CN1390640A - Nano CuZnAl catalyst for synthesizing methanol and dimethylether and its preparing process - Google Patents
Nano CuZnAl catalyst for synthesizing methanol and dimethylether and its preparing process Download PDFInfo
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- CN1390640A CN1390640A CN 02136295 CN02136295A CN1390640A CN 1390640 A CN1390640 A CN 1390640A CN 02136295 CN02136295 CN 02136295 CN 02136295 A CN02136295 A CN 02136295A CN 1390640 A CN1390640 A CN 1390640A
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Abstract
A nano Cu-Zn-Al catalyst for synthesizing methanol or dimethylether contains nano Cu (30-60 mol%), Zn (30-60) and A (10-15), and is prepared from nano (2-10 nm) copper, zinc oxide and aluminium oxide through reducing the carbonates or oxalates of Cu, Zn and Al by borohydride of alkali metal or hydrazine hydrate at 0-50 deg.C, filtering, washing, vacuum drying and calcining in inertial atmosphere. Its advantage is high catalytic performance.
Description
Technical field
The invention belongs to chemical technology field, relate to the new preparation method of a kind of synthesizing methanol and dimethyl ether catalyst, be specifically related to a kind of preparation method who is used for the nano CuZnAl catalyst of synthesizing methanol or dimethyl ether.
Methyl alcohol is synthetic to be a very important chemical process, and CuZnAl catalyst is the main component of present low pressure methanol synthesis catalyst and low temperature water gas conversion industrial catalyst.At present, the CuZnAl catalyst of industrial application all prepares with coprecipitation.As BP 1,296,211 and 1,296,212 coprecipitations that propose are to make precipitating reagent with sodium carbonate, copper zinc-aluminium nitrate mixed liquor is reached under the precipitation temperature condition of determining in the pH value of determining form carbonate sediment, clean sodium ion with distilled water, drying roasting then is processed into copper zinc-aluminium oxidation mixture.This method has sodium ion washing difficulty, the easy temperature runaway of reduction process and cause catalyst activity significantly to descend, a plurality of shortcomings such as catalyst activity poor repeatability.Particularly it is to be noted, above-mentioned industrial CuZnAl catalyst must can formally come into operation after the prereduction of complexity is handled before use, and activation process complex process and rather consuming time not only, and in the reduction activation process trickle condition change to the catalytic performance influence significantly.In addition, people also find the industrial Cu/ZnO/Al of traditional coprecipitation method preparation
2O
3Catalst for synthesis of methanol is used for CO
2When synthesizing methanol by hydrogenating and dimethyl ether reaction, methyl alcohol and dimethyl ether activity are very low.Therefore, design and exploitation preparation method are easy, and catalytic performance is stable, need not to carry out complicated prereduction technology promptly can be under temperate condition relatively abundant activation CO
2, and have higher methyl alcohol or the direct dimethyl ether synthesis of one-step method optionally new catalyst just seem very necessary.
On the other hand, along with being on the rise of environmental problems such as global industrial pollution and greenhouse effects, for how to control effectively and utilize the pilot study of carbon dioxide to cause that people pay attention to greatly efficiently.Be that catalytic material transforms that to produce chemicals such as methyl alcohol and dimethyl ether be one of most important forward position research topic in contemporary carbon one chemical industry with the carbon dioxide.Methyl alcohol and dimethyl ether are very important carbon one Elementary Chemical Industry raw materials, further the chemicals of directed synthetic many high added values.In recent years, methyl alcohol and dimethyl ether also are considered to a kind of substitute fuel of alternative petrol and diesel oil of extremely promising cleaning.Therefore, utilize direct synthesizing methanol of hydrogenation of carbon dioxide and dimethyl ether not only can significantly improve existent environment of people, can also alleviate serious day by day energy crisis and crisis of resource.
21st century is the century of new material.Nano material has caused that as one of most important basic material of new century personages of various circles of society more and more note.Nano-particle catalyst has characteristics such as high-ratio surface, high surface energy and surface-active position be many, shows the catalytic performance of the uniqueness that is different from conventional material, is used for carbon dioxide hydrogenation reaction as new catalyst and has development prospect preferably.At present, domestic and international research report in this respect is increasing.Therefore, according to the synthesizing methanol reaction characteristics, design and preparation are fit to the synthesizing methanol reaction characteristics and are convenient to implement and the nanocatalyst that uses seems extremely attractive.
