CN104610199B - The method of tetrahydrofurfuryl alcohol and the catalyst of use thereof are prepared in a kind of liquid-phase hydrogenatin - Google Patents
The method of tetrahydrofurfuryl alcohol and the catalyst of use thereof are prepared in a kind of liquid-phase hydrogenatin Download PDFInfo
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- CN104610199B CN104610199B CN201510036166.3A CN201510036166A CN104610199B CN 104610199 B CN104610199 B CN 104610199B CN 201510036166 A CN201510036166 A CN 201510036166A CN 104610199 B CN104610199 B CN 104610199B
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- tetrahydrofurfuryl alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract
The invention discloses a kind of method that tetrahydrofurfuryl alcohol is prepared in liquid-phase hydrogenatin, the load type palladium catalyst of the application present invention carries out high selectivity hydrogenation under the conditions of low-temp low-pressure to furfuryl alcohol, and reaction prepares described tetrahydrofurfuryl alcohol.The carrier of described load type palladium catalyst is titania meterial, and palladium nano metal ion load is on the carrier.The invention also discloses the preparation method of this load type palladium catalyst.It is gentle that the present invention has reaction condition, and catalysis activity is high, tetrahydrofurfuryl alcohol selectivity high.
Description
Technical field
The present invention relates to a kind of liquid phase hydrogenating method directly producing high-purity tetrahydrofurfuryl alcohol from furfuryl alcohol, and used in this process
Load type palladium catalyst.
Background technology
Tetrahydrofurfuryl alcohol, also known as tetrahydrofurfuryl carbinol, is green solvent and important organic intermediate, has wide in agricultural and industry
General application.It can be used to manufacture dihydrofuran, oxolane, lysine and bentiamine；May be used for producing acyl
Amine plastics, antifreezing agent, herbicide and insecticide；Printing and dyeing are used as lubricating oil dispersant and the decoloration and deodorization agent of medicine.
Industrial typically carrying out tetrahydrobiopterin synthesis furfuryl alcohol by the method for the continuous two-step catalyzing hydrogenation of furfural, basic process is, furfural first exists
Being hydrogenated to furfuryl alcohol on Cu-Cr catalyst, furfuryl alcohol generates tetrahydrofurfuryl alcohol by the final catalytic hydrogenation of noble metal catalyst again.According to document
Report, the catalyst used by preparing tetrahydrofurfuryl alcohol by furfuralcohol hydrogenation can be that alloy, metal-oxide, skeleton nickel and load type metal are urged
Agent.Wherein, the catalysis activity and selectivity of alloy and metal oxide catalyst is far below skeletal nickel catalyst；Skeleton nickel is urged
Although agent relative reactivity is higher, but reaction needs to carry out under the critical conditions of High Temperature High Pressure, and by-product is more；
Load type metal catalyst is also the study hotspot risen recently, although this kind of catalyst selectivity is the highest, but the reaction temperature needed
Spend the highest.Furfuryl alcohol Hydrogenation reported in prior art includes following for tetrahydrofurfuryl alcohol reaction process condition and catalyst situation:
United States Patent (USP) US2838523 describes the preparation method of a kind of load Raney nickel over celite and at Hydrogenation four
The application of hydrogen furfuryl alcohol.In the application of tetrahydrofurfuryl alcohol is prepared in furfuryl alcohol liquid-phase hydrogenatin, hydrogen-oil ratio 27110:1, temperature be 81-84 DEG C,
Under conditions of pressure is normal pressure, the yield of tetrahydrofurfuryl alcohol is 99%.
Patent US3652458 describes the preparation method of a kind of Raney nickel being supported on aerosil and at hydrogenation
Application in reaction.In the application of tetrahydrofurfuryl alcohol is prepared in furfuryl alcohol liquid-phase hydrogenatin, hydrogen-oil ratio 22500:1, temperature be 150 DEG C,
Under conditions of pressure is normal pressure, the conversion ratio of furfuryl alcohol is 99.8%, and the yield of tetrahydrofurfuryl alcohol is 89%.
