CN103191741B - Copper-iron core-shell catalyst for lower alcohol synthesis as well as preparation method and application thereof - Google Patents
Copper-iron core-shell catalyst for lower alcohol synthesis as well as preparation method and application thereof Download PDFInfo
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- CN103191741B CN103191741B CN201310095284.2A CN201310095284A CN103191741B CN 103191741 B CN103191741 B CN 103191741B CN 201310095284 A CN201310095284 A CN 201310095284A CN 103191741 B CN103191741 B CN 103191741B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a copper-iron core-shell catalyst for lower alcohol synthesis, comprising Fe2O3 and CuO. The catalyst is of a core-shell structure, the core of the catalyst is Fe2O3, and the shell of the catalyst is CuO; and the element mol ratio Cu:Fe of the catalyst is 1:8-8:1. The catalyst has the advantages of iron sintering prevention, high alcohol selectivity and good stability.
Description
Technical field
The present invention relates to a kind of formate low-carbon alcohol catalyst with and its preparation method and application, be specially the synthetic method and the application that relate to a kind of hud typed synthesis of low-carbon alcohol CuFe catalyst.
Background technology
Development along with the energy and chemical industry, oil is constantly consumed, single oil dependent form energy resource structure has caused the attention of various countries and has watched out for, and changes single energy resource structure, finds emphasis and direction that new alternative energy source and industrial chemicals source become research.Under this background, the coal that reserves will be far longer than oil becomes best selection, but due to the physical behavior of coal with and burning, processing characteristics, greatly limited its development, therefore the technology, through certain step, coal liquefaction being used again becomes study hotspot.
In recent years, C
1-C
6mAS has shown at fuel and chemical field the using value that it is important gradually, and MAS can be used as fuel additive, clean alternative fuel and high valuable chemicals intermediate etc.MAS is as alternative fuel, although its calorific value a little less than vapour, diesel oil, the existence of oxygen in alcohol, makes its ratio of combustion vapour, diesel oil abundant, CO, NO in tail gas
xand hydro carbons discharge capacity is few, be environmental friendliness fuel.MAS clean gasoline additive, has very high octane number, explosion-proof, anti-seismic performance is superior, also there is no serious pollution problem compared with MTBE, and wherein contained higher alcohol content is higher, and the intersolubility of itself and gasoline is better.In addition, MAS is further processed to a large amount of C of gained
2+ alcohol all can be used as industrial chemicals and chemicals intermediate utilizes.
At present, coal has a large amount of bibliographical informations through low carbon alcohol by synthetic gas, representative catalyst system mainly contains four classes: (1) modified methanol catalyst (Cu-Zn, Zn-Cr): such catalyst is for being used appropriate alkali metal or alkali-earth metal modified catalyst for methanol to obtain (patent has the EP-0034338-A2 of C.E.Hofstadt etc. and Snam company to subsidize the United States Patent (USP) 4513100 of Fattore etc.), this type of catalyst activity is higher, product is mainly methyl alcohol and isobutanol, but severe reaction conditions (14-20MPa, 350-450 ℃); (2) modification fischer-tropsch catalysts (Cu-Co): France Petroleum Institute (IFP) has first developed Cu-Co low-carbon alcohol catalyst (US Patent 4122110,4291126 and GB Patent 2118061,2158730), the synthetic primary product of this catalyst is C
1-C
6straight chain n-alkanol, accessory substance is mainly C
1-C
6aliphatic hydrocarbon, reaction condition is gentle, but less stable; (3) noble metal Rh catalyst (US Patent 4014913,4096164 etc.), such catalyst has higher active and outstanding C
2+ alcohol is selective, but it is expensive to be limited to the compound of noble metal Rh, and cost is higher, and Rh catalyst easily poisoning feature etc. limited the development of such catalyst; (4) such catalyst product of Mo series catalysts (being represented as the US Patent 4882360 of Stevens etc.) is mainly C
1-C
5straight chain n-alkanol, have the moisture feature such as few of unique resistance to sulphur and product, but catalyst stability and life-span is poor.
