CN102029166B - Catalyst for preparing low-carbon mixed alcohol by using synthesis gas and preparation method thereof - Google Patents
Catalyst for preparing low-carbon mixed alcohol by using synthesis gas and preparation method thereof Download PDFInfo
- Publication number
- CN102029166B CN102029166B CN2009101966121A CN200910196612A CN102029166B CN 102029166 B CN102029166 B CN 102029166B CN 2009101966121 A CN2009101966121 A CN 2009101966121A CN 200910196612 A CN200910196612 A CN 200910196612A CN 102029166 B CN102029166 B CN 102029166B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- synthesis gas
- percent
- mas
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing low-carbon mixed alcohol by using synthesis gas, which comprises the following components in percentage by weight: 54 to 75 percent of ZrO, 10 to 20 percent of MnO2, 0.4 to 1.0 percent of RxO, 3 to 5 percent of CuO, 4 to 20 percent of C and 0.5 to 1.5 percent of noble metal. The catalyst is prepared by adopting a co-precipitation method, wherein the precursors of the Zr, Mn and Cu elements are nitrates, and the precursor of the C is starch. The catalyst has mild reaction conditions, the selectivity of C2+ alcohol can be more than 36 weight percent, the selectivity of isobutyl alcohol can be more than 25 weight percent, and the selectivity of hydrocarbon (mainly comprising methane) can be less than 4 weight percent. By adding the starch in the preparation of the catalyst and forming amorphous porous carbon in the drying and roasting processes, the specific surface area of the catalyst can be improved, the dispersion of metal oxides is effectively improved, sintering is prevented, and the stability of the catalyst is remarkably improved.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, relate in particular to the Catalysts and its preparation method that a kind of synthesis gas is produced MAS.
Background technology
In the world today, energy strategy all is unusual important problem.Along with the exhaustion day by day of petroleum resources, energy resource consumption is main with coal and natural gas.Coal is the main energy sources of China, from resources effective utilization and environmental protection angle, is the coal indirect reformer research of liquid fuel and chemicals, has a wide range of applications.
By the synthetic MAS of co hydrogenation is to improve the desirable additive of leadless gasoline octane rating, neither contains fragrant same clan material, also sulfur-bearing not, and its octane number is high, has important environmental protection potentiality and economic worth.Therefore, co hydrogenation catalysis synthesizing low-carbon mixed alcohol is the research topic that has most important theories meaning and application prospect in the C1 chemical field.The development of low-carbon alcohol catalyst is the key of synthesizing low-carbon mixed alcohol reaction; The modification Cu-Zn-Al catalyst system and catalyzing of German Lurgi company and the Zn-Cr-K catalyst system and catalyzing (US4513100) of Italian Snam company are arranged in the technical process of this reaction at present than maturation; These two types of catalyst are all by the methanol synthesis catalyst modification, and employed modified additive is alkali metal or alkaline-earth metal; But C
2+The selectivity of alcohol in total alcohol is merely 30wt%, and another problem is that this type of catalyst service condition is comparatively harsh, and temperature requirement is higher than 400 ℃, and pressure is more than the 10MPa.French petroleum research and development develop with Cu-Co be catalyst IFP technology (patent US4122110, US4291126), C in this process products
2+Alcohol content is higher, but this catalyst is a modified additive with alkali metal and rare earth metal, and it forms comparatively complicacy, and preparation technology is comparatively loaded down with trivial details, and the selectivity of isobutanol and space-time yield are lower.
Cu-ZrO
2Catalyst basedly more and more receive publicity owing to have preferably the synthesizing methanol performance.At present, existing much about to Cu-ZrO
2Modification obtains the report of low-carbon alcohols synthetic catalyst.Like Chinese patent CN1075398 at Cu-ZrO
2Be added with group VIII element of Fe, the alkalies and alkaline earth, especially the K auxiliary agent that promote the carbochain growing ability in the catalyst, modification obtains the low-carbon alcohols synthetic catalyst; Chinese patent CN1085118 is at Cu-ZrO
2Be added with the group VIII element Ni, the alkalies and alkaline earth that promote the carbochain growing ability in the catalyst, modification obtains the low-carbon alcohols synthetic catalyst.The catalyst that is provided in these two pieces of patents, C in the product
2+The alcohol selectivity is higher, but the selectivity of alkene is also very high, and greater than 20%, product component is comparatively complicated, is unfavorable for separating.