Patent US4459419 describes the preparation method of a kind of load ruthenium catalyst over a molecular sieve and in hydrogenation reaction
Application.In the application of tetrahydrofurfuryl alcohol is prepared in furfuryl alcohol liquid-phase hydrogenatin, in methanol solvate, catalyst amount is about 10% and (accounts for
The mass percent of furfuryl alcohol), temperature is 45 DEG C, and pressure is to react 30 minutes under 12.7MPa, and the yield of tetrahydrofurfuryl alcohol is 100%.
Chinese patent CN1341483 describes the preparation method of a kind of load Raney nickel on alumina and at Hydrogenation four
Application in hydrogen furfuryl alcohol.In the application of tetrahydrofurfuryl alcohol is prepared in furfuryl alcohol liquid-phase hydrogenatin, air speed be 0.25, temperature be 120 DEG C,
Under conditions of reaction pressure is 4MPa, the conversion ratio of furfuryl alcohol is 99.8%, and the selectivity of tetrahydrofurfuryl alcohol is 97%.
One is supported on MnO reported in document Green Chem.2012,14,3402-3409xOn with noble metal Ru, Rh,
Pd and Pt is catalyst and the application in furfuryl alcohol liquid-phase hydrogenatin and hydrogenolysis thereof in active center.Wherein prepare in furfuryl alcohol liquid-phase hydrogenatin
In the application of tetrahydrofurfuryl alcohol, activity is the highest is Ru catalyst, 120 DEG C, 6MPa, react under aqueous conditions 4 little
Time, furfuryl alcohol conversion ratio 99.9%, the selectivity 78.7% of tetrahydrofurfuryl alcohol.
In the method that above-mentioned prior art proposes, it is required at height with the catalytic reaction technique that furfuryl alcohol produces tetrahydrofurfuryl alcohol for initiation material
Carrying out under conditions of the requirements such as temperature high pressure are higher, energy consumption is big.And, the high hydrogen-oil ratio in existing method, it is meant that reaction needs
Substantial amounts of hydrogen participates in reaction so that production cost is higher.
Summary of the invention
For the deficiency overcoming above-mentioned prior art to exist, the invention provides a kind of can realization under low-temp low-pressure directly from bran
Palladium catalyst used in the liquid phase hydrogenating method of alcohol production high-purity tetrahydrofurfuryl alcohol and this process.The side that the present invention proposes
Method, carries out high selectivity hydrogenation to furfuryl alcohol under low-temp low-pressure, prepares the tetrahydrofurfuryl alcohol of purity.Of the present invention
In load type palladium catalyst, catalyst carrier is titania meterial.
The present invention is for being directly loaded catalyst from furfuryl alcohol Hydrogenation for the catalyst of tetrahydrofurfuryl alcohol, and its carrier is titanium oxide material
Material, is further titanium oxide nanotubes.In this loaded catalyst, metal active centres is palladium.Specifically, this load
In type catalyst, palladium nano metal particles loads on the carrier, and palladium nano metal particles is uniformly dispersed, and size is 2-10nm.
In loaded catalyst of the present invention, the load capacity of metal active centres is 1-10wt.%.
The invention allows for the application of described loaded catalyst, utilize this loaded catalyst by the method for liquid-phase hydrogenatin from
Furfuryl alcohol prepares tetrahydrofurfuryl alcohol.
In the present invention, the preparation of load type palladium catalyst can use deposition sedimentation method of reducing to prepare.Wherein, the load of catalyst
Body can use hydrothermal synthesis method to prepare.The preparation of described load type palladium catalyst comprises the following steps:
(1) preparation of catalyst carrier: by TiO2Powder adds in NaOH concentrated solution, anti-under conditions of 100-150 DEG C
It is cooled to room temperature after answering 2-3 days, after filtering washing, is dried to obtain catalyst carrier.In a detailed description of the invention, described catalysis
Agent carrier is TiOx nano tube material.
(2) deposition sedimentation processes: be dispersed in carrier aqueous solution by slaine, adds filtration drying after reducing agent reduction.
In the present invention, in described step (1), NaOH strong solution concentration is 5-15M.
