CN108636453A - A kind of nano-noble metal catalyst and its preparation method and application of metal-organic framework material encapsulation - Google Patents

A kind of nano-noble metal catalyst and its preparation method and application of metal-organic framework material encapsulation Download PDF

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CN108636453A
CN108636453A CN201810305090.3A CN201810305090A CN108636453A CN 108636453 A CN108636453 A CN 108636453A CN 201810305090 A CN201810305090 A CN 201810305090A CN 108636453 A CN108636453 A CN 108636453A
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catalyst
metal
reaction
butanol
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CN108636453B (en
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江大好
方葛钱
童雨琴
王逸凡
洪东森
倪珺
李小年
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Zhejiang University of Technology ZJUT
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium

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Abstract

The invention discloses a kind of nano-noble metal catalysts and its preparation method and application of metal-organic framework material encapsulation, and catalyst is grouped as by the group of following mass percent：90% ~ 99.95% MOF carriers, 0.05% ~ 10% noble metal；For impregnation method, in preparation method, the inventory of material is grouped as the preparation method used by the group converts, and is condensed applied to alcohol dehydrogenase in the reaction of n-butanol processed.The method for preparing catalyst of the present invention is simple and efficient, has excellent performance, using when use fixed bed ethyl alcohol butanol continuous reaction, flow is simple, and reaction condition is relatively mild, the yield highest of n-butanol can reach 25wt% in product, and catalyst has the stability of height.

Description

A kind of nano-noble metal catalyst of metal-organic framework material encapsulation and its preparation side Method and application
Technical field
The invention belongs to technical field of catalytic chemistry, more particularly to what a kind of metal-organic framework material (MOF) encapsulated receives Rice Pd catalyst (Pd@MOF) and its preparation method and application, the catalyst can be used for alcohol dehydrogenase and be condensed n-butanol reaction processed.
Background technology
The biology base energy and chemicals reply Global climate change, implement substitution of resources strategy, ensure energy security and Promote chemical industry sustainable development etc. that can play significant role.Wood-based composites as a kind of renewable clean fuel Gasoline additive is widely used as in Europe, the U.S., Brazil and China to use.Although the addition of ethyl alcohol can reduce gasoline use Amount, but itself have the shortcomings that energy density is low, water imbibition is strong, perishable engine, therefore be not optimal gasoline tune And component.And for opposite ethyl alcohol, butanol is insoluble in water, energy resource density height, can mix (20% with gasoline with higher ratio Vs 10%), and it is small to automobile engine corrosivity, it can be used directly without being transformed to it, therefore as more than ethyl alcohol Ideal biofuel additive.Meanwhile n-butanol is also widely used for dibutyl phthalate (DBP), aliphatic fourth fat, phosphoric acid The synthesis of the plastics such as fourth fat and rubber product plasticizer.However, industrially butanol is mainly using petroleum base propylene as raw material, through carbonyl Change and hydrogenation reaction obtains.The raw material of the technology path is complexed from non-renewable oil, and using expensive rhodium Object catalyst.Although n-butanol can also be used zymotechnique similar with ethyl alcohol and be made with biomass material (being currently mostly cereal) It takes, but the efficiency that biological fermentation process produces butanol is very low, while producing butanol to be set with larger evaporation, heating and cooling It applies, investment cost is higher.And on the other hand, bio-ethanol can largely be given birth to by the fermented method of the biomass such as corn, wheat, stalk Production, raw material is renewable, small investment, environmental pollution are small.Especially the production technologies such as cellulosic ethanol, coal base ethyl alcohol are not in recent years Disconnected to make progress, the yield of global ethyl alcohol is constantly soaring, so that butanol is produced in alcohol catalysis conversion becomes catalytic field one A new research hotspot.