Summary of the invention
Goal of the invention of the present invention provides the catalyst that a kind of synthesis gas is produced MAS, adopts C in the product of this Preparation of Catalyst
2+The selectivity of alcohol is good, and reaction condition relaxes.
Goal of the invention of the present invention is achieved in that at Cu/ZrO
2Add C and Mn element in the series catalysts, and alkali metal or alkaline-earth metal, C during with raising CO hydrogenation reaction
2+The selectivity of alcohol.
The catalyst that one aspect of the present invention provides a kind of synthesis gas to produce MAS comprises following component in total weight percent:
ZrO
2: 54～75%, MnO
2: 10～20%, R
xO:0.4～1.0%, CuO:3～5%, C:4～20%, noble metal: 0.5～1.5%; Wherein, x=1 or 2, R are alkali metal or alkali earth metal.
Described alkali metal can be Li, Na, K or Cs etc., and described alkaline-earth metal can be Mg, Ca etc., preferred K element among the present invention.
Described noble metal can be noble metals such as Pd, Pt, Rh, and preferred noble metal is Pd among the present invention.The C when adding of noble metal can further improve the CO hydrogenation reaction
2+The selectivity of alcohol.
In the technique scheme, said catalyst is preferably in total weight percent: ZrO
2: 63～73%, MnO
2: 14～16%, R
xO:0.5%, CuO:4.2～4.8%, C:4.7～16.4%, noble metal: 1%.
The present invention provides above-mentioned Preparation of catalysts method on the other hand, may further comprise the steps:
A) be dissolved in fully in the deionized water by the predecessor of said ratio Zr, Mn, Cu element, under the normal temperature with above-mentioned solution and R (OH)
xAqueous solution co-precipitation, stir in the precipitation process and keep pH=12～13;
B) with gained precipitate with deionized water washing in the step a) to neutral, add starch and deionized water again, heating and stir make it become pasty state after, after the drying under 480-520 ℃ of inert atmosphere roasting 5-7 hour again;
C) step b) gained solid is broken for 20～40 orders after; Incipient impregnation R, the roasting 5～7 hours under 480～520 ℃ of inert atmospheres of dry back, the predecessor of incipient impregnation noble metal again; Roasting 5～7 hours under 310～350 ℃ of inert atmospheres more promptly gets required catalyst after the drying.
Among the above-mentioned preparation method, said drying can adopt conventional drying condition, as drying 20 hours at 90 ℃.
Preferably, the predecessor of said Zr, Mn, Cu element is nitrate, like Zr (NO
3)
4, Mn (NO
3)
2.4H
2O, Cu (NO
3)
2Said R is alkali metal or alkaline-earth metal, x=1 or 2; The predecessor of said noble metal is a nitrate, is Pd (NO like the predecessor of Pd
3)
2Said starch is the predecessor of C, and said inert atmosphere is inert gases such as nitrogen, argon gas.
Preferably, among the above-mentioned preparation method, the content of each raw material during the consumption proportion of each raw material is made up of prepared catalyst is confirmed.
The 3rd aspect of the present invention provides the purposes of above-mentioned catalyst, the i.e. application of this catalyst in co hydrogenation synthesizing low-carbon mixed alcohol technology.
Catalyst of the present invention is used for co hydrogenation synthesizing low-carbon mixed alcohol process conditions and can be: pressure 6.0MPa, 340 ℃ of temperature, GHSV=7200h
-1, H
2/ CO=1.
The present invention passes through to Cu/ZrO
2Add C and Mn element, alkali metal or alkaline-earth metal and precious metal additive in the series catalysts, obtained the low-carbon alcohols synthetic catalyst of modification.Catalyst of the present invention is used for co hydrogenation synthesizing low-carbon mixed alcohol technology, C in the time of can improving the CO hydrogenation reaction
2+The selectivity of alcohol.Compared with prior art have following advantage:
1, reaction condition is more gentle;
2, C
2+Selectivity can be greater than 36wt%;
3, the selectivity of isobutanol can be greater than 25wt%;
4, the selectivity of hydrocarbon can be less than 4wt%.
5, add starch in the Preparation of Catalyst, in dry and roasting process, form unformed porous charcoal, can improve the specific area of catalyst, improve the decentralization of metal oxide effectively, prevent sintering, the stability of catalyst significantly improves.