Summary of the invention
The objective of the invention is to propose a kind of catalytic efficiency height, need not complicated reduction activation processing before the reaction and can be directly used in the novel nano metal CuZnAl catalyst of synthesizing methanol or one-step method dimethyl ether synthesizing reaction, and propose this Preparation of catalysts method.
The catalyst that is used for synthesizing methanol or dimethyl ether provided by the invention, be a kind of nano metal copper-based catalysts that contains element state copper, it is made up of multicomponent reactive components such as copper, zinc, aluminium, and the mole proportioning of each component is as follows: Cu:25～65%, Zn:65～25%, Al:20～5%.The component total amount is 100%.Preferred mole proportioning is: Cu:30～60%, Zn:60～30%, Al:15～10%.Metallic copper is of a size of 2～10nm.Wherein, nanometer copper is highly dispersed on zinc oxide-alumina composite carrier.
The preparation method of the nano CuZnAl catalyst that the present invention proposes is as follows:
Press the content ratio of each component, make the coprecipitate slurries that contain copper, zinc, aluminium compound with coprecipitation earlier, this sediment is light blue; Then the sediment slurries are directly reacted with reducing agent, going back native copper, and discharge a large amount of hydrogen, the material after the reduction is a black precipitate; With the sediment suction filtration, wash (generally spend deionised water earlier, wash with ethanol again) vacuum drying again; At last the moulding of product directly compressible is got catalyst, perhaps product (is generally high-purity N at inert gas
2) protection in 250 ℃～400 ℃ roastings, makes catalyst down or under vacuum.
Among the present invention, used reducing agent can adopt alkali metal borohydride (as NaBH
4, KBH
4Deng) or hydrazine hydrate (N
2H
4) the aqueous solution or ethanolic solution, its consumption is excessive 50～200%.
Among the present invention, the temperature conditions of reduction reaction can be 0 ℃～50 ℃.
Among the present invention, the coprecipitate of copper, zinc, aluminium compound is the carbonate mixture of a kind of cupric, zinc, aluminium, or the alkaline color carbonate mixture of cupric, zinc, aluminium, or the oxalate mixtures of cupric, zinc, aluminium, perhaps be above-mentioned two kinds (comprising two kinds) above mixture.
Method of the present invention has been destroyed the class colloid form structure of the thickness of original coprecipitate owing to handle with reducing agent after precipitation process, make the Na harmful to catalytic activity
+Ion is washes clean very easily.Can prevent to precipitate the reunion with particle of subsiding of structure in the common dry run in the preparation process of the present invention to a certain extent with ethanol washing and vacuum drying treatment process.
This process is suitable for operating on thermopnore or fixed bed, perhaps intermittently carries out, and perhaps carries out continuously, preferably carries out continuously.Activity of such catalysts provided by the invention can be tested with the following method:
Activity rating carries out on continuous-flow pressurization stainless steel microreactor.Reactor (200mm * Φ 6mm) reaction bed temperature is controlled through the program temperature controller by chromel-alumel couple.Reaction pressure is by the constant pressure valve control of porch.Reaction gas flow speed is controlled by reset valve, and by mass flowmenter and soap film flowmeter monitoring.Product is by online gas chromatographic analysis.The chromatogram carrier gas is H
2, thermal conductivity cell detector detects.(Poropak-Q and TDX-01 2m) are used for separation of C H respectively to the chromatographic column of two parallel connections
3OH, dimethyl ether, higher alcohol and CO, CO
2, CH
4Deng product.
The inventive method is on the basis of carbonate or oxalate coprecipitation method, with the liquid-phase reduction agent coprecipitate slurry is handled, and can overcome many weak points of traditional co-precipitation method.The washing process of removing sodium ion in the preparation process is quick and convenient, last handling process gentleness, catalyst activity and selectivity height.
The present invention compared with prior art has following advantage:
1, the copper component is the element state nano particle in the catalyst, and other component is an oxidation state, and each component distributes more even, and has strong interaction between each component;
2, catalyst can directly use after roasting, does not need complexity, performance difficulty and permanent reduction activation process consuming time;
3, this method for preparing catalyst is simple, easy operating, and catalyst performance good reproducibility, and catalytic activity and selectivity all are better than traditional co-precipitated catalyst, realize the industry amplification easily.
The specific embodiment
The Catalysts and its preparation method that the invention is further illustrated by the following examples proposes, the embodiment that provides the catalyst for preparing with traditional sodium carbonate coprecipitation simultaneously as a comparison.