In the document published, the complex compounds homogeneous catalyst such as iridium, ruthenium, manganese is used for alcohol dehydrogenase condensation and makes positive fourth Alcohol reacts, and achieves higher butanol selectivity and yield, but it prepares complexity, uses sodium hydroxide, sodium ethoxide etc. Catalyst of the soluble highly basic as acetaldehyde aldol condensation step, especially its use tank reactor, catalyst separation is difficult, Reaction be unable to serialization progress, thus be unfavorable for butanol fuel in future large-scale production [Dowson, G.R.M., Haddow, M.F.,Wass,D.F.,Catalytic conversion of ethanol into an advanced biofuel: unprecedented selectivity for n-butanol,Angew.Chem.Int.Ed.,2013,52,9005-9008； Chakraborty,S.P,Piszel,E.P.,Cassandra,E.H.,Jones,W.D.,Highly selective formation of n-butanol from ethanol through the Guerbet process:A tandem catalytic approach,J.Am.Chem.Soc.,2015,137,14264-14267；Wingad,R.L.,Gates, P.J.,Street,S.T.G.,Wass,D.F.,Catalytic conversion of ethanol to n-butanol using ruthenium P-N Ligand complexes,ACS Catal.,2015,5,5822-5826；Fu S.M.,Shao Z.H.,Wang Y.J.,Liu Q.,Manganese-catalyzed upgrading of ethanol into 1- butanol.J.Am.Chem.Soc.,2017,139(34):11941-11948].Hydrotalcite, apatite, strontium phosphate, aluminium oxide The reaction that the solid catalysts such as load copper and mickel are condensed n-butanol processed for alcohol dehydrogenase is also reported there are many open, but its fourth The yield of alcohol is universal relatively low (generally below 10wt%), and reaction temperature and pressure it is higher (>300 DEG C,>4.0MPa) [Carvalho,D.L.,de Avillez,R.R.,Borges,L.E.P.,Mg and Al mixed oxides and the synthesis of n-butanol from ethanol,Appl.Catal.A.,2012,415-416,96-100； Tsuchida,T.,Sakuma,S.,Takeguchi,T.,Ueda,W.,Yoshioka,T.,Reaction of ethanol over hydroxyapatite affected by Ca/P ratio of catalyst,J.Catal.,2008,259,183- 189；OgO,S.,Onda,A.,Yanagisawa,K.,Selective synthesis of1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts,Appl.Catal.A.,2011,402,188- 195；OgO,S.,Onda,A.,Yanagisawa,K.,Iwasa,Y.,Hara,K.,Fukuoka,A.,1-Butanol synthesis from ethanol over strontium phosphate hydroxyapatite catalysts with various Sr/P ratios,J.Catal.,2012,296,24-30；Riittonen,T.,Toukoniitty,E., Madnani,D.K.,Leino,A.R.Kordas.,One-pot liquid-phase catalytic conversion of ethanol to 1-butanol over aluminium oxide—the effect of the active metal on the selectivity,Catalysts,2012,2,68-84；Dziugan,P.,Jastrzabek,K.G.,Binczarski, M.,Karski,S.Continuous catalytic coupling of raw bioethanol into butanol and higher homologues,Fuel,2015,158,81-90；Jordison,T.L.,Lira,C.T.,Miller.D.J., Condensed phase ethanol conversion to higher alcohols,Ind.Eng.Chem.Res.,2015, 54,10991-11000；Riittonen,T.,Eranen,K.,Maki-Arvela,P.,Shchukarev,A.,Rautio, A.R.,Continuous liquid-phase valorization of bio-ethanol towards bio-butanol over metal modified alumina,Renew.Energy,2015,74,369-378].Large ratio surface cerium oxide loads Copper (260 DEG C, 10MPa) be even more the ethanol conversion and 30% for showing up to 67% in supercritical CO 2 medium Butanol yield, but the reaction pressure for being up to 10MPa improves the requirement to consersion unit and its material, and unit volume is anti- Answer the production capacity of device butanol relatively low, thus its commercial Application is also by a degree of restriction [Earley J.H., Bourne R.A.,Watson M.J.,Poliakoff M.,Continuous catalytic upgrading of ethanol to n- butanol and>C4products over Cu/CeO2catalysts in supercritical CO2.Green Chem.,2015,17:3018-3025].And in newest document, activated carbon supported copper-cerium oxide catalyst is used for second Alcohol catalysis upgrades butanol processed reaction, and achieves 46% ethanol conversion and close under relatively mild reaction conditions The butanol yield of 20wt%, but its catalyst activity in long-time is evaluated has a degree of decline [Jiang D.H., Wu X.Y.,Mao J.,Ni J.,Li X.N.,Continuous catalytic upgrading ethanol to n-butanol over Cu-CeO2/AC catalysts,Chem.Commun.,2016,52:13749-13752；Activated carbon supported copper-metal Oxide catalyst and its preparation method and application, Chinese invention patent, 201610399455.4].
