CN103894193A - High-activity Pt-Ru bimetallic catalyst, and preparation method and use thereof - Google Patents
High-activity Pt-Ru bimetallic catalyst, and preparation method and use thereof Download PDFInfo
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- CN103894193A CN103894193A CN201210575780.3A CN201210575780A CN103894193A CN 103894193 A CN103894193 A CN 103894193A CN 201210575780 A CN201210575780 A CN 201210575780A CN 103894193 A CN103894193 A CN 103894193A
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Abstract
The invention relates to a high-activity Pt-Ru bimetallic catalyst, and a preparation method and a use thereof in order to mainly solve a problem that the reaction activity of present catalysts in acetic acid hydrogenation is low. The high-activity Pt-Ru bimetallic catalyst comprises 0.5-2.0wt% of Pt, 1.0-15.0wt% of Ru, 70.0-95.0wt% of SiO2, and 2.0-15.0wt% of at least one of Mg, Ca, Zr, Sn, Ba or oxides thereof. The above technical scheme well solves the problem, and the high-activity Pt-Ru bimetallic catalyst can be used in the industrial production of ethanol through acetic acid catalyzed hydrogenation.
Description
Technical field
The present invention relates to a kind of high activity PtRu bimetallic catalyst, preparation method and its usage.
Background technology
Pt is catalyst based is a kind of broad-spectrum catalyst, be applied to hydrogenation reaction, dehydrogenation reaction,, the reaction such as catalytic oxidation.Such catalyst is main mainly with infusion process greatly.With pt
2+for precursor, Na
2cO
3, NaOH, urea be precipitating reagent, preparation condition has a significant impact catalyst performance, the thing phase composition of catalyst precursor is the key factor that affects catalytic performance.Because Pt metal has good stability and resistance to corrosion, this metallic catalyst is widely used in the research of acetic acid hydrogenation in recent years.
Calendar year 2001, country determined to promote the use of vehicle-use alcohol gasoline in the whole nation, and started a large amount of exploitation alcohol fuels, reached more than 160 ten thousand tons by China's alcohol fuel total output in 2006, occupied the 3rd, the world.Since two thousand six, the no longer newly-increased fuel ethanol production ability take cereal as raw material of China, emphasis is supported the development of the non-grain raw material alcohol fuels such as sugar grass, cassava, cellulose.In Heilungkiang, the ground such as the Inner Mongol, Shandong, Xinjiang and Tianjin carried out plantation and the fuel ethanol production pilot of sugar grass, Heilongjiang Province's pilot project has reached year producing and ethanol 5 000t.At present, China cassava cultivated area is 1,000,000 hm
2, output is 2 100 ten thousand t left and right.Have expert to think, Chinese Cassava can be produced 4,000,000 t alcohol fuels, only plants cassava, just can produce the whole nation and promote 10% of alcohol fuel.In the long run, these are the transitional raw material of alcohol fuel, and cellulosic ethanol is only one of the final solution in Chinese biological mass-energy source, and many experts think that cellulose ethanol technology processed will be progressively ripe in coming 10 years.Tenth Five-Year Plan Period, the raw material of alcohol fuel is take grain in storage for years as main, for alleviating production area surplus of grain, and the Eleventh Five-Year Plan period, on raw material, to focus on suiting measures to local conditions, the non-grain of develop actively substitutes crop, more will realize technical breakthrough in realizing raw material diversification, meets the domestic demand to alcohol fuel.So far, ethanol petrol consumption figure accounts for 20% of national gasoline consumption figure, and China has become the third-largest fuel ethanol production and the consumer nation that are only second to Brazil, the U.S..Take coal as raw material, first coal gasification is prepared methyl alcohol, and then methyl alcohol acidylate is prepared acetic acid, and acetic acid is a kind of selective high through Hydrogenation for the method for ethanol, accessory substance few process route.Adopt this route, the research of acetic acid hydrogenation generation ethanol is less, and domestic and foreign literature and patent adopt noble metal catalyst to make some progress.
(Xinyang Normal College's journal, 2011,24 (2): 234～237) adopt PtNi catalyst to be applied to acetic acid hydrogenation, research shows, works as Pt, when Ni load capacity is respectively 0.3%, 15%, through 500 such as the strong mountain of well, Wang Jianxu
oc roasting, 600
oc reduces rear catalyst, and reaction temperature is 200
owhen C, acetic acid conversion ratio is 55.92, and generating ethyl acetate is selectively 48.94.
It is catalyst that U.S. Pat 2607807 adopts noble metal Ru base, and Dichlorodiphenyl Acetate hydrogenation is evaluated, and found that, under 70MPa condition, ethanol yield can reach 88%, reduces reaction pressure to 20Mpa, ethanol maximum yield 41%.