Embodiment 1
Get 10.22 gram copper chloride (CuCl
22H
2O), 4.09 gram zinc chloride (ZnCl
2) and 2.42 gram aluminium chloride (AlCl
36H
2O) add water wiring solution-forming (100mL); Other gets 11.13 gram sodium carbonate (Na
2CO
3) wiring solution-forming (100mL); In 100mL water, add hybrid metal solution and sodium carbonate liquor simultaneously under the vigorous stirring, keep the pH value in the precipitation process about 7.0, prepare the mixed sediment of copper zinc-aluminium azury; Add 200ml under the vigorous stirring in the fresh sediment and be dissolved with 19.4 gram KBH
4The aqueous solution, the precipitation blackening and is emitted a large amount of hydrogen.The suction filtration black precipitate spends deionised water respectively 3 times rapidly, after ethanol washs 3 times, and vacuum drying.The moulding of sample directly compressible is used for catalytic reaction or is used for catalytic reaction after 350 ℃ of roasting.The loading amount of catalyst is 0.5g on the flow-type reaction unit, and catalyst is handled without prereduction and promptly reacted CO
2/ H
2Be 1/3 (reaction stagnation pressure 2.0MPa), air speed is 3600h
-1, the methyl alcohol yield is 6.0% in the time of 240 ℃.
Embodiment 2
Under the room temperature, under vigorous stirring toward the KBH that drips 0.2 M during concentration is the aqueous solution of copper chloride of 0.5 M
4The aqueous solution, vigorous reaction is also emitted a large amount of hydrogen, obtains the nano metal Cu catalyst of brownish black after washing and the vacuum drying.Implement the methyl alcohol synthetic reaction on the flow-type reaction unit in embodiment 1, catalyst is handled without prereduction and is promptly reacted, and the loading amount of catalyst is 0.5g, CO
2/ H
2Be 1/3 (2.0MPa), air speed is 3600h
-1, the methyl alcohol yield is 0.8% in the time of 240 ℃.
The comparative example 1
Get 10.22 gram copper chloride (CuCl
22H
2O), 4.09 gram zinc chloride (ZnCl
2) and 2.42 gram aluminium chloride (AlCl
36H
2O) add water wiring solution-forming (100mL); Other gets 11.13 gram sodium carbonate wiring solution-formings (100mL); In 100mL water, add hybrid metal solution and sodium carbonate liquor simultaneously under the vigorous stirring, prepare the mixed sediment of copper zinc-aluminium; With deionized water washing sediment 6 times, to go out remaining Na ion, after 110 ℃ of oven dry, 350 ℃ of roastings 5 hours.The loading amount of catalyst is 0.5g on the flow-type reaction unit, CO
2/ H
2(2.0 MPa) is 1/3, and air speed is 3600h
-1, catalyst is not handled through prereduction and is promptly reacted, and the yield of methyl alcohol is 0.6% in the time of 240 ℃.
The comparative example 2
Get 10.22 gram copper chloride (CuCl
22H
2O), 4.09 gram zinc chloride (ZnCl
2) and 2.42 gram aluminium chloride (AlCl
36H
2O) add water wiring solution-forming (100mL); Other gets 11.13 gram sodium carbonate wiring solution-formings (100mL); In 100mL water, add hybrid metal solution and sodium carbonate liquor simultaneously under the vigorous stirring, prepare the mixed sediment of copper zinc-aluminium; With deionized water washing sediment 6 times, to go out remaining Na ion, after 110 ℃ of oven dry, 350 ℃ of roastings 5 hours.The loading amount of catalyst is 0.5g on the flow-type reaction unit, CO
2/ H
2(2.0 MPa) is 1/3, and air speed is 3600h
-1, catalyst reacts after 16 hours 260 ℃ of prereduction, and the yield of methyl alcohol is 3.6% in the time of 240 ℃.
Embodiment 3
Get 10.22 gram copper chloride (CuCl
22H
2O), 4.09 gram zinc chloride (ZnCl
2) and 2.42 gram aluminium chloride (AlCl
36H
2O) add water wiring solution-forming (100mL); Other gets 11.13 gram sodium carbonate wiring solution-formings (100mL); In 100mL water, add hybrid metal solution and sodium carbonate liquor simultaneously under the vigorous stirring, prepare the mixed sediment of copper zinc-aluminium; Add 20ml hydrazine hydrate solution (40wt%) under the vigorous stirring, obtain yellow mercury oxide, use deionized water washing sediment 6 times, to go out remaining Na
+Ion is after 110 ℃ of oven dry, 350 ℃ of roastings.The loading amount of catalyst is 0.5g on the flow-type reaction unit, CO
2/ H
2(2.0 MPa) is 1/3, and air speed is 3600h
-1, catalyst is handled without prereduction and is promptly reacted, and the yield of methyl alcohol is 2.2% in the time of 240 ℃.