Alcohol dehydrogenase coupling reaction be typically considered via Guerbet coupling mechanisms realize [Scalbert J., Thibault-Starzyk F.,Jacquot R.,Morvan D.,Meunier F.,Ethanol condensation to butanol at high temperatures over a basic heterogeneous catalyst:How relevant is acetaldehyde self-aldolization,J.Catal.,2014,311:28-32；Meunier F.C., Scalbert J.,Thibault-Starzyk F.,Unraveling the mechanism of catalytic reactions through combined kinetic and thermodynamic analyses:Application to the condensation of ethanol,C.R.Chimie,2015,18:345-350].The reaction mechanism is mainly by four Cascade reaction forms (attached drawing 1)：Alcohol dehydrogenase generates acetaldehyde (I), acetaldehyde aldol condensation generates 3- hydroxybutyraldehydes (II), 3- hydroxyls Butyraldehyde dehydration generates crotonaldehyde (III) and crotonaldehyde is hydrogenated to butanol (IV).Wherein reaction step (I) and (IV) are usually with mistake Metal is crossed as activated centre；And for other transition metal, the dehydrogenation of metal Pd and Hydrogenation are all very excellent, It is suitable as alcohol dehydrogenase and reaction intermediates crotonaldehyde adds the activated centre of hydrogen.Reaction step (II) is alkaline on a catalyst Center or Acid and basic sites collaboration are completed, and acidic site (including Lewis acid and Bronsted acid) is then less is individually used for aldol Condensation reaction, in the presence of especially having Bronsted acid, ethyl alcohol is easy dehydration and generates the by-products such as ethylene, diethyl ether.The present invention Metal-organic framework material (MOF) is utilized for the first time, such as UiO-66, MIL-53 (Al) are active component, using in its Lewis acid The heart is catalyzed aldol condensation step.Relative to the basic anhydride with alkali center or acid-base pair, hydrotalcite, apatite isoreactivity group Point, MOF materials show higher aldol condensation activity in the reaction of ethyl alcohol butanol.Meanwhile MOF also have topological structure and Duct confinement effect, with its package metals nano-particle, can prevent the sintering of metal nanoparticle from growing up, to obtain efficiently And the metal load type ethyl alcohol butanol catalyst stablized.
Invention content
The present invention is with typical MOF materials, such as UiO-66, MIL-53 (AL) are carrier and active component, by simple Efficient dipping-reaction method, metal Pd is encapsulated in the ducts MOF, and the height for realizing palladium active component in MOF inner surfaces is divided It is scattered and Pd nano particle to be stabilized, while MOF itself a large amount of L acid activities site is utilized, it is efficient, steady to prepare Fixed Pd@MOF ethyl alcohol butanol multifunction catalysts.Wherein it is continuous to be applied to fixed bed ethyl alcohol for 2wt%Pd@UiO-66 catalyst Dehydrogenative condensation n-butanol reacts, in 250 DEG C, 2MPa, LHSV=2h-1, nitrogen/ethyl alcohol=250：The reaction item of 1 (volume ratio) Under part, the butanol yield of up to 25wt% is shown, especially it is constantly in highly stable shape in 200h pilot plant tests State.
UiO, MIL series are more typical metal-organic framework materials, and using most such as UiO-66, structural formula is [ZrIV 6O4(OH)4(bdc)12]；UiO-67, structural formula are [ZrIV 6O4(OH)4(bpdc)12]；UiO-68, structural formula are [ZrIV 6O4(OH)4(tpdc)12]；MIL-47 (V), structural formula are [VIV(OH)(bdc)]；MIL-53 (Al), structural formula are [AlIII(OH)(bdc)]；MIL-53 (Fe), structural formula are [FeIII(OH)(bdc)]；MIL-69 (Al), structural formula are [AlIII(OH)(ndc)].Wherein：bdc:1,4- phthalic acids；bpdc:4,4'- biphenyl dicarboxylic acids；tpdc:Para-terpheny -4, 4 "-dioctyl phthalate；tbapy:1,3,6,8- tetra- (para Toluic Acid) pyrene；ndc:2,6 naphthalene dicarboxylic acid.
Therefore, the present invention provides a kind of nano Pd catalysts (Pd@MOF) of metal-organic framework material (MOF) encapsulation And its preparation method and application；The catalyst is applied to the fixed bed continuous catalytic reaction that alcohol dehydrogenase is condensed n-butanol processed, tool Have the characteristics that ethyl alcohol activity of conversion and butanol selectivity and high income, stability are good.