It is that 1%Pd-10%Co-89%C is catalyst that U.S. Pat 7608744 adopts weight metal percentage, in reaction temperature 250
oc, under reaction pressure 2.2MPa reaction condition, acetic acid conversion ratio is 18.5%, generating ethanol is selectively 97.5%.
U.S. Pat 7608744B1 adopts precious metals pt catalyst, and in catalyst composition, Pt content is that 1%, Co content is while being 10%, in reaction temperature 250
oc, Hydrogen Vapor Pressure 22 bar, acetic acid conversion ratio reaches 38%, generates ethanol and selectively reaches 96%.
In sum, noble metal catalyst prepared by prior art, is applied to acetic acid catalytic hydrogenation and prepares in ethanol process, has the problem that catalyst activity is low.
Summary of the invention
One of technical problem to be solved by this invention is that noble metal catalyst prepared by prior art is applied to acetic acid Hydrogenation in ethanol process, has the problem of poor catalyst activity, and a kind of new high activity PtRu bimetallic catalyst is provided.This catalyst is prepared ethanol process for acetic acid catalytic hydrogenation and is had advantages of that catalytic activity is good.Two of technical problem solved by the invention is to provide a kind of preparation method of the catalyst corresponding with one of technical solution problem.Three of technical problem solved by the invention is to provide the purposes of the described catalyst of one of a kind of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of high activity PtRu bimetallic catalyst, comprises following component by weight percentage:
a)?0.5～2.0%Pt；
b)?0.5～15.0%Ru；
c)?70.0～95.0%?SiO
2；
D) 2.0～15.0% at least one that are selected from Mg, Ca, Zr, Sn, Ba or its oxide.
Preferably, by weight percentage, the consumption of Pt is 0.5～1.5%; Ru consumption be 1.0～10.0%; SiO
2consumption be 70.0～90.0%; At least one the consumption being selected from Mg, Ca, Zr, Sn, Ba or its oxide is 5.0～10.0%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of high activity PtRu bimetallic catalyst, comprises the following steps:
A) adopt infusion process by the Mg that is selected from of aequum
2+, Ca
2+, Zr
4+, Sn
4+or Ba
2+be immersed in SiO Deng at least one in soluble-salt
2surface, obtains catalyst precursor I through 400～1000 ℃ of roastings after being dried;
B) by the Pt that contains of aequum
2+be immersed in presoma I, be then dried, obtain presoma II through 300～800 ℃ of roastings;
C) by the Ru of aequum
3be immersed in presoma II, described catalyst is reduced to obtain in then dry, 300～600 ℃ of roastings, 200～600 ℃.
Preferably, the sintering temperature of presoma I is 500～800 ℃; The sintering temperature of presoma II is 400～600 ℃; The sintering temperature of catalyst is 300～500 ℃.
Preferably, the reduction temperature of catalyst is 250～450 ℃.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: high activity PtRu bimetallic catalyst for acetic acid Hydrogenation for the reaction of ethanol.
Preferably, take acetic acid and hydrogen as raw material, the mol ratio of hydrogen/acetic acid is 1:(0.01～0.1), reaction temperature is 150～250 ℃, and reaction pressure is 0.5～5.0MPa, and acetic acid liquid volume space velocity is 0.1～1.0 hour
-1.
More preferably, the liquid volume air speed of acetic acid is 0.1～0.5 hour
-1.
More preferably, reaction temperature is 160～220 ℃, and reaction pressure is 1.0～4.0 MPa.
Preferably, in raw material, the concentration of acetic acid is 10～100% by weight percentage.