Embodiment 4
Get 10.22 gram copper chloride (CuCl
22H
2O), 4.09 gram zinc chloride (ZnCl
2) and 2.42 gram aluminium chloride (AlCl
36H
2O) add water wiring solution-forming (100mL); Other gets 22.63 gram oxalic acid wiring solution-formings (100mL); In 100mL water, add hybrid metal solution and oxalic acid solution simultaneously under the vigorous stirring, prepare the mixed sediment of copper zinc-aluminium; Add 200ml under the vigorous stirring and be dissolved with 19.4 gram KBH
4The aqueous solution, obtain black precipitate, rapidly the suction filtration black precipitate spends deionised water respectively 3 times, after the ethanol washing 3 times, after the vacuum drying, 350 ℃ of roastings.The loading amount of catalyst is 0.5g on the flow-type reaction unit, CO
2/ H
2(2.0 MPa) is 1/3, and air speed is 3600h
-1, catalyst is handled without prereduction and is promptly reacted, and the yield of methyl alcohol is 6.2% in the time of 240 ℃.
Embodiment 5
Get 13.40 gram copper nitrate (Cu (NO
3)
22H
2O), 5.68 gram zinc nitrate (Zn (NO
3)
2) and 2.80 gram aluminum nitrate (Al (NO
3)
36H
2O) add water wiring solution-forming (100mL); Other gets 22.63 gram oxalic acid wiring solution-formings (100mL); In 100mL water, add hybrid metal solution and oxalic acid solution simultaneously under the vigorous stirring, prepare the mixed sediment of copper zinc-aluminium; Add 200ml under the vigorous stirring and be dissolved with 19.4 gram KBH
4The aqueous solution, obtain black precipitate, rapidly the suction filtration black precipitate spends deionised water respectively 3 times, after the ethanol washing 3 times, after the vacuum drying, 350 ℃ of roastings.The loading amount of catalyst is 0.5g on the flow-type reaction unit, CO
2/ H
2(2.0 MPa) is 1/3, and air speed is 3600h
-1, catalyst is handled without prereduction and is promptly reacted, and the yield of methyl alcohol is 6.5% in the time of 240 ℃.
Embodiment 6
Connect example 1.With the catalyst sample after the vacuum drying and γ-Al
2O
3Mix by weight about 3: 1 ratios, obtain Composite Double function nano copper-based catalysts, be used for the direct dimethyl ether synthesis of one-step method.The loading amount of catalyst is 1.5g on the flow-type reaction unit, CO/CO
2/ H
2(4.0 MPa) is 33/3/64, and air speed is 1800h
-1, catalyst is handled without prereduction and is promptly reacted, and the yield of dimethyl ether is 84% in the time of 240 ℃.
Claims (8)
1. the nano CuZnAl catalyst of synthesizing methanol or dimethyl ether, it is characterized in that containing the nano-metallic copper base of element state copper, be made up of copper, zinc, aluminium active ingredient, the molar percentage of each component is: Cu:25～65%, Zn:65～25%, Al:20～5%; The component total amount is 100%, and metallic copper is of a size of 2～10nm.
2, nano CuZnAl catalyst according to claim 1 is characterized in that the molar percentage of each component is: Cu:30～60%, and Zn:60～30%, Al:15～10%, total amount is 100%.
3, the nano-metallic copper zinc-aluminium Preparation of catalysts method of a kind of synthesizing methanol as claimed in claim 1 or dimethyl ether is characterized in that the first coprecipitate slurries of making cupric, zinc, aluminium compound with coprecipitation; Direct and the reducing agent reaction with the coprecipitate slurries then is to go back native copper; With the sediment suction filtration, wash vacuum drying again; At last with the moulding of product direct tablet compressing, perhaps with product fusing in 250 ℃～400 ℃ under the inert gas shielding or under vacuum, make catalyst.
4, according to the preparation method of the described nano CuZnAl catalyst of claim 3, the coprecipitate that it is characterized in that copper, zinc, aluminium compound is the carbonate mixture of a kind of cupric, zinc, aluminium.
5, according to the preparation method of the described nano CuZnAl catalyst of claim 3, the coprecipitate that it is characterized in that copper, zinc, aluminium compound is the basic carbonate salt mixture of a kind of cupric, zinc, aluminium.