In recent years, lot of documents has been reported the special construction of " nucleocapsid " has been applied to conventional nano particle, improves its surface nature as its surface charge density, functional group's kind etc.In addition, also have by this special construction of nucleocapsid, two kinds of catalysts are combined to reach the object that substep catalytic reaction is combined into a step catalytic process, greatly saved time and energy consumption.Modification fischer-tropsch catalysts in synthol catalyst was not also reported the impact of bimetallic nucleocapsid structure on alcohol product at present.
Summary of the invention
The object of the present invention is to provide a kind of iron sintering that prevents, alcohol is selectively high, synthesis of low-carbon alcohol copper iron nucleocapsid catalyst and the preparation method and application of good stability.
Catalyst of the present invention is by Fe
2o
3forming with CuO, is a kind of nucleocapsid structure, and the core of catalyst is Fe
2o
3, shell is CuO, it is 1:8-8:1 that catalyst elements mol ratio consists of Cu:Fe.
Method of the present invention comprises the steps:
First by Cu (NO
3)
2, Fe (NO
3)
3, urea is dissolved in ionized water and forms mixed solution, makes Cu in mixed solution
2+, Fe
3+total concentration 0.08-0.1molL
-1, urea concentration 0.8-1molL
-1mixed solution is refluxed at 60-100 ℃, and the mixing speed at 100-500rpm stirs simultaneously, and constantly the pH of detection architecture is until pH value of solution=7, under reflux temperature and mixing speed permanence condition, continue return stirring 30-60min, centrifugation, dry 6-12h at 60-80 ℃, at 200-500 ℃, calcine 1-5h, product, is 100-300 ℃ at reduction temperature, reducing gas volume space velocity 3000-4000h
-1, reduction pressure is 0.1-1.0MPa H
2/ CO mol ratio is under the synthesis gas condition of 1-3:1, and product reduces 10-15h in fixed bed reactors, obtains catalyst.
Application process of the present invention is as follows:
Reaction is carried out in fixed bed reactors.Reaction condition is H
2/ CO mol ratio is 1-3:1, and reaction temperature is 200-260 ℃, and pressure is 3.0-5.0MPa, and air speed is 4000-5000h
-1.
The present invention has the following advantages:
1, this catalyst has novel structure and the simple advantage of synthetic method.
2, this catalyst has the advantages that to prevent Fe sintering.
3, this catalyst has C
2 +the selective high feature of alcohol.
4, this catalyst has good stability.
5, this catalyst has the poor feature of heteroion.
Accompanying drawing explanation
Fig. 1 be the present invention prepared Fe
2o
3the TEM figure of@CuO catalyst, this figure is applicable to all embodiment.
The Fe of the nucleocapsid structure of known synthesized from accompanying drawing
2o
3@CuO catalyst is uniformly dispersed, and has the tiny chip of part, and catalyst granules is spindle, each other without reuniting, and regular shape.Concerning with individual particle, light-colored part is CuO, middle dark part is Fe
2o
3.
The specific embodiment
Embodiment 1:
By 2.42gCu (NO
3)
23H
2o, 32.32gFe (NO
3)
39H
2o, 60g urea are dissolved in 1000ml deionized water, mechanical agitation (mixing speed 500rpm) simultaneously refluxes mixed solution at 90 ℃, constantly detection architecture pH is until pH value of solution=7, under reflux temperature and mixing speed permanence condition, continue stirring and refluxing 30min, centrifugation, dry 9h at 80 ℃, at 450 ℃, calcine 2h, make catalyst, be designated as CF-1.It is 1:8 that catalyst elements mol ratio consists of Cu:Fe.
Make catalyst in fixed bed reactor, in the synthesis gas of 200 ℃, (mol ratio is H
2/ CO=2) reduction in, reducing gas volume space velocity 3000h
-1, reduction pressure is 0.1MPa, the recovery time is 15h.After cooling, switching synthesis gas reacts.Reactant is collected by hot trap, cold-trap respectively.Reaction condition is: unstripped gas mol ratio H
2/ CO=2, reaction temperature is 240 ℃, and pressure is 4.0MPa, and air speed is 5000h
-1.CF-1 catalyst synthol reaction result is as shown in table 1.
