cu-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 99】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The LaCu supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A also It is former to obtain Co/Cu-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 100】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The LaCu supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A reduces to obtain Co/Cu-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols. Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 101】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The LaCu supported0.1Co0.60Ga0.30O3 Catalyst；Co/Cu-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low The test condition 3A of carbon alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 102】
Mol ratio according to lanthanum nitrate, copper nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The LaCu supported0.1Co0.60Ga0.30O3 Catalyst；Co/Cu-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 103】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The LaRu supported0.05Co0.60Ga0.35O3Catalyst；Reduced through step 2A Obtain Co/Ru-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 104】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The LaRu supported0.05Co0.60Ga0.35O3Catalyst；Reduced through step 2A Obtain Co/Ru-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 105】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The LaRu supported0.05Co0.60Ga0.35O3Catalyst；Reduced through step 2A Obtain Co/Ru-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 106】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The LaRu supported0.05Co0.60Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ru-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 107】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The LaRu supported0.05Co0.60Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ru-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 108】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The LaRu supported0.05Co0.60Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Ru-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition of low-carbon alcohols 3A.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 109】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The LaRu supported0.05Co0.60Ga0.35O3 Catalyst；Co/Ru-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 110】
Mol ratio according to lanthanum nitrate, nitric acid ruthenium, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.05：0.60： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The LaRu supported0.05Co0.60Ga0.35O3 Catalyst；Co/Ru-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low-carbon The test condition 3A of alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 111】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The LaNi supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Ni-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 112】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The LaNi supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Ni-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 113】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The LaNi supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Ni-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 114】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The LaNi supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Ni-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 115】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The LaNi supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A also It is former to obtain Co/Ni-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 116】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The LaNi supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A reduces to obtain Co/Ni-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols. Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 117】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The LaNi supported0.1Co0.60Ga0.30O3 Catalyst；Co/Ni-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low The test condition 3A of carbon alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 118】
Mol ratio according to lanthanum nitrate, nickel nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The LaNi supported0.1Co0.60Ga0.30O3 Catalyst；Co/Ni-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low The test condition 3A of carbon alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 119】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The LaFe supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Fe-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 120】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The LaFe supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Fe-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 121】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The LaFe supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Fe-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 122】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The LaFe supported0.1Co0.60Ga0.30O3Catalyst；Reduced through step 2A Obtain Co/Fe-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Carbon dioxide Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 123】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The LaFe supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A also It is former to obtain Co/Fe-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 124】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The LaFe supported0.1Co0.60Ga0.30O3Catalyst；Through step 2A reduces to obtain Co/Fe-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols. Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 125】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2The LaFe supported0.1Co0.60Ga0.30O3 Catalyst；Co/Fe-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Ti0.2O2Catalyst.Co hydrogenation prepares low The test condition 3A of carbon alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 126】
Mol ratio according to lanthanum nitrate, ferric nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.1：0.60： 0.30：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2The LaFe supported0.1Co0.60Ga0.30O3 Catalyst；Co/Fe-La is reduced to obtain through step 2A2O3-La4Ga2O9-Ce0.8Zr0.2O2Catalyst.Co hydrogenation prepares low The test condition 3A of carbon alcohol.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 127】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio mixing salt solution is impregnated into SiO for 30%2 On carrier；SiO is obtained through step 1B2The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares low-carbon alcohols Test condition 4A.
【Embodiment 128】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio mixing salt solution is impregnated into ZrO for 30%2 On carrier；ZrO is obtained through step 1B2The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares low-carbon alcohols Test condition 4A.