For this purpose, the present invention adopts the following technical scheme that：
A kind of nano-noble metal catalyst of metal-organic framework material encapsulation, is grouped by the group of following mass percent At：
MOF carriers 90%~99.95%
Noble metal 0.05%~10%
Preferably, the nano-noble metal catalyst of metal-organic framework material encapsulation is by following mass percent Group is grouped as：
MOF carriers 95~99.9%
Noble metal 0.1~5%
In the present invention, the MOF carriers are powdered, and specific surface is 500~3000m2/ g, most probable pore size 0.2 0.2~1ml/g of~5nm, Kong Rongwei.
In the catalyst composition, MOF is indicated respectively with Zr6O4(OH)4, Al (OH) etc. be node, and with terephthaldehyde Acid, 2- hydroxyls are to the organic metal framework material (such as UiO-66, MIL-53 (AL)) that dibenzoic acid etc. is ligand, the gold It is Pd to belong to, and can also be other noble metals such as Pt, Ru, Ir.
As in catalyst of the present invention dehydrogenation and hydrogenation sites, the precious metals pd, Pt, Ru, Ir etc. be with Its acetylacetonate is prepared by presoma, and the noble-metal-supported amount is preferably 0.2~5wt% of MOF carriers.Wherein Metal Pd has highest alcohol dehydrogenase and crotonaldehyde hydrogenation activity, thus Pd@MOF catalyst is condensed butanol processed in alcohol dehydrogenase Highest ethyl alcohol activity of conversion and butanol selectivity are shown in reaction.
The present invention utilizes the dipping being simple and efficient-reaction legal system using MOF materials such as UiO-66, MIL-53 (AL) as carrier It is standby go out MOF encapsulation metal nano catalyst.On the high-ratio surface and node of MOF between hydroxyl and metal acetylacetonate salt Reaction is advantageously implemented the high dispersive of metal, and its topological structure and duct confinement effect limit the burning of metal nanoparticle It ties and grows up.Meanwhile a large amount of acid sites Lewis of MOF carrier surfaces have been catalyzed the aldol reaction of acetaldehyde.Therefore, MOF is sealed The metal nano catalyst of dress is condensed in butanol reaction processed in ethyl alcohol fixed bed continuous dehydrogenation and shows higher activity, butanol choosing Selecting property and stability.
The present invention also provides the preparation method of the nano-noble metal catalyst of metal-organic framework material encapsulation, institutes The preparation method stated is the dipping-reaction method being simple and efficient, and the inventory of material presses the component of above-mentioned catalyst in preparation method Composition converts.
The operating procedure of the infusion process is：
MOF carriers are immersed in the solution of metal precursor, 2~48h of reaction is stirred at room temperature, then by solvent 40~ 120 DEG C of stirrings are evaporated.By crude product dry 4 in 80~200 DEG C of air dry ovens~remove solvent remaining in duct for 24 hours, The metallic catalyst of MOF encapsulation is obtained after cooling.
In above-mentioned preparation method, the solvent for preparing the metal front liquid solution is acetylacetone,2,4-pentanedione, methanol, positive penta The organic solvents such as alkane, the metal precursor are the acetylacetonate of above-mentioned various metals.
The nano-noble metal catalyst of metal-organic framework material encapsulation of the present invention is condensed applied to alcohol dehydrogenase N-butanol reaction processed, the reaction are carried out continuously in fixed bed reactors, and the best catalyst of the present invention can show The butanol yield of 51% ethanol conversion, 49% butanol selectivity and 25wt%.
Catalyst of the present invention is pre-processed before use, the pretreatment be the nitrogen in flowing, hydrogen or Volume ratio 1：It is carried out in 10 hydrogen/nitrogen gaseous mixture, air speed is 100~3000h-1, temperature be 250-300 DEG C, the time be 1~ 4h。
Preferably, the reaction condition of alcohol dehydrogenase condensation n-butanol processed is：200~280 DEG C of temperature, reaction pressure 0.1~3.0MPa, 1~8.0h of liquid air speed-1, nitrogen/ethyl alcohol=100~600：1 (volume ratio).Under this condition, described Butanol selectivity and yield highest, and there is extraordinary stability (as shown in Figure 2).The Main By product of reaction have acetaldehyde, Butyraldehyde, ethyl acetate, 2- ethyl butanols, n-hexyl alcohol etc., unreacted ethyl alcohol is recyclable.
