CN101428213A - Uses of carbon carried noble metal catalysts in cellulose hydrogenation hydrolytic reaction - Google Patents
Uses of carbon carried noble metal catalysts in cellulose hydrogenation hydrolytic reaction Download PDFInfo
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- CN101428213A CN101428213A CNA2007101579933A CN200710157993A CN101428213A CN 101428213 A CN101428213 A CN 101428213A CN A2007101579933 A CNA2007101579933 A CN A2007101579933A CN 200710157993 A CN200710157993 A CN 200710157993A CN 101428213 A CN101428213 A CN 101428213A
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Abstract
The invention relates to a hydrogenation hydrolysis reaction of celluloses, particularly relates to the application of a carbon-carried noble metal catalyst in a hydrogenation hydrolysis reaction of celluloses. The catalyst has the following general formula: AxByC/Z carried catalyst, wherein A is Mo or W; B is V, Ni, Co, Fe, Ta, Nb, Ti, Cr or Zr; C is C, N or P; Z is a carbon carrier; the loading of the active components in the catalyst ranges from 5wt% to 90wt%; x is more than or equal to 0 but less than or equal to 2; and y is more than or equal to 0 but less than or equal to 2. The catalyst has the similar cellulose catalytic conversion performance to the best noble metal catalyst Pt/gamma-Al2O3 in the prior art, and also has the advantages of low cost and good application prospects.
Description
Technical field
The present invention relates to cellulose hydrogenation hydrolytic reaction, specifically a kind of is the application of loaded catalyst in cellulose hydrogenation hydrolytic reaction of active component with single constituent element or multicomponent transition metal carbide, nitride or phosphide.
Background technology
Energy problem is the long problem of generally being concerned about since this of human society, from the seventies in last century, along with the growing tension of nonrenewable resourceses such as oil, to the exploitation of renewable resource and utilize and become our instant task.Biomass resource is existing renewable resource the most widely in the world, comprise materials such as cellulose, hemicellulose, lignin and starch, wherein, the ratio maximum that cellulose is shared, account for about 40% of living beings total amount, therefore, study the key point that its trans-utilization technology will become the living beings transformation technology.
Cellulosic transformation technology has experienced research courses such as acid-hydrolysis method, enzyme hydrolysis method, supercritical water conversion method.But, more than the equal imperfection of each method, and all have many shortcoming problems, therefore, research and develop the extensive concern that a kind of quick, efficient, green cellulose conversion method is subjected to scholars.Not long ago, professor Fukuoka of Japan had reported a kind of new method of cellulose catalyzed conversion, he first with inorganic oxide support noble metal catalyst successfully catalysis cellulose conversion processes [Angew.Chem.Int.Ed.2006,45,5161-5163].This method catalyzed conversion cellulose is that cellulose at first is hydrolyzed to glucose molecule under the effect of catalyst, secondly under the condition that hydrogen exists glucose is reduced to D-sorbite and sweet mellow wine.Secondly these two kinds of micromolecule sugar alcohols have important prospects for commercial application, and they are not only a kind of important sweetener, can be used as again to produce ethylene glycol, glycerine, lactic acid and ascorbic presoma, and also can be used for producing H
2And C
5, C
6In hydrocarbon, having very at energy field, important use is worth.That the used catalyst activity of Fukuoka professor is best is Pt/ γ-Al
2O
3Catalyst, the productive rate of its catalyzed conversion cellulose gained reproducibility sugar alcohol is up to 31%, and still, this catalyst is a kind of noble metal catalyst, the loading of active component Pt is also up to 2.5%, so very high from the cost of this catalyst of angle of commercial Application.Therefore, develop a kind of novel, the cellulose conversion catalyst becomes the research emphasis of various countries' researcher cheaply.
1973, " science " magazine reported first of the U.S. tungsten carbide in a series of catalytic reactions, have the catalysis characteristics [Science, 1973,181,547-549] of class noble metal.Hereafter transition metal nitride and carbide have caused that as the new catalysis material of a class people pay close attention to greatly in the catalysis subject.Similar and the group VIII noble metals of the surface nature of transition metal nitride and carbide and characterization of adsorption, so it is on the characteristic reaction of catalyst that people always concentrate on the noble metal the research of the catalytic property of nitride and carbide, particularly be associated with hydrogenation reaction, hope can substitute noble metal catalysts such as Pt, Pd.Class noble metal catalysts such as various transition metal nitrides, carbide and phosphide are applied to cellulose hydrogenation hydrolytic reaction yet there are no patent and bibliographical information so far.