【Embodiment 129】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The La supported0.9Na0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Na-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 130】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The La supported0.9Na0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Na-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 131】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The La supported0.9Na0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Na-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 132】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The La supported0.9Na0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Na-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 133】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The La supported0.9Na0.1Co0.65Ga0.35O3Catalyst；Through step 2A Reduce to obtain Co/Na-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 134】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The La supported0.9Na0.1Co0.65Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Na-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition of low-carbon alcohols 3A.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 135】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2Support La0.9Na0.1Co0.65Ga0.35O3Catalyst；Co/Na-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Ti0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 136】
Mol ratio according to lanthanum nitrate, sodium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2Support La0.9Na0.1Co0.65Ga0.35O3Catalyst；Co/Na-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Zr0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 137】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier S iO2Mass ratio for 30% by salt-mixture Solution is impregnated into SiO2On carrier；SiO is obtained through step 1B2The La supported0.9Ba0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ba-La2O3-La4Ga2O9-SiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 138】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier ZrO2Mass ratio for 30% by salt-mixture Solution is impregnated into ZrO2On carrier；ZrO is obtained through step 1B2The La supported0.9Ba0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ba-La2O3-La4Ga2O9-ZrO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 139】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio for 30% by salt-mixture Solution is impregnated into TiO2On carrier；TiO is obtained through step 1B2The La supported0.9Ba0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ba-La2O3-La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 140】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C eO2Mass ratio for 30% by salt-mixture Solution is impregnated into CeO2On carrier；CeO is obtained through step 1B2The La supported0.9Ba0.1Co0.65Ga0.35O3Catalyst；Through step 2A also It is former to obtain Co/Ba-La2O3-La4Ga2O9-CeO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Titanium dioxide Carbon Hydrogenation for low-carbon alcohols test condition 4A.
【Embodiment 141】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Al2O3Mass ratio for 30% by salt-mixture Solution is impregnated into Al2O3On carrier；Al is obtained through step 1B2O3The La supported0.9Ba0.1Co0.65Ga0.35O3Catalyst；Through step 2A Reduce to obtain Co/Ba-La2O3-La4Ga2O9-Al2O3Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Dioxy Change carbon Hydrogenation for the test condition 4A of low-carbon alcohols.
【Embodiment 142】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and carrier Y-ZrO2Mass ratio for 30% will mixing Salt solution impregnation is to Y-ZrO2On carrier；Y-ZrO is obtained through step 1B2The La supported0.9Ba0.1Co0.65Ga0.35O3Catalyst；Through step Rapid 2A reduces to obtain Co/Ba-La2O3-La4Ga2O9-Y-ZrO2Catalyst.Co hydrogenation prepares the test condition of low-carbon alcohols 3A.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 143】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Ti0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Ti0.2O2On carrier；Ce is obtained through step 1B0.8Ti0.2O2Support La0.9Ba0.1Co0.65Ga0.35O3Catalyst；Co/Ba-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Ti0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 144】
Mol ratio according to lanthanum nitrate, barium nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 0.9：0.1：0.65： 0.35：2.4：0.48 proportions mixing salt solution；According to perovskite and support C e0.8Zr0.2O2Mass ratio for 30% will Mixing salt solution is impregnated into Ce0.8Zr0.2O2On carrier；Ce is obtained through step 1B0.8Zr0.2O2Support La0.9Ba0.1Co0.65Ga0.35O3Catalyst；Co/Ba-La is reduced to obtain through step 2A2O3-La4Ga2O9- Ce0.8Zr0.2O2Catalyst. Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test condition 4A of low-carbon alcohols.
【Embodiment 145】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1C0.65Ga0.35O3；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4A.
【Embodiment 146】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1D0.65Ga0.35O3；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4A.
【Embodiment 147】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1A0.65Ga0.35O3；Co/La is reduced to obtain through step 2B2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4A.
【Embodiment 148】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1A0.65Ga0.35O3；Co/La is reduced to obtain through step 2C2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4A.
【Embodiment 149】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1A0.65Ga0.35O3；Co/La is reduced to obtain through step 2D2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4A.
【Embodiment 150】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1A0.65Ga0.35O3；Co/La is reduced to obtain through step 2E2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4A.
【Embodiment 151】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1A0.65Ga0.35O3；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3B of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4B.
【Embodiment 152】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1A0.65Ga0.35O3；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3C of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4C.