6, according to the preparation method of the described nano CuZnAl catalyst of claim 3, the coprecipitate that it is characterized in that copper, zinc, aluminium compound is the oxalate mixtures of a kind of cupric, zinc, aluminium.
7, according to the preparation method of the described nano CuZnAl catalyst of claim 1, the coprecipitate that it is characterized in that copper, zinc, aluminium compound is following two or more mixture: the carbonate mixture of cupric, zinc, aluminium, basic carbonate salt mixture, oxalate mixtures.
8,, it is characterized in that reducing agent adopts the aqueous solution or the ethanolic solution of alkali metal borohydride or hydrazine hydrate, the consumption of reducing agent excessive 50～200% according to the preparation method of the described nano CuZnAl catalyst of claim 3.
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| CN1301793C (en) * | 2004-07-29 | 2007-02-28 | 复旦大学 | Nano carbon material modified copper base catalyst and its preparing method |
| CN100500285C (en) * | 2005-08-11 | 2009-06-17 | 中国科学院山西煤炭化学研究所 | Catalyst, production and use for producing dimethyl ether by dewatering methanol |
| CN102240552A (en) * | 2011-05-16 | 2011-11-16 | 中国石油化工集团公司 | Method for preparing high-performance methanol synthesis catalyst |
| CN101745403B (en) * | 2008-12-18 | 2012-09-12 | 中国石油化工股份有限公司 | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas |
| CN101745397B (en) * | 2008-12-18 | 2015-05-20 | 中国石油化工股份有限公司 | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas |
| CN105457641A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Preparation of copper, zinc and aluminum methanol synthesizing catalyst by virtue of reduction deposition method |
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| CN110833834A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of supported ruthenium-copper bimetallic catalyst, product and application thereof |
| CN111545209A (en) * | 2020-04-30 | 2020-08-18 | 鞍钢股份有限公司 | Method for synthesizing Cu/ZnO catalyst based on hard template copper oxide nanosheets |
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|---|---|---|---|---|
| CN1301793C (en) * | 2004-07-29 | 2007-02-28 | 复旦大学 | Nano carbon material modified copper base catalyst and its preparing method |
| CN100500285C (en) * | 2005-08-11 | 2009-06-17 | 中国科学院山西煤炭化学研究所 | Catalyst, production and use for producing dimethyl ether by dewatering methanol |
| CN101745403B (en) * | 2008-12-18 | 2012-09-12 | 中国石油化工股份有限公司 | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas |
| US8552074B2 (en) | 2008-12-18 | 2013-10-08 | China Petroleum & Chemical Corporation | Process for preparing methanol, dimethyl ether, and low carbon olefins from syngas |
| CN101745397B (en) * | 2008-12-18 | 2015-05-20 | 中国石油化工股份有限公司 | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas |
| CN102240552A (en) * | 2011-05-16 | 2011-11-16 | 中国石油化工集团公司 | Method for preparing high-performance methanol synthesis catalyst |
| CN105457641A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Preparation of copper, zinc and aluminum methanol synthesizing catalyst by virtue of reduction deposition method |
| CN105457641B (en) * | 2014-09-09 | 2018-05-22 | 中国石油化工股份有限公司 | Reduction sedimentation prepares copper-zinc-aluminium methanol synthetic catalyst |
| CN109937089A (en) * | 2016-11-15 | 2019-06-25 | 巴斯夫欧洲公司 | Method of the production for the mechanically stable catalyst of hydrogenating carbonyl compounds, the catalyst and method for hydrogenation |
| CN109937089B (en) * | 2016-11-15 | 2022-07-26 | 巴斯夫欧洲公司 | Process for producing a mechanically stable catalyst for the hydrogenation of carbonyl compounds, said catalyst and hydrogenation process |
| CN107011120A (en) * | 2017-05-09 | 2017-08-04 | 西北大学 | A kind of method of recycling treatment carbon dioxide and water high selectivity ethanol |
| CN107011120B (en) * | 2017-05-09 | 2020-05-05 | 西北大学 | Method for high-selectivity synthesis of ethanol by resource treatment of carbon dioxide and water |
| CN110833834A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of supported ruthenium-copper bimetallic catalyst, product and application thereof |
| WO2021171316A1 (en) * | 2020-02-27 | 2021-09-02 | Amol Carbons Private Limited | Fixed bed reactor with layered dimethyl ether synthesis catalysts |
| CN111545209A (en) * | 2020-04-30 | 2020-08-18 | 鞍钢股份有限公司 | Method for synthesizing Cu/ZnO catalyst based on hard template copper oxide nanosheets |
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