CN104107701B - High activity Pt base catalyst, preparation method and its usage - Google Patents
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Abstract
The present invention relates to a kind of high activity Pt base catalyst, preparation method and its usage, mainly solve existing catalyst and be applied in the reaction of acetic acid preparation of ethanol by hydrogenating, there is the problem that acetic acid hydrogenation activity is low.The present invention includes following component by weight percentage by using: a) 0.3～2.0%Pt, b) 65.0～95.0% SiO2C) 1.0～15.0%Sn or its oxide, d) 2.0～10.0% Co or its oxide, e) 2.0～15.0% the technical scheme of at least one in Mg, Ca, Ba or its oxide preferably solve this problem, can be used in the commercial production of acetic acid preparation of ethanol by hydrogenating.
Description
Technical field
The present invention relates to a kind of high activity Pt base catalyst, preparation method and its usage.
Background technology
Ethanol is widely used in the industries such as food, medicine, chemical industry, fuel, national defence, is a kind of highly important clean energy resource.It is possible not only to substitute lead tetraethyl as clean energy resource and makees the anti-knock agent of gasoline, it is also possible to as motor vehicle fuel, be substantially reduced the environmental pollution that burns gasoline causes.[+B.^0T is current, and in world wide, the 60% of ethanol production is used as motor vehicle fuel, and the production method of ethanol mainly uses grain fermentation method and the chemical synthesis with petroleum material as raw material, such as ethylene hydration reaction on phosphoric acid/kieselguhr catalyst for/d3Y6.Ethanol Production by Fermentation mainly utilizes the starchy materials such as Semen Maydis, Oryza glutinosa, Sorghum vulgare Pers., Semen Tritici aestivi, fermented under microbial action, distillation and generate ethanol.The whole world recyclable fuel alliance and F.O.Licht on February 14th, 2011 combine issued global year ethanol production prediction address.It is expected to reach 88,700,000,000 liters according to this report global ethanol production in 2011, meets the more demand substituting crude oil in the world every day.This predictive display, within 2011, global ethanol production amplification was more than 3%, higher than the yield data of 85,800,000,000 liters in 2010.Present Global ethanol production is more than 5.5 hundred million barrels/year.
The U.S. is the first big country of current fuel ethanol production, ethanol production is growing steadily always, after especially 2006, ethanol production explosion, and anticipated this trend the most also will keep, the production of U.S.'s ethanol mainly uses maize zymosis method, and along with the raising of provision price, the method produces the cost of ethanol and is also continuously increased.Brazil of Brazil has advantageous raw material advantage, use with Caulis Sacchari sinensis for raw material production ethanol, its yield is only second to the U.S., not only meet domestic demands, its production cost of ethanol preparation method that Brazil also becomes maximum alcohol fuel exported country traditional is gradually increased, and finds new preparation method and is just causing everybody highest attention.
United States Patent (USP) US2607807 uses noble metal Ru base to be catalyst, and Dichlorodiphenyl Acetate hydrogenation is evaluated, it was found that under the conditions of 70MPa, ethanol yield can reach 88%, reduces reaction pressure to 20MPa, ethanol maximum yield 41%.
United States Patent (USP) US7608744 use metal weight percent be 1%Pd-10%Co-89%C be catalyst, in reaction temperature 250oC, under reaction pressure 2.2MPa reaction condition, acetic acid conversion ratio is 18.5%, and generating ethanol selectivity is 97.5%.
United States Patent (USP) US7608744B1 uses precious metals pt catalyst, and in catalyst composition, Pt content is 1%, when Co content is 10%, in reaction temperature 250oC, Hydrogen Vapor Pressure 22bar, acetic acid conversion ratio reaches 38%, generates ethanol selectivity and reaches 96%.
In sum, catalyst prepared by prior art, during being applied to acetic acid preparation of ethanol through hydrogenation, there is the problem that catalyst acetic acid hydrogenation activity is low.
Summary of the invention
One of the technical problem to be solved is that catalyst prepared by prior art is applied to acetic acid preparation of ethanol through hydrogenation and there is the problem that catalyst activity is low, it is provided that a kind of new high activity Pt base catalyst.This catalyst has, in acetic acid preparation of ethanol through hydrogenation is reacted, the advantage that catalyst activity is high.The two of technical problem solved by the invention are to provide the preparation method of a kind of catalyst corresponding with solving one of technical problem.The three of technical problem solved by the invention are to provide a kind of purposes solving the described catalyst of one of technical problem.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of highly active Pt base catalyst, includes following component by weight percentage:
A) 0.3～2.0%Pt,
B) 65.0～95.0%SiO2,
C) 1.0～15.0%Sn or its oxide,
D) 2.0～10.0%Co or its oxide,
E) 2.0～15.0% it is selected from least one in Mg, Ca, Ba or its oxide.