【Embodiment 153】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio mixing salt solution is impregnated into TiO for 30%2 On carrier；TiO is obtained through step 1E2The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares low-carbon alcohols Test condition 4A.
【Embodiment 154】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio mixing salt solution is impregnated into TiO for 30%2 On carrier；TiO is obtained through step 1F2The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares low-carbon alcohols Test condition 4A.
【Embodiment 155】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio mixing salt solution is impregnated into TiO for 5%2 On carrier；TiO is obtained through step 1F2The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9-TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares low-carbon alcohols Test condition 4A.
【Embodiment 156】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；According to perovskite and carrier TiO2Mass ratio mixing salt solution is impregnated into TiO for 40%2 On carrier；TiO is obtained through step 1F2The LaCo supported0.65Ga0.35O3Catalyst；Co/La is reduced to obtain through step 2A2O3-La4Ga2O9- TiO2Catalyst.Co hydrogenation prepares the test condition 3A of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the test-strips of low-carbon alcohols Part 4A.
【Embodiment 157】
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：0.65：0.35：2.4：0.48 Proportions mixing salt solution；Catalyst LaCo is obtained through step 1A0.65Ga0.35O3；Co/La is reduced to obtain through step 2A2O3- La4Ga2O9Catalyst.Co hydrogenation prepares the test condition 3D of low-carbon alcohols.Hydrogenation of carbon dioxide prepares the survey of low-carbon alcohols Strip part 4D.
Table one：CO is hydrogenated with
Two：CO2 is hydrogenated with

Claims (9)

1. a kind of cobalt gallium base catalyst, it is characterized in that molecular formula is LaCo1-αGaαO3, wherein α span is 0.1~0.99.
2. catalyst as claimed in claim 1, it is characterized in that La or Co or Ga one or more are partly replaced, molecular formula is La1-δAδCo1-β-γGaβBγO3, wherein A is Y, Ce, K, Sr, Cs, Ca, Na or Ba one or more of；B be Rh, In, Mn, Cu, Ru, Ni or Fe is one or more of；δ, β, γ span are respectively 0~0.3,0.1~0.99,0~0.3, δ it is different with γ when be 0.
3. catalyst as claimed in claim 1 or 2, it is characterized in that LaCo1-αGaαO3Or La1-δAδCo1-β-γGaβBγO3It is carried on Carrier, consisting of LaCo1-αGaαO3/ carrier or La1-δAδCo1-β-γGaβBγO3/ carrier, wherein the carrier is SiO2、ZrO2、 TiO2、CeO2、Al2O3、Y-ZrO2、CexTi1-xO2、CexZr1-xO2In one or more combination；LaCo1-αGaαO3Or La1-δAδ Co1-β-γGaβBγO3Mass fraction span in the catalyst is 5~40.
4. a kind of preparation method of catalyst as claimed in claim 1, it is characterized in that step is as follows：
Mol ratio according to lanthanum nitrate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol is 1：(0.1~0.99)：(0.99~ 0.1)：(0.5~3.0)：The proportions mixed-salt aqueous solution of (0.1~5.0)；Salting liquid is put in 60~100 DEG C of water-baths Stirring is evaporated, and product dries 6~24h in 80~200 DEG C of drying bakers, and dried product exhibited is warming up to 250 with 2~10 DEG C/min~ 500 DEG C of 1~6h of roasting, are continuously heating to 600~900 DEG C of 3~10h of roasting, it is LaCo to obtain catalyst composition1-αGaαO3, with calcium Titanium ore type composite oxides structure, α span is 0.1~0.99.