The specific embodiment
Further set forth the utility model below in conjunction with specific embodiment, should be understood that these embodiment only be used to the utility model is described and be not used in the restriction the utility model protection domain.
Embodiment 1
Press ZrO
2: 69.7wt%, MnO
2: 15.3wt%, K
2O:0.5wt%, Pd:1wt%, CuO:4.6wt%, the composition of C:8.9wt%; Zr, Mn, the nitrate of Cu element is dissolved in the deionized water, at normal temperatures with the co-precipitation of KOH solution; Fully stir in the precipitation process and keep pH=13, sediment, adds starch, deionized water and stirs to neutral through the deionized water washing in sediment, heating, stirs and makes it become pasty state; 90 ℃ dry 20 hours down, roasting is 6 hours under 500 ℃ of nitrogen atmospheres, be broken for 20～40 orders after, incipient impregnation K; Drying is 20 hours under 90 ℃, and roasting is 6 hours under 500 ℃ of nitrogen atmospheres, again incipient impregnation Pd (Pd (NO
3)
2As predecessor), drying is 20 hours under 90 ℃, and roasting is 6 hours under 330 ℃ of nitrogen atmospheres, promptly gets required catalyst.CO+H
2Be reflected in the 10mm internal diameter stainless steel tube reactor and carry out, the catalyst of producing before reaction to contain H
210% N
2+ H
2Gaseous mixture switches to synthesis gas and reacts 300 ℃ of reduction 8 hours.Service condition is P=6.0MPa, T=340 ℃, and GHSV=7200h
-1, H
2/ CO=1 collects liquid product with water-bath, and the product that obtains is as shown in table 1 through the gas chromatographic analysis result:
Table 1 gas chromatographic analysis result
Embodiment 2
Catalyst consists of ZrO
2: 73wt%, MnO
2: 16wt%, K
2O:0.5wt%, Pd:1wt%, CuO:4.8wt%, C:4.7wt%, service condition is P=6.0MPa, T=340 ℃, GHSV=7200h
-1, H
2/ CO=1, all the other conditions are with embodiment 1, and the gained result is as shown in table 2:
Table 2 gas chromatographic analysis result
Embodiment 3
Catalyst consists of ZrO
2: 63.9wt%, MnO
2: 14.0wt%, K
2O:0.5wt%, Pd:1wt%, CuO:4.2wt%, C:16.4wt%, service condition is P=6.0MPa, T=340 ℃, GHSV=7200h
-1, H
2/ CO=1, all the other conditions are with embodiment 1, and the gained result is as shown in table 3:
Table 3 gas chromatographic analysis result
Embodiment 4
1 controlling catalyst of embodiment is called catalyst A.
Prepare carbon-free catalyst B by following method:
ZrO
2：76.6wt％，MnO
2：16.8wt％，CuO：5.1wt％，Pd：1wt％，K
2O：0.5wt％。
The identical point of A and B catalyst is (ZrO
2: MnO
2: CuO)
A=(ZrO
2: MnO
2: CuO)
B(wt%), identical (P=6.0MPa, T=340 ℃, GHSV=7200h of preparation method with appreciation condition
-1, H
2/ CO=1); A and B catalyst difference are not carbon containing of A carbon containing, B.Both catalytic performances see the following form with the variation contrast situation in reaction time:
Table 4 gas chromatographic analysis result
When reaction proceeded to 24 hours, the catalytic performance of A and B was basic identical, and products distribution is as broad as long basically.In 100 hours, each item index of A catalyst does not change basically in time.And B carries out along with reaction, and each item index obviously descends, and reaction proceeds to 100 hours, and the CO conversion ratio of B has descended 2.5%, alcohol has descended 5.4% in products distribution, and the content of C2+ alcohol in total alcohol has descended 14.8%.It is thus clear that add the stability that C can improve catalyst.