Preferably, by weight percentage: Pt consumption is 0.5～1.5%, SiO2Consumption is 75.0～95.0%, and the consumption of Sn or its oxide is 3.0～10.0%, and Co or its oxide consumption are 3.0～8.0%, and the consumption of at least one in Mg, Ca, Ba or its oxide is 5.0～10.0%.
For solving the two of above-mentioned technical problem, the present invention uses technical scheme as follows: the preparation method of a kind of high activity Pt base catalyst, comprises the following steps:
A) use infusion process by the desired amount of selected from Mg2+、Ca2+、Ba2+In at least one solution impregnation at SiO2Surface, obtains support precursor I through 400～900 DEG C of roastings after being dried；
B) by the desired amount of SnCl4Solution impregnation is on presoma I, and at 400～800 DEG C, roasting obtains presoma II after drying；
C) by the desired amount of containing Pt2+Solution impregnation is on presoma II, and at 400～700 DEG C, roasting obtains presoma III after drying；
D) by the desired amount of containing Co2+Water/alcoholic solution is immersed on presoma III, and at 400～700 DEG C, roasting obtains described catalyst after drying.
Preferably, a) sintering temperature of presoma I is 600～800 DEG C in step；B) in step, the sintering temperature of presoma II is 500～700 DEG C；C) in step, the sintering temperature of presoma III is 500～600 DEG C；D) in step, the sintering temperature of catalyst is 450～550 DEG C.
For solving the three of above-mentioned technical problem, the present invention uses technical scheme as follows: high activity Pt base catalyst is used for acetic acid Hydrogenation in the reaction of acetic acid.
Preferably, with acid and hydrogen as raw material, the mol ratio of hydrogen/acetic acid is 20 ~ 70, and reaction temperature is 220～280 DEG C, and reaction pressure is 0.5～5.0MPa, and acetic acid liquid volume space velocity is 0.1～1.0 hour-1。
It is highly preferred that reaction temperature is 240～275 DEG C, reaction pressure is 1.0～4.0MPa, and the mol ratio of hydrogen/acetic acid is 30 ~ 60, and the liquid volume air speed of acetic acid is 0.1～0.5 hour-1。
Preferably, in raw material, the concentration of acetic acid is 1～100% by weight percentage.
Acetic acid catalytic hydrogenation is main during generating ethanol there are three kinds of side reactions, and the ethanol that the first generates and acetic acid react generation ethyl acetate further；Its two be generate ethanol be dehydrated generation ethylene further, ethylene is hydrogenated to ethane further；It three is that acetic acid moiety adds hydrogen evolution acetaldehyde.Therefore, the acid site quantity of catalyst needs to mate well with active center.The Pt base catalyst that the present invention relates to, modifies SiO2 carrier by introducing MgO, CaO, BaO one at least within, reduces the acidity of carrier, effectively suppress the generation of the by-product such as acetaldehyde, ether.By introducing SnO2Improve the model of action of Pt and carrier, be effectively improved the dispersion of Pt, improve catalysis activity.Using the catalyst of the present invention, in entrance reaction temperature 245 DEG C, reaction pressure 2.5MPa, acetic acid air speed is 0.3 hour-1, it being applied to acetic acid selection preparation of ethanol through hydrogenation under hydrogen and the reaction condition that mol ratio is 30 of acetic acid, acetic acid conversion ratio reaches 88.9%, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Catalyst 1: by 50g silicon dioxide and Mg2+Content is the aqueous solution incipient impregnation of 5%, is dried, obtains the presoma I that MgO modifies after roasting, uses this carrier containing 5%Sn4+Solution impregnation, through being dried, obtaining SnO after roasting2The presoma II that-MgO modifies, consisting of: 5%MgO-5%SnO2-90%SiO2；By 1.0gPt (NH3)4Cl2Solution is dissolved in the ethanol and aqueous solution that 53.0g mass ratio is 1:1, and adds 3.0g acetic acid and obtain solution I.According to the method for incipient impregnation, being immersed on presoma II by solution I, at 600 DEG C, roasting obtains presoma III after drying；According to the method for incipient impregnation, by a certain amount of containing 5%Co2+Ethanol solution is immersed on Pt catalyst, and at 500 DEG C, roasting obtains Pt-Co catalyst after drying.
The composition of catalyst is by weight percentage:
1%Pt-5%Co-4.7%SnO2-4.7%MgO-84.6%SiO2
With 40mlTi compo pipe as fixed bed reactors, loading catalyst 30ml, in reaction pressure 2.5MPa, reaction temperature 245 DEG C, acetic acid liquid air speed 0.3h-1, H2/ acetic acid mol ratio 30.Carry out hydrogenation reaction, the results are shown in Table 2.