Three kinds of side reactions of main generation in the process of acetic acid catalytic hydrogenation generation ethanol, the ethanol that the first generates further reacts generation ethyl acetate with acetic acid; It two is the ethanol generation ethene that further dewaters generating, and the further hydrogenation of ethene generates ethane; Its three be acetic acid partial hydrogenation form acetaldehyde.Therefore, the acid site quantity of catalyst need to be mated well with activated centre.The quantity in the acid site of catalyst and acid strength regulate by kind and the content of oxide, thereby make the catalyst of preparation have good selective and stability.The PtRu bimetallic catalyst the present invention relates to, by introducing MgO, CaO, ZrO
2, SnO
2or BaO one at least is wherein to SiO
2carrier is modified, and the carrier after modification is conducive to improve the decentralization of Pt, and the catalyst with better dispersion effect has better hydrogenation activity.Introduce after the second metal Ru, improved the carbonyl hydrogen effect of catalyst, thereby under lower reaction temperature, can realize the conversion of acetic acid to ethanol.Use catalyst of the present invention, at 160～250 ℃ of entrance reaction temperatures, reaction pressure 1.0～4.0MPa, take acetic acid as raw material, reaction liquid air speed is 0.1～0.4 hour
-1, under the reaction condition that the mol ratio of hydrogen and acetic acid is 10～50, being applied to acetic acid catalytic hydrogenation and preparing ethanol, acetic acid conversion ratio reaches 89%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
The specific embodiment
[embodiment 1]
Catalyst 1: by 100 g silica, with 100 g 3.0%Mg
2+solution incipient impregnation, after being dried, at 600 ℃, roasting obtains the SiO that MgO modifies
2carrier, by this carrier and 100 g 1%Pt
2+aqueous solution incipient impregnation, through 120 ℃ dry 12 hours, 550 ℃ of roastings 4 hours.Sample and 100 g 5%Ru after roasting
3+aqueous solution incipient impregnation, through 120 ℃ dry 12 hours, 450 ℃ of roastings after 4 hours through 450 ℃ of hydrogen reducings 2 hours catalyst 1 (composition of catalyst is by weight percentage: 0.9%Pt-4.5%Ru%-4.5%MgO-90.1% SiO
2)
[embodiment 2]
Catalyst 2: by 100 g silica, with 100 g 3.0%Mg
2+solution incipient impregnation, after being dried, at 600 ℃, roasting obtains the SiO that MgO modifies
2carrier, by this carrier and 100 g 5%Ru
3+aqueous solution incipient impregnation, through 120 ℃ dry 12 hours, 450 ℃ of roastings 4 hours.Sample and 100 g 1%Pt after roasting
2+aqueous solution incipient impregnation, through 120 ℃ dry 12 hours, 450 ℃ of roastings after 4 hours through 450 ℃ of hydrogen reducings 2 hours catalyst 2 (composition of catalyst is by weight percentage: 0.9%Pt-4.5%Ru%-4.5%MgO-90.1% SiO
2)
[embodiment 3]
Catalyst 3: by 100 g silica, with 100 g 3.0%Mg
2+solution incipient impregnation, after being dried, at 600 ℃, roasting obtains the SiO that MgO modifies
2carrier, contains 1%Pt by this carrier and 100 g
2+, 5%Ru
3+aqueous solution incipient impregnation, through 120 ℃ dry 12 hours, 450 ℃ of roastings after 4 hours through 450 ℃ of hydrogen reducings 2 hours catalyst 3 (composition of catalyst is by weight percentage: 0.9%Pt-4.5%Ru%-4.5%MgO-90.1% SiO
2)
[embodiment 4～17]
(corresponding catalyst 2～15), according to each step Kaolinite Preparation of Catalyst in [embodiment 1], just changes each material composition, preparation condition, and wherein the preparation condition of catalyst and material form in table 1.
The composition of the each catalyst of table 1 and preparation condition
[comparative example]
Prepare Pt catalyst according to U.S. Pat 7608744B1, in catalyst composition, Pt content is that 1%, Co content is 10%.
Catalyst adopts H before use
2at a certain temperature reduction after for acetic acid catalytic hydrogenation reaction.Take 40 ml Ti compo pipes as fixed bed reactors, loading catalyst 30 ml, reaction pressure 2.5 MPa, 170 ℃ of reaction temperatures, acetic acid flow 0.2 ml/min, H
2/ acetic acid mol ratio 30, reaction result is in table 2.Comparative example catalyst reaction condition is: loading catalyst 30 ml, reaction pressure 2.5 MPa, 245 ℃ of reaction temperatures, acetic acid liquid air speed 0.3 h
-1, H
2/ acetic acid mol ratio 30.
The acetic acid hydrogenation reaction performance of table 2 different catalysts
As seen from Table 2, the efficient PtRu bimetallic catalyst of preparing with method provided by the invention, under the reaction condition that is 30.0 in the mol ratio of 170 ℃ of reaction temperatures, 2.5MPa, hydrogen and acetic acid, be applied to acetic acid catalytic hydrogenation and prepare ethanol, acetic acid conversion ratio reaches 89.3%, there is good hydrogenation activity, compared with the catalyst providing in [comparative example], catalyst has better hydrogenation activity, has obtained good technique effect.
[embodiment 18]
Selecting catalyst 6, has investigated the Hydrogenation under differential responses condition, in table 3.
Acetic acid catalytic hydrogenation catalyst evaluation result under table 3 differential responses condition
Can find out from table 2, table 3, this technology is applied to acetic acid hydrogenation and prepares ethanol, in 160～220 ℃ of reaction temperatures, reaction pressure 1.0～4.0 MPa, acetic acid liquid air speed 0.1～0.5 hour
-1, the activity of catalyst is good, and this catalyst reaction temperatures is low simultaneously, has obtained good technique effect.
