CN101773834A - Method used for preparing mixed alcohol catalyst of C1 to C4 by CO hydrogenation - Google Patents
Method used for preparing mixed alcohol catalyst of C1 to C4 by CO hydrogenation Download PDFInfo
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- CN101773834A CN101773834A CN200910237630A CN200910237630A CN101773834A CN 101773834 A CN101773834 A CN 101773834A CN 200910237630 A CN200910237630 A CN 200910237630A CN 200910237630 A CN200910237630 A CN 200910237630A CN 101773834 A CN101773834 A CN 101773834A
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- catalyst
- zro
- hydrogenation
- alcohol
- mixed alcohol
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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
- 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
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Abstract
The invention relates to a method used for preparing a mixed alcohol catalyst of C1 to C4 by CO hydrogenation, which belongs to the technical field of chemical engineering. The method is characterized by comprising the following steps: preparing a Cu-(CeO2-ZrO2) catalyst by adopting a fractional precipitation method, precipitating a CeO2-ZrO2 component firstly and then precipitating a Cu component. The preparation method is simple. The Cu-(CeO2-ZrO2) catalyst prepared by using the fractional precipitation method carries out a CO hydrogenation reaction under the heating and pressurizing conditions. Compared with a catalyst prepared by a traditional coprecipitation method, the Cu-(CeO2-ZrO2) catalyst has higher activity and selectivity of generating alcohol of C1 to C4.
Description
Technical field
The present invention relates to the synthetic C of a kind of CO of being used for hydrogenation
1～C
4The Preparation of catalysts method of mixed alcohol, a kind of preparation Cu-(CeO more specifically says so
2-ZrO
2) catalyst method and make C
1～C
4The method of mixed alcohol belongs to chemical technology field.
Background technology
Along with the exhaustion day by day of petroleum resources and countries in the world to alternative energy source with to the pay attention to day by day of environmental requirement, make people to synthetic C
1～C
4Mixed alcohol has produced bigger interest.The directly synthetic C of synthesis gas
1～C
4Mixed alcohol becomes one of field relatively more active in the domestic and international chemical industry technical research.At present, states such as Germany, the U.S., Canada, Italy and China all bring into use methyl alcohol or ethanol to act as a fuel, and add MAS or methyl tertiary butyl ether(MTBE) (MTBE) simultaneously and burn with gasoline as cosolvent.Take all factors into consideration from Technological Economy,, make C from synthesis gas again by coal or the natural gas production synthesis gas that sets out
1～C
4Mixed alcohol acts as a fuel or gasoline additive is reasonably, and good Application in Chemical Engineering prospect is arranged.From the world energy sources structure, coal accounts for 78.9%, and oil only accounts for 6.6%.As coal producer the biggest in the world, the energy resource structure characteristics of the few oil of the rich coal of China are more obvious.From the utilization of resources and point of view of environment protection, utilize high effect cleaning coal resources technology, exploitation " green fuel " has important strategic meaning and application prospect.The CO catalytic hydrogenation synthesizes C
1～C
4Mixed alcohol is one of important channel of coal resources clean utilization, C in recent years
1～C
4Mixed alcohol progressively shows especially in the using value in fuel field, and correlative study becomes increasingly active.
The CO catalytic hydrogenation synthesizes C
1～C
4The existing many reports of the patented technology of mixed alcohol.As the cooperative development of The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, and union carbide corporation with MoS
2Sygmol technology (US4675344 and EP0235886) for catalyst; France Petroleum Institute's exploitation is the IFP technology (US 4122110) of catalyst with Cu-Co; What Germany Lurgi company developed is the Octamix technology (US 4031123 and US 2327066) of catalyst with Cu-Zn; Italy Snam and Denmark Tops Φ e company develops is the MAS (technology WO/1989/011468) etc. of catalyst with Cu-Cr.These patented technologies differ from one another, wherein C in the product of Sygmol and IFP technology
2+Alcohol content is higher; Octamix process using low-pressure process Cu-series catalyst, space-time yield height, water content are low, and its product structure is expected further to improve.But the composition of the catalyst that uses in these patented technologies is comparatively complicated, and preparation technology is comparatively loaded down with trivial details, and the space-time yield of mixed alcohol is also not high.Chinese patent CN1428192, CN1481934, CN1179993 have reported CO hydrogenation preparing C
1～C
4The Preparation of catalysts method of alcohol, Preparation of catalysts need the multistep dipping, and catalyst activity also needs to add Mn, various alkaline-earth metal even noble metal Rh, complicated process of preparation except Cu.In addition, the catalyst with traditional coprecipitation method preparation may make active component be embedded in the granule interior of other carrier component, is difficult to bring into play efficiently catalytic action.