Compared with prior art, beneficial effects of the present invention are embodied in：
(1) nano-noble metal catalyst of the metal-organic framework material encapsulation described in is first applied to ethyl alcohol fourth The MOF base heterogeneous solid catalysts of alcohol.The catalyst utilizes a large amount of hydroxyl on the high-ratio surface and node of MOF carriers Reacting between metal acetylacetonate salt realize metal its surface high degree of dispersion, while using MOF carriers it is a large amount of The acid sites Lewis realize the efficient condensation of acetaldehyde intermediary, to finally realize Efficient Conversion of the ethyl alcohol to butanol.Especially It is that the distinctive topological structure of MOF carriers and duct confinement effect limit the sintering of metal nanoparticle and grow up, to realize Metal-supported catalyst it is highly stable.
(2) Metal Packaging there are into vapour deposition process, Double solvent method, in-situ synthesis etc. into the method in MOF, these methods Although it is also higher effectively, to operate excessively cumbersome, time-consuming and cost.Hydroxyl and metal on MOF nodes are utilized in the present invention Metal Pd can be encapsulated in the ducts MOF by the effect between acetylacetonate using simple dipping-reaction method, and real The high dispersive of metal Pd is showed.In this way, the MOF of other noble metal nano particles such as Pt, Ru, Ir equally may be implemented Encapsulation and high dispersive illustrate that this method has certain universality.
In conclusion the method for preparing catalyst of the present invention is simple and efficient, has excellent performance, fixed bed ethyl alcohol is used when application Butanol continuous reaction processed, flow is simple, and reaction condition is relatively mild, and the yield highest of n-butanol can reach in product 25wt%, and catalyst has the stability of height.
Description of the drawings
Fig. 1 is the Guerbet coupling mechanisms that alcohol dehydrogenase is condensed n-butanol processed；
Fig. 2 is the schematic diagram that ethyl alcohol continuous dehydrogenation is condensed n-butanol fixed-bed reactor processed；
1- metering pumps, 2- vaporizers, 3- fixed bed reactors, 4- catalyst beds, 5- temperature measuring points,
6- condensers, A- liquid charging stock imports, B- nitrogen inlets, C- reactor heads, D- reactor bottoms, E- products go out Mouthful.
Fig. 3 is the evaluation knot that ethyl alcohol fixed bed continuous dehydrogenation is condensed n-butanol 200h processed on catalyst C made from embodiment 3 Fruit；Reaction condition is：250 DEG C, pressure 2.0MPa of temperature, liquid air speed are 2.0h-1, nitrogen/ethyl alcohol=250：1 (volume ratio).
Specific implementation mode
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in This.
Embodiment 1
By 0.0573g bis- (acetylacetone,2,4-pentanedione) palladium (Pd (acac)2) be dissolved in the beaker for filling 57.3mL acetylacetone,2,4-pentanediones, it stirs It mixes after making it dissolve, 1g UiO-66 powder is added, reacted for 24 hours then at being stirred at room temperature.The beaker for filling said mixture is placed in In oil bath pan, 110 DEG C of stirrings are evaporated, and obtained solid powder, which is transferred to 150 DEG C of dry 12h in air dry oven, removes duct The solvent of middle remnants obtains the 2wt%Pd@UiO-66 catalyst, is denoted as catalyst A after cooling.Wherein metal Pd is negative Carrying capacity is 2wt%, remaining is UiO-66 carriers.
Embodiment 2
The preparation method is the same as that of Example 1 by catalyst B, but two (acetylacetone,2,4-pentanedione) palladium (Pd (acac)2) quality be 0.0143g.The weight content of its metal Pd is 0.5wt%, remaining is UiO-66 carriers.
Embodiment 3
The preparation method is the same as that of Example 1 by catalyst C, but two (acetylacetone,2,4-pentanedione) palladium (Pd (acac)2) quality be 0.0287g.The weight content of its metal Pd is 1wt%, remaining is UiO-66 carriers.
Embodiment 4
The preparation method is the same as that of Example 1 by catalyst D, but two (acetylacetone,2,4-pentanedione) palladium (Pd (acac)2) quality be 0.086g. The weight content of its metal Pd is 3wt%, remaining is UiO-66 carriers.
Comparative example 1
The preparation method is the same as that of Example 1 by catalyst E, but metal precursor used is 0.079g acetylacetone,2,4-pentanedione rutheniums (Ru (acac)3).The weight content of its metal Ru is 2wt%, remaining is UiO-66 carriers.