5. a kind of preparation method of catalyst as claimed in claim 2, it is characterized in that step is as follows：
According to lanthanum nitrate, substitution La or Co or Ga elements one or more of nitrate, cobalt nitrate, gallium nitrate, citric acid and second The mol ratio of glycol is (0~1)：(0~0.3)：(0.1~0.99)：(0.99~0.1)：(0.5~3.0)：(0.1~5.0) Proportions mixed-salt aqueous solution；Salting liquid is put in into 60-100 DEG C of water-bath stirring to be evaporated, product is in 80~200 DEG C of drying bakers Middle 6~24h of drying, dried product exhibited is warming up to 250~500 DEG C of 1~6h of roasting with 2~10 DEG C/min, it is continuously heating to 600~ 900 DEG C of 3~10h of roasting, it is La to obtain catalyst composition1-δAδCo1-β-γGaβBγO3, with perovskite composite oxide structure, δ, β, γ span are respectively 0~0.3,0.1~0.99,0~0.3, δ it is different with γ when be 0.
6. catalyst as claimed in claim 3, its preparation method is as follows：
According to lanthanum nitrate, substitution La or Co or Ga elements one or more of nitrate, cobalt nitrate, gallium nitrate, citric acid and second The mol ratio of glycol is (0~1)：(0~0.3)：(0.1~0.99)：(0.99~0.1)：(0.5~3.0)：(0.1~5.0) Proportions mixed-salt aqueous solution, according to LaCo1-αGaαO3Or La1-δAδCo1-β-γGaβBγO3In La1-δAδCo1-β-γGaβBγO3/ The ratio of mass fraction 5~40% in carrier by carrier impregnation in salting liquid, 1~48h of aging, product is at 60~110 DEG C 6~24h is dried, desciccate is warming up to 250~500 DEG C of 1~6h of roasting with 2~10 DEG C/min, is continuously heating to 600~900 DEG C roasting 3~10h, obtain carrier loaded catalyst, its structure be LaCo1-αGaαO3/ carrier or La1-δAδCo1-β-γGaβBγO3/ Carrier, wherein carrier are SiO2、ZrO2、TiO2、CeO2、Al2O3、Y-ZrO2、CexTi1-xO2、CexZr1-xO2；It is characterized in that described Carrier it is as claimed in claim 3.
7. the catalyst reduction method as prepared by claim 1,2 or 3, it is characterized in that catalyst is placed in reactor, to Volume space velocity is passed through in reactor for 300~3000mL/ (gcatH) reduction reaction gas, is then reduced to catalyst, its Middle heating rate is 2~20 DEG C/min；Temperature is 500~900 DEG C；Recovery time is 0.1~6h, the cobalt gallium base after being reduced Catalyst, wherein reduction reaction gas are one or more gaseous mixtures in hydrogen, carbon monoxide, methane, or anti-in above-mentioned reduction One or more inert gases in nitrogen, argon gas, helium should be added in gas, with reproducibility reaction gas collectively as also Primordial Qi, The volume fraction of inert gas is 1~99% wherein in gaseous mixture.
8. the catalyst that claim 7 restoring method is obtained is used for the application that co hydrogenation prepares low-carbon alcohols, it is characterized in that Catalyst after reduction is added in reactor, under conditions of temperature is 200~350 DEG C and pressure is 1~10MPa, to anti- Answer in device using volume space velocity as 500~30000mL/ (gcatH) hydrogen and carbon monoxide being passed through, are made low carbon mixed alcohol, and it is special Levying is described hydrogen and carbon monoxide mole ratios are (1~4)：1, wherein, in described hydrogen and the gaseous mixture of carbon monoxide The carbon dioxide with carbon monoxide mole ratios 0~20% can be contained.
9. the catalyst that claim 7 restoring method is obtained is used for the application that hydrogenation of carbon dioxide prepares low-carbon alcohols, after reduction Catalyst add in reactor, under conditions of temperature is 200~350 DEG C and pressure is 1~10MPa, into reactor with Volume space velocity is 500~30000mL/ (gcatH) hydrogen and carbon dioxide being passed through, are made low carbon mixed alcohol, it is characterized in that described Hydrogen and carbon dioxide mol ratio be (1~6)：1；Wherein, it can contain in the gaseous mixture of described hydrogen and carbon dioxide With the carbon monoxide of carbon dioxide mol ratio 0~20%.
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