Summary of the invention
The object of the present invention is to provide the catalyst of a kind of low cost, high performance support type cellulose hydrogenation hydrolyzation, its carrier is a material with carbon element, and active component is single constituent element or multicomponent transition metal carbide, nitride or phosphide.Such catalyst has simultaneously that cost is low, specific area is high, be easy to advantages such as moulding, makes further practical application become possibility.
For achieving the above object, technical scheme of the present invention is:
A kind of cellulose catalytic converting catalyst can be represented by the formula A
xB
yThe C/Z loaded catalyst.Wherein A is Mo or W, and B is V, Ni, Co, Fe, Ta, Nb, Ti, Cr, Zr, and C is carbon, nitrogen element or P elements, and Z is a carrier, wherein 0≤x≤2,0≤y≤2.
Catalyst carrier is the charcoal carrier, comprises various raw material of wood-charcoal material such as active carbon, carbon black, CNT, activated carbon fiber, carbon nano-fiber, mesopore raw material of wood-charcoal material.Wherein various charcoal carriers comprise that the charcoal carrier after the acidification reaches without the charcoal carrier after the acidification; CNT comprises SWCN, double-walled carbon nano-tube, multi-walled carbon nano-tubes and short nanotube; Described multi-walled carbon nano-tubes or short carbon nanometer tube, their outer electrical path length can be 10-20nm, 20-30nm, 30-50nm or 50nm, interior electrical path length can be 1-5nm, 5-10nm or 5-15nm; Wherein the multi-walled carbon nano-tubes carrier comprises the multi-walled carbon nano-tubes of hydroxylated multi-walled carbon nano-tubes, carboxylated and the multi-walled carbon nano-tubes of not functionalized again.Active component is single constituent element or multicomponent transition metal carbide, nitride or phosphide, and the loading of active component is 5-90wt%.
Described cellulose hydrogenation hydrolyzation catalytic reaction is carried out in closed reactor, the mass ratio of reaction raw materials microcrystalline cellulose and water is 1:200-1:50, the mass ratio of microcrystalline cellulose and catalyst is 1:1-10:1, under the room temperature in the reactor initial pressure of hydrogen be 1-10MPa, reaction temperature is 120-250 ℃, reaction time is 3-72 hour, and mixing speed is 100r/min-1500r/min.
Its optimal conditions can be: the initial pressure of hydrogen is 3-5MPa under the room temperature, reaction temperature is 180-200 ℃, reaction time is 24 hours, the mass ratio of microcrystalline cellulose and water is 1:125-1:100, the mass ratio of microcrystalline cellulose and catalyst is 3:1-10:3, and mixing speed is 500r/min-1000r/min.
This catalyst preparation process is as follows:
Transition metal A or/and in the mixed solution of the water-soluble and ethanol of the solubility ammonium salt of B (volume content of ethanol is 0-100%), adopt the method for incipient impregnation to support on the charcoal carrier, is obtained catalyst precursor through 120 ℃ of oven dry, 450 ℃ of roastings.With the method for this presoma, can prepare different transition metal carbides or nitride catalyst with temperature programming carbonization or nitrogenize.With diammonium hydrogen phosphate and transition metal A or/and the solubility ammonium salt of B molten aqueous solution evaporate to dryness altogether, roasting obtains catalyst precursor, this presoma is carried out the method for temperature programming reaction again and can prepare different supported type transition metal phosphide catalysts under hydrogen atmosphere.
Advantage of the present invention is:
1. such catalyst is owing to adopt the class noble metal as active component, and it is with low cost, and have the specific area height simultaneously, be easy to moulding, advantage such as preparation technology is simple, make further practical application become possibility.
2. such catalyst has and the Pt/ γ-Al that openly reports at present
2O
3The cellulose catalyzed conversion activity that catalyst is close, the productive rate of its gained reproducibility sugar alcohol can partially or completely substitute Pt/ γ-Al up to 21%
2O
3Catalyst.