Claims (10)
1. a high activity PtRu bimetallic catalyst, comprises following component by weight percentage:
a)?0.5～2.0%Pt；
b)?0.5～15.0%Ru；
c)?70.0～95.0%?SiO
2；
D) 2.0～15.0% at least one that are selected from Mg, Ca, Zr, Sn, Ba or its oxide.
2. high activity PtRu bimetallic catalyst according to claim 1, is characterized in that by weight percentage, the consumption of Pt is 0.5～1.5%; Ru consumption be 1.0～10.0%; SiO
2consumption be 70.0～90.0%; At least one the consumption being selected from Mg, Ca, Zr, Sn, Ba or its oxide is 5.0～10.0%.
3. the preparation method of high activity PtRu bimetallic catalyst claimed in claim 1, comprises the following steps:
A) adopt infusion process by the Mg that is selected from of aequum
2+, Ca
2+, Zr
4+, Sn
4+or Ba
2+be immersed in SiO Deng at least one in soluble-salt
2surface, obtains catalyst precursor I through 400～1000 ℃ of roastings after being dried;
B) by the Pt that contains of aequum
2+be immersed in presoma I, be then dried, obtain presoma II through 300～800 ℃ of roastings;
C) by the Ru of aequum
3be immersed in presoma II, described catalyst is reduced to obtain in then dry, 300～600 ℃ of roastings, 200～600 ℃.
4. the preparation method of high activity PtRu bimetallic catalyst according to claim 3, the sintering temperature that it is characterized in that presoma I is 500～800 ℃; The sintering temperature of presoma II is 400～600 ℃; The sintering temperature of catalyst is 300～500 ℃.
5. the preparation method of high activity PtRu bimetallic catalyst according to claim 3, the reduction temperature that it is characterized in that catalyst is 250～450 ℃.
6. high activity PtRu bimetallic catalyst claimed in claim 1 reaction for ethanol for acetic acid Hydrogenation.
7. the purposes of catalyst according to claim 6, it is characterized in that the mol ratio of hydrogen/acetic acid is 1:(0.01～0.1 take acetic acid and hydrogen as raw material), reaction temperature is 150～250 ℃, reaction pressure is 0.5～5.0MPa, and acetic acid liquid volume space velocity is 0.1～1.0 hour
-1.
8. according to the purposes of catalyst described in claim 6, the liquid volume air speed that it is characterized in that acetic acid is 0.1～0.5 hour
-1.
9. according to the purposes of catalyst described in claim 6, the concentration that it is characterized in that acetic acid in raw material is 10～100% by weight percentage.
10. according to the purposes of catalyst described in claim 6, it is characterized in that reaction temperature is 160～220 ℃, reaction pressure is 1.0～4.0 MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105582927A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 1,4-cyclohexanedimethanol catalyst and preparation method thereof |
| CN106881085A (en) * | 2017-03-16 | 2017-06-23 | 兰州理工大学 | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation |
| CN107282045A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | 1,4 cyclohexane dimethanol catalyst |
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| EP0285420A1 (en) * | 1987-03-31 | 1988-10-05 | The British Petroleum Company p.l.c. | The catalysed hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters |
| CN102557871A (en) * | 2009-10-26 | 2012-07-11 | 国际人造丝公司 | Catalyst comprising platinum and tin on silica-containing supporter for producing ethanol by adding hydrogen to acetic acid |
| CN102600842A (en) * | 2012-03-02 | 2012-07-25 | 山西盛驰科技有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof |
| CN102688758A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof |
-
2012
- 2012-12-27 CN CN201210575780.3A patent/CN103894193A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0285420A1 (en) * | 1987-03-31 | 1988-10-05 | The British Petroleum Company p.l.c. | The catalysed hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters |
| CN102557871A (en) * | 2009-10-26 | 2012-07-11 | 国际人造丝公司 | Catalyst comprising platinum and tin on silica-containing supporter for producing ethanol by adding hydrogen to acetic acid |
| CN102688758A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof |
| CN102600842A (en) * | 2012-03-02 | 2012-07-25 | 山西盛驰科技有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105582927A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 1,4-cyclohexanedimethanol catalyst and preparation method thereof |
| CN105582927B (en) * | 2014-10-24 | 2018-04-06 | 中国石油化工股份有限公司 | 1,4 cyclohexanedimethanol catalyst and its preparation method |
| CN107282045A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | 1,4 cyclohexane dimethanol catalyst |
| CN107282045B (en) * | 2016-04-12 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing 1, 4-cyclohexanedimethanol |
| CN106881085A (en) * | 2017-03-16 | 2017-06-23 | 兰州理工大学 | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation |
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