Embodiment 5
Press ZrO
2: 54wt%, MnO
2: 20wt%, MgO:1wt%, Pt:1.5wt%, CuO:3.5wt%, the composition of C:20wt% is dissolved in the nitrate of Zr, Mn, Cu element in the deionized water, at normal temperatures with Mg (OH)
2The solution co-precipitation is fully stirred in the precipitation process and maintenance pH=12, and sediment is extremely neutral through the deionized water washing; In sediment, add starch, deionized water and stir, heating, stir and make it become pasty state, 90 ℃ dry 20 hours down; Roasting is 7 hours under 480 ℃ of nitrogen atmospheres, be broken for 20～40 orders after, incipient impregnation Mg; Drying is 20 hours under 90 ℃, and roasting is 7 hours under 480 ℃ of nitrogen atmospheres, again incipient impregnation Pt; Drying is 20 hours under 90 ℃, and roasting is 7 hours under 310 ℃ of nitrogen atmospheres, promptly gets required catalyst.
Embodiment 6
Press ZrO
2: 75wt%, MnO
2: 10wt%, Na
2O:0.4wt%, Rh:0.5wt%, CuO:5wt%, the composition of C:9.1wt%; Zr, Mn, the nitrate of Cu element is dissolved in the deionized water, at normal temperatures with the co-precipitation of NaOH solution; Fully stir in the precipitation process and keep pH=13, sediment, adds starch, deionized water and stirs to neutral through the deionized water washing in sediment, heating, stirs and makes it become pasty state; 90 ℃ dry 20 hours down, roasting is 5 hours under 520 ℃ of nitrogen atmospheres, be broken for 20～40 orders after, incipient impregnation K; Drying is 20 hours under 90 ℃, and roasting is 5 hours under 520 ℃ of nitrogen atmospheres, again incipient impregnation Rh; Drying is 20 hours under 90 ℃, and roasting is 5 hours under 350 ℃ of nitrogen atmospheres, promptly gets required catalyst.
Claims (6)
1. a synthesis gas is produced the catalyst of MAS, it is characterized in that, comprises following component: ZrO in total weight percent
2: 54～75%, MnO
2: 10～20%, R
xO:0.4～1.0%, CuO:3～5%, C:4～20%, noble metal: 0.5～1.5%; Wherein, R is alkali metal or alkali earth metal, and x=1 or 2, C are amorphous porous charcoal.
2. synthesis gas as claimed in claim 1 is produced the catalyst of MAS, it is characterized in that, R is the K element.
3. synthesis gas as claimed in claim 1 is produced the catalyst of MAS, it is characterized in that, described noble metal is Pd.
4. produce the Preparation of catalysts method of MAS like the described synthesis gas of arbitrary claim among the claim 1-3 for one kind, may further comprise the steps:
A) be dissolved in the deionized water by the predecessor of proportioning Zr, Mn, Cu element, under the normal temperature with above-mentioned solution and R (OH)
xAqueous solution co-precipitation, and keep pH=12～13;
B) spend deionised water and be precipitated to pH for neutral, add starch and deionized water again, it is dry that it is become behind the pasty state, roasting 5～7 hours under 480～520 ℃ of inert atmospheres again;
C) step b) gained solid is broken for 20～40 orders after; Incipient impregnation R, the roasting 5～7 hours under 480～520 ℃ of inert atmospheres of dry back, the predecessor of incipient impregnation noble metal again; Roasting 5～7 hours under 310～350 ℃ of inert atmospheres more promptly gets required catalyst after the drying.
5. synthesis gas as claimed in claim 4 is produced the Preparation of catalysts method of MAS, it is characterized in that, the predecessor of said Zr, Mn, Cu element is nitrate, and said starch is the predecessor of C.