The specific embodiment
Further specify the present invention below in conjunction with embodiment.Be noted that these embodiment only are in order to demonstrate the invention, in office where face does not constitute limitation of the scope of the invention.
Embodiment 1 Preparation of catalysts
Taking by weighing the 0.5587g ammonium metatungstate is dissolved in the deionized water; be on 33% active carbon (AC) carrier of 80 ℃ of water bath processing of nitric acid after 24 hours through weight concentration with the settled solution incipient impregnation that obtains to 1g; dried in the shade under the room temperature 12 hours; in 120 ℃ of baking ovens, dried by the fire 2 hours then; roasting is 4 hours under 500 ℃ of nitrogen protections, makes WO
3/ AC presoma.With WO
3/ AC presoma, program temperature reaction in hydrogen atmosphere is raised to 450 ℃ with the speed of 10 ℃/min from room temperature, the speed with 1 ℃/min is raised to 800 ℃ again, keeps 1 hour under this temperature, be cooled to room temperature after, feed 1%O
2/ N
2(V/V) the passivating gas passivation is 12 hours.The loading of this catalyst W is 30wt%, is labeled as W
2C/AC.
Embodiment 2 Preparation of catalysts
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, changes absorbent charcoal carrier the carbon nanotube carrier of carboxylated into, and this catalyst is labeled as W
2C/CNTs-COOH.
Embodiment 3 Preparation of catalysts
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, the pure hydrogen in the temperature programming course of reaction is changed make ammonia, and will reduce final temperature and be reduced to 700 ℃ from 800 ℃.This catalyst is labeled as W
2N/AC.
Embodiment 4 Preparation of catalysts
It is soluble in water altogether to take by weighing 0.264g diammonium hydrogen phosphate and 0.5055g ammonium metatungstate, be on 33% the absorbent charcoal carrier of 80 ℃ of water bath processing of nitric acid after 24 hours through concentration with this maceration extract incipient impregnation in 1g, 120 ℃ of dryings 12 hours, 500 ℃ of roastings 5 hours obtain predecessor.Under hydrogen atmosphere predecessor was raised to 350 ℃ from room temperature in 1 hour, the heating rate with 1 ℃/min is raised to 850 ℃ again, and keeps under this temperature 1 hour, after be cooled to room temperature.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before the sample ingress of air, uses O earlier
2/ N
2(1%V/V) passivation is 2 hours.The loading of this catalyst WP is 30wt%, is labeled as WP/AC.
Comparative example 1 Preparation of catalysts
The 0.0676g chloroplatinic acid is dissolved in the 1ml water, and incipient impregnation is to 1g γ-Al
2O
3On the carrier, dried in the shade under the room temperature 12 hours, baking 2 hours in 120 ℃ of baking ovens then, roasting is 4 hours in 450 ℃ of air, and reductase 12 hour under 450 ℃ of hydrogen atmospheres again makes the Pt/ γ-Al of 2.5wt%Pt content
2O
3Catalyst.
The evaluation of embodiment 5 catalyst
Catalyst of the present invention is to carry out in the batch reactor of a 100ml.In reaction forward reaction still, add 0.5g microcrystalline cellulose, 0.15g catalyst and 50ml distilled water.Under the room temperature, initial hydrogen pressure is 5MPa, and reactor is heated to 190 ℃, and mixing speed is 1000r/min, reacts 24 hours.Reaction end back question response still temperature is reduced to room temperature product is carried out centrifugation, gets supernatant liquid and with liquid chromatogram products obtained therefrom is analyzed, and calculates the productive rate of target product D-sorbite (S) and sweet mellow wine (M).
Different catalysts cellulose catalyzed conversion specific activity, evaluation result sees Table 1.
The specific activity of table 1 different catalysts
The evaluation of embodiment 6 catalyst
Difference from Example 5 is that catalyst is W
2C/AC, wherein the loading of W is respectively 20%, 30%, 40%, 50%, 60%, and method for preparing catalyst is with embodiment 1, and purpose is to investigate the influence of different active component loadings to reaction result.