The present invention adopts step-by-step precipitation method to prepare Cu-(CeO
2-ZrO
2) catalyst, first deposit C eO
2-ZrO
2Carrier component, deposit C u active component again, the preparation method is simple, can improve Cu-(CeO
2-ZrO
2) catalyst selectivity and raising C to generating alcohol product in the CO hydrogenation reaction
1～C
4The mixed alcohol space-time yield.
Summary of the invention
The purpose of this invention is to provide the synthetic C of a kind of CO of being used for hydrogenation
1～C
4Cu-(the CeO of mixed alcohol
2-ZrO
2) the Preparation of catalysts method, use the Cu-(CeO that this method makes
2-ZrO
2) catalyst that makes than traditional coprecipitation method of catalyst has higher activity and generate C
1～C
4The selectivity of alcohol.
The CO hydrogenation that is used for that the present invention proposes synthesizes C
1～C
4Cu-(the CeO of mixed alcohol
2-ZrO
2) the Preparation of catalysts method, it is characterized in that: adopt step-by-step precipitation method to prepare catalyst: at first, with the inorganic salts mixed aqueous solution of the inorganic salts of Ce and Zr as raw material, with K
2CO
3The aqueous solution is as precipitating reagent, first deposit C e-Zr component; Then, add the inorganic salt solution of Cu, with K
2CO
3The aqueous solution is precipitating reagent, and deposit C u component through washing, dry, roasting, obtains Cu-(CeO then again
2-ZrO
2) catalyst precarsor, obtain Cu-(CeO through reduction again
2-ZrO
2).Use the Cu-(CeO of the inventive method preparation
2-ZrO
2) as catalyst, with CO and H
2Be raw material, under the condition of pressurization of heating, can make C effectively
1～C
4Mixed alcohol.
Cu-(CeO
2-ZrO
2) the concrete preparation process of catalyst comprises:
(1) preparation Ce (NO
3)
3-ZrO (NO
3)
2Mixed aqueous solution; Preparation K
2CO
3The aqueous solution; Stir down to Ce (NO
3)
3-ZrO (NO
3)
2Mixed aqueous solution drips K
2CO
3The aqueous solution dropwises the pH=7 that the precipitation slurries are regulated in the back; Continue to stir and static wearing out;
(2) preparation Cu (NO
3)
2The aqueous solution, and with this Cu (NO
3)
2The aqueous solution adds above-mentioned Ce (OH)
3-ZrO (OH)
2Also stir in the precipitation slurries, drip K to slurries again
2CO
3The aqueous solution is regulated final precipitation slurries pH=7; Continue to stir and static wearing out;
(3) will precipitate dope filtration, washing, and 3 times repeatedly, filter and obtain filter cake; Place filter cake baking oven dry, place the Muffle furnace roasting again, promptly obtain catalyst precursor CuO-(CeO
2-ZrO
2).Catalyst precursor is through H
2Reduction can obtain Cu-(CeO
2-ZrO
2).
99.99%) and hydrogen (H the synthesis gas that the present invention uses is carbon monoxide (CO purity:
2Purity: gaseous mixture (CO/H 99.999%)
2Ratio be 1: 2), at Cu-(CeO
2-ZrO
2) catalyst carries out the CO hydrogenation reaction under existing.
Carry out above-mentioned reaction by method of the present invention, under heating, carry out.Reaction temperature is 300 ℃.
Carry out above-mentioned reaction by the inventive method, carry out adding to depress.The pressure of synthesis gas is 6MPa.
The specific embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further.