Embodiment 2:
By 2.42gCu (NO
3)
23H
2o, 16.16gFe (NO
3)
39H
2o, 60g urea are dissolved in 1000ml deionized water, mechanical agitation (mixing speed 500rpm) simultaneously refluxes mixed solution at 90 ℃, constantly detection architecture pH is until pH value of solution=7, under reflux temperature and mixing speed permanence condition, continue stirring and refluxing 30min, centrifugation, dry 9h at 80 ℃, at 450 ℃, calcine 2h, make catalyst, be designated as CF-2.It is 1:4 that catalyst elements mol ratio consists of Cu:Fe.
Make catalyst in fixed bed reactor, in the synthesis gas of 200 ℃, (mol ratio is H
2/ CO=2) reduction in, reducing gas volume space velocity 3500h
-1, reduction pressure is 0.1MPa, the recovery time is 15h.After cooling, switching synthesis gas reacts.Reactant is collected by hot trap, cold-trap respectively.Reaction condition is: unstripped gas mol ratio H
2/ CO=2, reaction temperature is 240 ℃, and pressure is 4.0MPa, and air speed is 5000h
-1.CF-2 catalyst synthol reaction result is as shown in table 1.
Embodiment 3:
By 2.42gCu (NO
3)
23H
2o, 4.04gFe (NO
3)
39H
2o, 60g urea are dissolved in 1000ml deionized water, mechanical agitation (mixing speed 500rpm) simultaneously refluxes mixed solution at 90 ℃, constantly detection architecture pH is until pH value of solution=7, under reflux temperature and mixing speed permanence condition, continue stirring and refluxing 30min, centrifugation, dry 9h at 80 ℃, at 450 ℃, calcine 2h, make catalyst, be designated as CF-3.It is 1:1 that catalyst elements mol ratio consists of Cu:Fe.
Make catalyst in fixed bed reactor, in the synthesis gas of 200 ℃, (mol ratio is H
2/ CO=2) reduction in, reducing gas volume space velocity 4000h
-1, reduction pressure is 0.1MPa, the recovery time is 15h.After cooling, switching synthesis gas reacts.Reactant is collected by hot trap, cold-trap respectively.Reaction condition is: unstripped gas mol ratio H
2/ CO=2, reaction temperature is 240 ℃, and pressure is 4.0MPa, and air speed is 5000h
-1.CF-3 catalyst synthol reaction result is as shown in table 1.
Embodiment 4:
By 9.66gCu (NO
3)
23H
2o, 4.04gFe (NO
3)
39H
2o, 60g urea are dissolved in 1000ml deionized water, mechanical agitation (mixing speed 500rpm) simultaneously refluxes mixed solution at 90 ℃, constantly detection architecture pH is until pH value of solution=7, under reflux temperature and mixing speed permanence condition, continue stirring and refluxing 30min, centrifugation, dry 9h at 80 ℃, at 450 ℃, calcine 2h, make catalyst, be designated as CF-4.It is 4:1 that catalyst elements mol ratio consists of Cu:Fe.
Make catalyst in fixed bed reactor, in the synthesis gas of 200 ℃, (mol ratio is H
2/ CO=2) reduction in, reducing gas volume space velocity 4500h
-1, reduction pressure is 0.1MPa, the recovery time is 15h.After cooling, switching synthesis gas reacts.Reactant is collected by hot trap, cold-trap respectively.Reaction condition is: unstripped gas mol ratio H
2/ CO=2, reaction temperature is 240 ℃, and pressure is 4.0MPa, and air speed is 5000h
-1.CF-4 catalyst synthol reaction result is as shown in table 1.
Embodiment 5:
By 19.33gCu (NO
3)
23H
2o, 4.04gFe (NO
3)
39H
2o, 60g urea are dissolved in 1000ml deionized water, mechanical agitation (mixing speed 500rpm) simultaneously refluxes mixed solution at 90 ℃, constantly detection architecture pH is until pH value of solution=7, under reflux temperature and mixing speed permanence condition, continue stirring and refluxing 30min, centrifugation, dry 9h at 80 ℃, at 450 ℃, calcine 2h, make catalyst, be designated as CF-5.It is 8:1 that catalyst elements mol ratio consists of Cu:Fe.