The catalyst activity of the different loadings of table 2 relatively
The investigation of embodiment 7 reaction conditions
Difference from Example 5 is that catalyst is W
2C/AC, wherein the loading of W is 30%, the initial pressure of hydrogen is respectively 3MPa under the room temperature, 4MPa, 5MPa, 6MPa, purpose is to investigate the influence of different initial hydrogen pressures to reaction result.
The comparison of productive rate under the table 3 different hydrogen initial pressure
The investigation of embodiment 8 reaction conditions
Difference from Example 5 is that catalyst is W
2C/AC, wherein the loading of W is 30%, and reaction temperature is respectively 170 ℃, and 180 ℃, 190 ℃, 200 ℃, purpose is to investigate the influence of different reaction temperatures to reaction result.
Productivity ratio under the table 4 differential responses temperature
The investigation of embodiment 9 reaction conditions
Difference from Example 5 is that catalyst is W
2C/AC, wherein the loading of W is 30%, the mixing speed during reaction is respectively 400r/min, 600r/min, 800r/min, 1000r/min, 1200r/min, purpose is to investigate the influence of different mixing speeds to reaction result.
Productivity ratio under the different mixing speeds of table 5
Embodiment 10 Preparation of catalysts
Method for preparing catalyst is at first with embodiment 1, and next gets the W that 1g prepares
2The C/AC catalyst is the nickel nitrate of incipient impregnation 0.6409g thereon, and the loading of this Ni only is 30%, dries in the shade 120 ℃ of oven dry 2 hours, 450 ℃ of reductase 12s hour under hydrogen atmosphere at last, O under the room temperature under the room temperature 12 hours
2/ N
2(1%V/V) passivation is 2 hours.This catalyst is labeled as WNiC/AC.
Embodiment 11 Preparation of catalysts
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, is raw material with the 0.46g ammonium molybdate, and the loading that is prepared into Mo is the catalyst of 20wt%, is labeled as Mo
2C/AC;
Method by embodiment 5 is estimated catalyst, the productive rate 6% of S+M.
Claims (8)
1. the application of carbon carried noble metal catalysts in cellulose hydrogenation hydrolytic reaction, it is characterized in that: described catalyst can be represented by the formula, A
xB
yC/Z loaded catalyst, A are Mo or W, and B is V, Ni, Co, Fe, Ta, Nb, Ti, Cr or Zr, and C is carbon, nitrogen element or P elements, and Z is the charcoal carrier, and the loading of active component is 5-90wt% in the catalyst, wherein 0≤x≤2,0≤y≤2.
2. application according to claim 1 is characterized in that: described charcoal carrier is active carbon, carbon black, CNT, activated carbon fiber, carbon nano-fiber or mesopore raw material of wood-charcoal material.
3. application according to claim 2 is characterized in that: described CNT is SWCN, double-walled carbon nano-tube, multi-walled carbon nano-tubes or short nanotube.
4. application according to claim 3 is characterized in that: described multi-walled carbon nano-tubes or short carbon nanometer tube, their outer electrical path length can be 10-20nm, 20-30nm, 30-50nm or 50nm, interior electrical path length can be 1-5nm, 5-10nm or 5-15nm.
5. application according to claim 1 is characterized in that: described catalyst can be represented by the formula: A
xThe C/Z loaded catalyst, wherein A is W or Mo, wherein 0≤x≤2.
6. application according to claim 5 is characterized in that: described catalyst can be represented by the formula: A
2The C/Z loaded catalyst, wherein A is W or Mo.
7. application according to claim 1, it is characterized in that: described cellulose hydrogenation hydrolyzation catalytic reaction is carried out in airtight autoclave, the mass ratio of reaction raw materials microcrystalline cellulose and water is 1:200-1:50, the mass ratio of microcrystalline cellulose and catalyst is 1:1-10:1, mixing speed is 100r/min-1500r/min, under the room temperature in the reactor initial pressure of hydrogen be 1-10MPa, reaction temperature is 120-250 ℃, the reaction time is 3-72 hour.