6. like the application of the described catalyst of arbitrary claim in co hydrogenation synthesizing low-carbon mixed alcohol technology among the claim 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101966121A CN102029166B (en) | 2009-09-27 | 2009-09-27 | Catalyst for preparing low-carbon mixed alcohol by using synthesis gas and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101966121A CN102029166B (en) | 2009-09-27 | 2009-09-27 | Catalyst for preparing low-carbon mixed alcohol by using synthesis gas and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102029166A CN102029166A (en) | 2011-04-27 |
| CN102029166B true CN102029166B (en) | 2012-07-18 |
Family
ID=43882946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101966121A Active CN102029166B (en) | 2009-09-27 | 2009-09-27 | Catalyst for preparing low-carbon mixed alcohol by using synthesis gas and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102029166B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3024572A1 (en) | 2013-06-27 | 2016-06-01 | Clariant Corporation | Manganese oxide-stabilized zirconia catalyst support materials |
| CN105727982B (en) * | 2014-12-11 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of catalyst of synthesis of low-carbon alcohol and preparation method thereof |
| CN107213905A (en) * | 2016-03-21 | 2017-09-29 | 中国石油化工股份有限公司 | Catalyst of isobutanol and its preparation method and application is synthesized by synthesis gas |
| CN108855048A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of composite catalyst carrier and its preparation method and application containing zirconium oxide |
| CN109201096B (en) * | 2017-07-03 | 2021-08-03 | 中国石油化工股份有限公司 | CO2Catalyst for preparing low-carbon mixed alcohol by hydrogenation and application thereof |
| CN107376937B (en) * | 2017-08-14 | 2018-08-28 | 河南省科学院能源研究所有限公司 | A kind of order mesoporous composite catalyst and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123789A (en) * | 1994-08-08 | 1996-06-05 | Basf公司 | Preparation of amines |
| CN1298865A (en) * | 1999-12-06 | 2001-06-13 | 巴斯福股份公司 | Amine prep. method |
| CN101003023A (en) * | 2006-01-19 | 2007-07-25 | 清华大学 | Method for preparing catalyst to purify automobile tail gas |
-
2009
- 2009-09-27 CN CN2009101966121A patent/CN102029166B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123789A (en) * | 1994-08-08 | 1996-06-05 | Basf公司 | Preparation of amines |
| CN1298865A (en) * | 1999-12-06 | 2001-06-13 | 巴斯福股份公司 | Amine prep. method |
| CN101003023A (en) * | 2006-01-19 | 2007-07-25 | 清华大学 | Method for preparing catalyst to purify automobile tail gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102029166A (en) | 2011-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102247852B (en) | Cu-Fe-Co base catalyst used for synthesizing low carbon alcohol by utilizing synthesis gas as well as preparation method and application thereof in low carbon alcohol synthesizing process by virtue of synthesis gas | |
| CN102029166B (en) | Catalyst for preparing low-carbon mixed alcohol by using synthesis gas and preparation method thereof | |
| CN113145155B (en) | Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof | |
| CN110102313B (en) | Preparation of ruthenium-nickel core-shell bimetallic nano-catalyst with limited domain structure and application of ruthenium-nickel core-shell bimetallic nano-catalyst in catalyzing selective hydrogenation of dimethyl terephthalate | |
| WO2013150305A2 (en) | Alcohol production process | |
| KR101437072B1 (en) | Catalyst for efficient co2 conversion and method for preparing thereof | |
| CN104588023A (en) | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN108997274A (en) | A kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran | |
| CN103785391B (en) | A kind of high activity fischer-tropsch synthetic catalyst and its preparation method and application | |
| CN102746100A (en) | Preparation method of cumene | |
| CN102350355A (en) | Iron-based water gas transformation catalyst and preparation method thereof | |
| CN102463121A (en) | High-stability Cu-based catalyst and preparation method thereof | |
| CN109529912B (en) | Composite nano-structure copper catalyst for preparing furfuryl alcohol by furfural hydrogenation and preparation method thereof | |
| CN103157490B (en) | Catalyst for producing ethanol by hydrogenation of acetic ester, and preparation method thereof | |
| CN104230641B (en) | Produce the method for isopropyl benzene | |
| CN114984952B (en) | Carbon-coated copper material and preparation method and application thereof | |
| CN102649746A (en) | Method for producing glycolic acid ester through adding hydrogen in oxalic ester | |
| CN111036284A (en) | Catalyst, preparation method thereof and method for preparing low-carbon olefin from synthesis gas | |
| CN101524644B (en) | Cobalt-based catalyst for the oil-wax co-production of synthetic natural gas, preparation method and application thereof | |
| CN114570374A (en) | Cobalt-based catalyst, preparation method and application | |
| CN110773194B (en) | CO (carbon monoxide)2Catalyst for preparing methane by hydrogenation and preparation method thereof | |
| CN109158107B (en) | Method for preparing liquid hydrocarbon by directly hydrogenating carbon dioxide | |
| CN102794166A (en) | Dimethyl ether (DME) steam reforming hydrogen production catalyst and preparation and application thereof | |
| CN103769098B (en) | A kind of syngas conversion catalyst and its preparation method and application | |
| CN109647492B (en) | Catalyst for directly producing low-carbon olefin by synthesis gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER NAME: SHANGHAI COKING CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee before: Shanghai Coking Co., Ltd. |