Embodiment 1
(1) CuO-(CeO
2-ZrO
2) preparation (step-by-step precipitation method)
(a) with the Ce (NO of 86.85g
3)
36H
2ZrO (the NO of O and 53.45g
3)
22H
2O is dissolved in the 200ml deionized water, makes Ce (NO
3)
3-ZrO (NO
3)
2Mixed aqueous solution; K with 69.1g
2CO
3Be dissolved in the 250ml deionized water, make K
2CO
3The aqueous solution; Stir down to Ce (NO
3)
3-ZrO (NO
3)
2Mixed aqueous solution drips K
2CO
3The aqueous solution dropwises the pH=7 that the precipitation slurries are regulated in the back; Continue to stir 1h, static aging 3h;
(b) with the Cu (NO of 30.50g
3)
26H
2O is dissolved in the 100ml deionized water, makes Cu (NO
3)
2The aqueous solution, and with this Cu (NO
3)
2The aqueous solution adds above-mentioned Ce (OH)
3-ZrO (OH)
2Also stir in the precipitation slurries, drip pre-configured K to slurries again
2CO
3The aqueous solution (the K of 14.26g
2CO
3Be dissolved in the 51ml deionized water), regulate final precipitation slurries pH=7; Continue to stir 2h, static aging 10h;
(c) will precipitate dope filtration, washing, and 3 times repeatedly, filter and obtain filter cake; Filter cake is placed 110 ℃ of following dry 10h of baking oven, place 550 ℃ of following roasting 5h of Muffle furnace again.Catalyst is labeled as Cu-(CeO
2-ZrO
2) (step-by-step precipitation method).
(2) reduction activation of catalyst
Before reaction to catalyst precursor CuO-(CeO
2-ZrO
2) carry out reduction activation.The reduction of catalyst is carried out in miniature fixed-bed tube reactor.Tubular reactor is the stainless steel tube of liner quartz ampoule (internal diameter 10mm, high 350mm), and loaded catalyst is 0.5ml.Reducing gases is H
2And N
2Gaseous mixture (H
2/ N
2=1/4, volume ratio), after reducing gases (100ml/min) is warming up to 250 ℃ with beds mobile time, at 250 ℃ of reduction 12h.
(3) the synthetic C of CO hydrogenation
1～C
4The reaction of mixed alcohol
Catalyst reduction rises to 300 ℃ with reaction bed temperature after finishing, and switches to CO/H
2Unstripped gas (air speed 10000h
-1) under 6Mp pressure, react, raw gas flow is controlled by mass flowmenter, and reaction pressure is by pressure maintaining valve and counterbalance valve control, and reaction bed temperature is measured and control by thermocouple and temperature controller.Post reaction mixture is analyzed with gas chromatograph, and the product of reaction has alcohol product, hydrocarbon product and CO
2Comprise methyl alcohol, dimethyl ether, C in the alcohol product
2～C
4Alcohol is because of the easy hydrolysis of dimethyl ether is converted into methyl alcohol, so when calculating the total space-time yield of alcohol product dimethyl ether is returned in alcohol product; Hydrocarbon product is mainly methane.
Analysis result shows, the CO conversion ratio is 17.8%, the alcohol product selectivity is 76.3%, the total space-time yield of alcohols is 763.3g/ (Kgh).
Reaction result is listed in table 1.
Comparative example 1
Preparation of catalysts and reduction activation are with embodiment 1; The CO hydrogenation synthesizes C
1～C
4The reaction of mixed alcohol, except that reaction temperature is 250 ℃, other is with embodiment 1.
Analysis result shows, the CO conversion ratio is 12.6%, the alcohol product selectivity is 77.8%, the total space-time yield of alcohols is 564.2g/ (Kgh).
Reaction result is listed in table 2.
Comparative example 2
Preparation of catalysts and reduction activation are with embodiment 1; The CO hydrogenation synthesizes C
1～C
4The reaction of mixed alcohol, except that reaction temperature is 350 ℃, other is with embodiment 1.
Analysis result shows, the CO conversion ratio is 17.2%, the alcohol product selectivity is 25.0%, the total space-time yield of alcohols is 234.0g/ (Kgh).
Reaction result is listed in table 3.