8. application according to claim 7, it is characterized in that: described cellulose hydrogenation hydrolyzation catalytic reaction condition can be: the initial pressure of hydrogen is 3-5MPa under the room temperature, reaction temperature is 180-200 ℃, reaction time is 24 hours, the mass ratio of microcrystalline cellulose and water is 1:125-1:100, the mass ratio of microcrystalline cellulose and catalyst is 3:1-10:3, and mixing speed is 500r/min-1000r/min.
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| CN102671672A (en) * | 2011-03-15 | 2012-09-19 | 中国科学院大连化学物理研究所 | Preparation method and application of carbon-supported nickel-based catalyst |
| CN102049273B (en) * | 2009-10-27 | 2013-05-01 | 中国科学院大连化学物理研究所 | Mesoporous carbon-supported tungsten carbide catalyst and preparation and application thereof |
| CN104072335A (en) * | 2013-03-28 | 2014-10-01 | 中国石油大学(北京) | Method of cellulose catalytic conversion to prepare dihydric alcohol, hexahydric alcohol and gamma-valerolactone |
| US9352304B2 (en) | 2010-03-17 | 2016-05-31 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Methods for preparing ethylene glycol from polyhydroxy compounds |
| CN110961093A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Cr-Zr-O/TiO2-C nanotube catalyst, preparation method and application thereof |
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Family Cites Families (4)
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| CN1044488C (en) * | 1994-11-09 | 1999-08-04 | 中国石油化工总公司抚顺石油化工研究院 | Hydrogen refining catalyst |
| FR2755625B1 (en) * | 1996-11-13 | 1998-12-11 | Inst Francais Du Petrole | PHOSPHORUS-CONTAINING CATALYST AND METHOD FOR HYDROPROCESSING OIL LOADS WITH THIS CATALYST |
| CN1101454C (en) * | 2000-08-22 | 2003-02-12 | 中国石油化工股份有限公司 | Hydrodesulfurizing catalyst for fraction oil and its preparing method |
| CN101394928A (en) * | 2006-03-01 | 2009-03-25 | 国立大学法人北海道大学 | Catalyst for hydrolysis of cellulose and/or reduction of hydrolysis product thereof, and method for producing sugar alcohol from cellulose |
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2007
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| CN102049273B (en) * | 2009-10-27 | 2013-05-01 | 中国科学院大连化学物理研究所 | Mesoporous carbon-supported tungsten carbide catalyst and preparation and application thereof |
| US8889585B2 (en) | 2009-10-27 | 2014-11-18 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Mesoporous carbon supported tungsten carbide catalysts, preparation and applications thereof |
| US9352304B2 (en) | 2010-03-17 | 2016-05-31 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Methods for preparing ethylene glycol from polyhydroxy compounds |
| CN102671672A (en) * | 2011-03-15 | 2012-09-19 | 中国科学院大连化学物理研究所 | Preparation method and application of carbon-supported nickel-based catalyst |
| CN102671672B (en) * | 2011-03-15 | 2014-07-23 | 中国科学院大连化学物理研究所 | Preparation method and application of carbon-supported nickel-based catalyst |
| CN104072335A (en) * | 2013-03-28 | 2014-10-01 | 中国石油大学(北京) | Method of cellulose catalytic conversion to prepare dihydric alcohol, hexahydric alcohol and gamma-valerolactone |
| CN104072335B (en) * | 2013-03-28 | 2016-10-05 | 中国石油大学(北京) | A kind of cellulose catalytic converts dihydroxylic alcohols processed, hexahydroxylic alcohols and the method for gamma-valerolactone |
| CN110961093A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Cr-Zr-O/TiO2-C nanotube catalyst, preparation method and application thereof |
| CN113652708A (en) * | 2021-09-02 | 2021-11-16 | 广西师范大学 | Pt/Ni alloy3N@Mo2Preparation method of C hydrogen hydroxide evolution electrocatalyst |
| CN115999595A (en) * | 2023-01-04 | 2023-04-25 | 中国石油大学(华东) | Phosphoric acid compound modified activated carbon supported metal catalyst and preparation method and application thereof |
| CN115999595B (en) * | 2023-01-04 | 2024-05-07 | 中国石油大学(华东) | Phosphoric acid compound modified activated carbon supported metal catalyst and preparation method and application thereof |
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