[embodiment 2～12]
(corresponding catalyst 2～12), prepares catalyst according to each step in [embodiment 1], simply changes each material composition, preparation condition, and wherein preparation condition and the material composition of catalyst is shown in Table 1.Hydrogenation reaction the results are shown in Table 2.
The composition of each catalyst of table 1 and preparation condition
[comparative example]
United States Patent (USP) US7608744B1 method prepares PtCo-SiO2Catalyst, uses precious metals pt catalyst, and in catalyst composition, Pt content is 1%, when Co content is 10%, is 250 DEG C in reaction temperature, and when Hydrogen Vapor Pressure is 22bar, acetic acid conversion ratio reaches 38%, generates ethanol selectivity and reaches 95%.
Catalyst uses H before use2For acetic acid catalytic hydrogenation reaction after reduction.With 40mlTi compo pipe as fixed bed reactors, loading catalyst 30ml, reaction pressure 2.5Mpa, reaction temperature 245 DEG C, acetic acid liquid air speed 0.3h-1, H2/ acetic acid mol ratio 30, reaction result is shown in Table 2.
The acetic acid hydrogenation reaction performance of table 2 different catalysts
As seen from Table 2, high activity Pt base catalyst prepared by the method provided with the present invention, at reaction temperature 245 DEG C, 2.5MPa, acetic acid volume space velocity 0.3h-1, it is applied to acetic acid catalytic hydrogenation under the reaction condition that mol ratio is 30.0 of hydrogen and acetic acid and prepares ethanol, there is good hydrogenation activity, compared with the catalyst provided in comparative example, catalyst has more preferable hydrogenation activity, achieves good technique effect.
[embodiment 13]
Investigate catalyst 1 effect of acetic acid catalytic hydrogenation under the conditions of differential responses.The results are shown in Table 3.
Acetic acid catalytic hydrogenation catalyst evaluation result under the conditions of table 3 differential responses
Claims (3)
1. the preparation method of high activity Pt base catalyst, described catalyst includes following component by weight percentage:
A) 0.3～2.0%Pt,
B) 65.0～95.0%SiO2,
C) 1.0～15.0%Sn or its oxide,
D) 2.0～10.0%Co or its oxide,
E) 2.0～15.0% it is selected from least one in Mg, Ca, Ba or its oxide；
Comprise the following steps:
A) use infusion process by the desired amount of selected from Mg2+、Ca2+、Ba2+In at least one solution impregnation at SiO2Surface, obtains support precursor I through 400～900 DEG C of roastings after being dried；
B) by the desired amount of SnCl4Solution impregnation is on presoma I, and at 400～800 DEG C, roasting obtains presoma II after drying；
C) by the desired amount of containing Pt2+Solution impregnation is on presoma II, and at 400～700 DEG C, roasting obtains presoma III after drying；
D) by the desired amount of containing Co2+Water/alcoholic solution is immersed on presoma III, and at 400～700 DEG C, roasting obtains described catalyst after drying.
Preparation method the most according to claim 1, it is characterised in that by weight percentage: Pt consumption is 0.5～1.5%, SiO2Consumption is 75.0～95.0%, and the consumption of Sn or its oxide is 3.0～10.0%, and Co or its oxide consumption are 3.0～8.0%, and the consumption of at least one in Mg, Ca, Ba or its oxide is 5.0～10.0%.
The preparation method of high activity Pt base catalyst the most according to claim 1, it is characterised in that a) in step, the sintering temperature of presoma I is 600～800 DEG C；B) in step, the sintering temperature of presoma II is 500～700 DEG C；C) in step, the sintering temperature of presoma III is 500～600 DEG C；D) in step, the sintering temperature of catalyst is 450～550 DEG C.
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| CN102149661A (en) * | 2008-07-31 | 2011-08-10 | 国际人造丝公司 | Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst |
| CN102300635A (en) * | 2009-10-26 | 2011-12-28 | 国际人造丝公司 | Catalyst for the production of ethanol by hydrogenation of acetic acid comprising platinum-tin on silicaceous support |
| CN102421521A (en) * | 2010-02-02 | 2012-04-18 | 国际人造丝公司 | Preparation and use of catalysts comprising crystalline support modifiers for the production of ethanol |
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| CN102149661A (en) * | 2008-07-31 | 2011-08-10 | 国际人造丝公司 | Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst |
| CN102300635A (en) * | 2009-10-26 | 2011-12-28 | 国际人造丝公司 | Catalyst for the production of ethanol by hydrogenation of acetic acid comprising platinum-tin on silicaceous support |
| CN102421521A (en) * | 2010-02-02 | 2012-04-18 | 国际人造丝公司 | Preparation and use of catalysts comprising crystalline support modifiers for the production of ethanol |
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