Comparative example 3
(1) CuO-CeO
2-ZrO
2Preparation (coprecipitation)
(a) with the Cu (NO of 30.50g
3)
26H
2Ce (the NO of O, 86.85g
3)
36H
2ZrO (the NO of O, 53.45g
3)
22H
2O is dissolved in the 300ml deionized water, makes Cu (NO
3)
2-Ce (NO
3)
3-ZrO (NO
3)
2Mixed aqueous solution; K with 83.36g
2CO
3Be dissolved in the 300ml deionized water, make K
2CO
3The aqueous solution; Stir down to Cu (NO
3)
2-Ce (NO
3)
3-ZrO (NO
3)
2Mixed aqueous solution drips K
2CO
3The aqueous solution dropwises the pH=7 that the precipitation slurries are regulated in the back; Continue to stir 2h, static aging 10h;
(b) will precipitate dope filtration, washing, and 3 times repeatedly, filter and obtain filter cake; Filter cake is placed 110 ℃ of following dry 10h of baking oven, place 550 ℃ of following roasting 5h of Muffle furnace again.Catalyst is labeled as Cu-CeO
2-ZrO
2(coprecipitation).
(2) reduction activation of catalyst
With embodiment 1.
(3) the synthetic C of CO hydrogenation
1～C
4The reaction of mixed alcohol
With embodiment 1.
Analysis result shows, the CO conversion ratio is 28.8%, the alcohol product selectivity is 35.8%, the total space-time yield of alcohols is 522.1g/ (Kgh).Though the Cu-CeO of coprecipitation preparation
2-ZrO
228.8% CO conversion ratio is arranged, but the alcohol product selectivity has only 35.8%.
Reaction result is listed in table 4.
The reaction result of table 1 embodiment 1
Table 1 (continuing)
The reaction result of table 2 comparative example 1
Table 2 (continuing)
The reaction result of table 3 comparative example 2
Table 3 (continuing)
The reaction result of table 4 comparative example 3
Table 4 (continuing)
Claims (3)
1. one kind is used for CO hydrogenation preparing C
1～C
4The method of mixed alcohol catalyst is characterized in that: adopt step-by-step precipitation method to prepare Cu-(CeO
2-ZrO
2) catalyst, first deposit C eO
2-ZrO
2Component, deposit C u component again; With CO and H
2Be raw material, at pressurization and the Cu-(CeO of heating
2-ZrO
2) prepare C under the condition that exists of catalyst
1～C
4Mixed alcohol.
2. method according to claim 1 is characterized in that: with the inorganic salts of Ce, the inorganic salts of Zr and the inorganic salts of Cu is raw material, with K
2CO
3Be precipitating reagent, first deposit C eO
2-ZrO
2Component, deposit C u component again.
3. method according to claim 1 is characterized in that: described CO hydrogenation reaction is carried out under the pressurized conditions of heating, and described reaction temperature is 300 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910237630A CN101773834B (en) | 2009-11-20 | 2009-11-20 | Method for preparing mixed alcohol catalyst of C1 to C4 by CO hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910237630A CN101773834B (en) | 2009-11-20 | 2009-11-20 | Method for preparing mixed alcohol catalyst of C1 to C4 by CO hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101773834A true CN101773834A (en) | 2010-07-14 |
| CN101773834B CN101773834B (en) | 2012-10-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910237630A Expired - Fee Related CN101773834B (en) | 2009-11-20 | 2009-11-20 | Method for preparing mixed alcohol catalyst of C1 to C4 by CO hydrogenation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727982A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Catalyst for synthesizing lower alcohols and preparation method for catalyst |
| CN110252275A (en) * | 2019-05-21 | 2019-09-20 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide of high-specific surface area and its preparation method and application |
| CN112264025A (en) * | 2020-11-18 | 2021-01-26 | 西南化工研究设计院有限公司 | Simple, energy-saving and environment-friendly preparation method of methanol synthesis catalyst |
-
2009
- 2009-11-20 CN CN200910237630A patent/CN101773834B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727982A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Catalyst for synthesizing lower alcohols and preparation method for catalyst |
| 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 |
| CN110252275A (en) * | 2019-05-21 | 2019-09-20 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide of high-specific surface area and its preparation method and application |
| CN110252275B (en) * | 2019-05-21 | 2021-11-19 | 山东国瓷功能材料股份有限公司 | Cerium-zirconium composite oxide with high specific surface area, and preparation method and application thereof |
| CN112264025A (en) * | 2020-11-18 | 2021-01-26 | 西南化工研究设计院有限公司 | Simple, energy-saving and environment-friendly preparation method of methanol synthesis catalyst |
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|---|---|
| CN101773834B (en) | 2012-10-10 |
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