Comparative example 2
The preparation method is the same as that of Example 1 by catalyst F, but metal precursor used is 0.04g acetylacetone,2,4-pentanedione platinum (Pt (acac)2).The weight content of its Pt metal is 2wt%, remaining is UiO-66 carriers.
Comparative example 3
The preparation method is the same as that of Example 1 by catalyst G, but solvent for use is pentane, and metal precursor used is 0.051g acetylacetone,2,4-pentanediones iridium (Ir (acac)3).The weight content of its metal Ir is 2wt%, remaining is UiO-66 carriers.
Catalyst A, B, C, D, E, F and G are condensed the reaction condition in n-butanol reaction processed in fixed bed ethyl alcohol continuous dehydrogenation With the results are shown in Table 1.
Catalytic performance of the 1 difference MOF encapsulation metallic catalysts of table in the reaction of ethyl alcohol butanol
Note：The calculating of ethanol conversion, butanol selectivity and butanol yield is on the basis of product liquid, each catalyst upper liquid Body product total recovery is as follows：A, 86.06%；B, 94.52%；C, 89.65%；D, 87.19%；E, 96.72%；F, 90.14%； G, 98.32%)
By the result of table 1 it is recognised that compared with embodiment catalyst A, B, C and D, second on comparative example catalyst E, F and G Alcohol conversion and butanol yield are all relatively low, and have apparent deactivation phenomenom；Compared with metal Pd, the ethyl alcohol of metal Ru, Pt, Ir Dehydrogenation activity is not high, and their Hydrogenation is also poor, perhaps causes reaction intermediate crotonaldehyde that cannot be added in time Hydrogen generates butanol, instead in catalyst surface polymerization coking, to make catalyst activity, selectivity and stability all be deteriorated.

Claims (8)

1. a kind of nano-noble metal catalyst of metal-organic framework material encapsulation, which is characterized in that the catalyst is by such as The group of lower mass percent is grouped as：
Metal-organic framework material carrier 90%~99.95%
Noble metal 0.05%~10%
Metal-organic framework material refers to respectively with Zr6O4(OH)4, Al (OH) be node, and with terephthalic acid (TPA) or 2- hydroxyls pair two Benzoic acid is the organic metal framework material of ligand.
2. catalyst as described in claim 1, which is characterized in that the catalyst is grouped by the group of following mass percent At：
Metal-organic framework material carrier 95~99.9%
Noble metal 0.1~5%.
3. catalyst as claimed in claim 2, which is characterized in that the noble metal is Pd.
4. catalyst as claimed in claim 3, which is characterized in that the metal-organic framework material carrier be it is powdered, Specific surface is 500~3000m2/ g, most probable pore size are 0.2~5nm, 0.2~1ml/g of Kong Rongwei.
5. the preparation method of catalyst described in a kind of claim 4, which is characterized in that the preparation method is dipping-reaction Method, the inventory of material is grouped as by the group in preparation method converts, and concrete operation step is：
Metal-organic framework material carrier is immersed in the solution of Pd presomas, 2~48h of reaction is stirred at room temperature, it then will be molten Agent is evaporated in 40~120 DEG C of stirrings；By crude product dry 4 in 80~200 DEG C of air dry ovens~remove for 24 hours it is remaining in duct Solvent, the catalyst is obtained after cooling.
6. the preparation method of catalyst as claimed in claim 5, which is characterized in that the solvent for preparing Pd precursor solutions is The organic solvents such as acetylacetone,2,4-pentanedione, methanol, pentane, the Pd presomas are palladium acetylacetonate.
7. the catalyst described in claim 4 is applied to alcohol dehydrogenase to be condensed in the reaction of n-butanol processed.
8. catalyst as claimed in claim 7 is condensed the application in n-butanol reaction processed in alcohol dehydrogenase, which is characterized in that institute The reaction stated is carried out continuously in fixed bed reactors, and the reaction condition that the alcohol dehydrogenase is condensed n-butanol processed is：Temperature 200 ~280 DEG C, 0.1~3.0MPa of reaction pressure, 1~8.0h of liquid air speed-1, nitrogen/ethyl alcohol=100~600：1 (volume ratio)；
The catalyst is pre-processed before use, and the pretreatment is the nitrogen, hydrogen or volume in flowing Than 1：It is carried out in 10 hydrogen/nitrogen gaseous mixture, air speed is 100~3000h-1, temperature is 250-300 DEG C, and the time is 1~10h.
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