Make catalyst in fixed bed reactor, in the synthesis gas of 200 ℃, (mol ratio is H
2/ CO=2) reduction in, reducing gas volume space velocity 5000h
-1, reduction pressure is 0.1MPa, the recovery time is 15h.After cooling, switching synthesis gas reacts.Reactant is collected by hot trap, cold-trap respectively.Reaction condition is: unstripped gas mol ratio H
2/ CO=2, reaction temperature is 240 ℃, and pressure is 4.0MPa, and air speed is 5000h
-1.CF-5 catalyst synthol reaction result is as shown in table 1.
Table 1 catalyst reaction performance
Claims (1)
1. a copper iron nucleocapsid catalyst for synthesis of low-carbon alcohol, is characterized in that catalyst is by Fe
2o
3forming with CuO, is a kind of nucleocapsid structure, and the core of catalyst is Fe
2o
3, shell is CuO, it is 1:8-8:1 that catalyst elements mol ratio consists of Cu:Fe;
And preparation by the following method:
First by Cu (NO
3)
2, Fe (NO
3)
3, urea is dissolved in ionized water and forms mixed solution, makes Cu in mixed solution
2+, Fe
3+total concentration 0.08-0.1molL
-1, urea concentration 0.8-1molL
-1mixed solution is refluxed at 60-100 ℃, simultaneously the mixing speed at 100-500rpm stirs, and constantly the pH of detection architecture is until pH value of solution=7, under reflux temperature and mixing speed permanence condition, continue return stirring 30-60min, centrifugation, dry 6-12h at 60-80 ℃, calcines 1-5h at 200-500 ℃, at reduction temperature, be 100-300 ℃, reducing gas volume space velocity 3000-4000h
-1, reduction pressure is 0.1-1.0MPa, H
2/ CO mol ratio is under the synthesis gas condition of 1-3:1, and product reduces 10-15h in fixed bed reactors, obtains catalyst.
2. the application of the copper iron nucleocapsid catalyst of a kind of synthesis of low-carbon alcohol as claimed in claim 1, is characterized in that comprising the steps:
Reaction is carried out in fixed bed reactors, and reaction condition is H
2/ CO mol ratio is 1-3:1, and reaction temperature is 200-260 ℃, and pressure is 3.0-5.0MPa, and air speed is 4000-5000h
-1.
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| CN104148119B (en) * | 2014-09-08 | 2016-09-28 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of catalyst rolling molding |
| CN104841449B (en) * | 2015-04-09 | 2017-03-15 | 中国科学院山西煤炭化学研究所 | A kind of copper nucleocapsid catalyst of synthesis of low-carbon alcohol and preparation method and application |
| CN104841432B (en) * | 2015-05-22 | 2017-02-01 | 厦门大学 | Catalyst for preparing low-carbon alcohol from synthetic gas and preparation method for catalyst |
| CN107282942A (en) * | 2017-06-14 | 2017-10-24 | 中国科学院山西煤炭化学研究所 | A kind of thermal decomposition method prepares the preparation method of the CuFe nano-particles of size adjustable |
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| CN101185899A (en) * | 2007-12-21 | 2008-05-28 | 中国科学院山西煤炭化学研究所 | Copper base catalyst for producing low carbon mixed alcohol by synthesis gas and preparation method and application |
| CN102872881B (en) * | 2012-09-17 | 2014-08-20 | 中国科学院山西煤炭化学研究所 | Copper-based catalyst used in process of synthesizing low carbon mixed alcohol and preparation method and application of catalyst |
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Inventor after: Sun Yuhan Inventor after: Han Xinyou Inventor after: Fang Kegong Inventor after: Lin Minggui Inventor after: Wu Xiuzhang Inventor after: Lu Weimin Inventor after: Li Kejian Inventor after: Zhang Xuwen Inventor after: Li Yi Inventor before: Sun Yuhan Inventor before: Han Xinyou Inventor before: Fang Kegong Inventor before: Lin Minggui Inventor before: Wang Jungang Inventor before: Guo Heqin |
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