In the present invention, in described step (2), slaine can be chloride, nitrate or carbonate；Specifically, slaine
Can be PdCl2、Pd(NO3)2Or Pd (Ac)2.Preferably, slaine is PdCl2。
In the present invention, in described step (2), reducing agent can be sodium borohydride, hydrazine hydrate, formaldehyde or sodium citrate；Preferably
Ground, reducing agent is sodium borohydride.
The present invention apply this load type palladium catalyst directly by furfuryl alcohol Hydrogenation for the method for tetrahydrofurfuryl alcohol, be to use liquid-phase hydrogenatin
Process, carries out high selectivity hydrogenation to furfuryl alcohol, and catalysis prepares tetrahydrofurfuryl alcohol.
The method that the present invention directly prepares high-purity tetrahydrofurfuryl alcohol from furfuryl alcohol liquid-phase hydrogenatin, under conditions of low-temp low-pressure, to furfuryl alcohol
Carry out high selectivity Hydrogenation for tetrahydrofurfuryl alcohol.The catalyst used is load type palladium catalyst, wherein, catalyst carrier
For titania meterial.Further, described titania meterial is titanium oxide nanotubes, and it can be prepared by water heat transfer
Obtain.In the catalysis of described load type palladium, palladium nano metal particles loads on the carrier.
In the present invention, in described load type palladium catalyst, palladium nano metal particles is dispersed.
The present invention prepares in the method for high-purity tetrahydrofurfuryl alcohol, and the consumption of described load type palladium catalyst accounts for furfuryl alcohol mass percent
1-10%.
The present invention prepares in the method for high-purity tetrahydrofurfuryl alcohol, it is possible under conditions of the temperature and pressure less than existing preparation method
Realize directly being prepared tetrahydrofurfuryl alcohol by furfuryl alcohol.Preferably, in the present invention, reaction temperature is at 15-30 DEG C, and reaction pressure is 0.1-0.5
MPa。
The catalyst of the inventive method and employing is applicable to water or majority of organic solvent.In the present invention, reaction dissolvent is water, common
Alcohols and halogenated hydrocarbon solvent.Preferably, reaction dissolvent is alcohols.More specifically, alcohols solvent includes ethanol, isopropanol etc.；
Halogenated hydrocarbon solvent includes 1,2-dichloroethanes, chloroform etc..
Compared with prior art, it is gentle that the inventive method has reaction condition, and catalysis activity is high, and tetrahydrofurfuryl alcohol selectivity is high
The feature of marked improvement, and this reaction process is simple to operate, and energy consumption is low.
Accompanying drawing explanation
Fig. 1 show the XRD figure of titanium nano-tube material；
Fig. 2 (a) show the SEM figure of titanium nano-tube material；
Fig. 2 (b) show the TEM figure of palladium catalyst.
Detailed description of the invention
In conjunction with specific examples below and accompanying drawing, the present invention is described in further detail.Implement the process of the present invention, condition,
Reagent, experimental technique etc., outside the lower content mentioned specially, be universal knowledege and the common knowledge of this area, this
Bright content is not particularly limited.
The preparation of embodiment 1 catalyst:
By TiO2Powder adds in 5-15M NaOH concentrated solution, is cooled to room after reacting 2-3 days under conditions of 100-150 DEG C
Temperature, is dried to obtain titanium nano-tube material after filtering washing, and its XRD figure is as shown in Figure 1.Scheme from the SEM shown in Fig. 2 (a)
Visible, titanium nano-tube material prepared by the present invention is highly uniform, and has good nanotube pattern.
Take appropriate PdCl2Solution adds in titanium oxide nanotubes aqueous solution, regulates pH to Pd after stirring2+Precipitation completely, adds
Entering filtration drying after sodium borohydride reduction, prepare load type palladium catalyst, its specific surface area is 95-120m2/ g, from Fig. 2
Shown in (b) TEM figure visible, palladium metal nanoparticle is uniformly distributed on carrier, its size at 2-10nm, average chi
Very little essentially 5.3nm.
The present embodiment uses PdCl2, it is also possible to it is Pd (NO3)2Or Pd (Ac)2, all can realize same effect.
Using sodium borohydride in the present embodiment is reducing agent.In the inventive method, reducing agent can also is that hydrazine hydrate, formaldehyde or lemon
Lemon acid sodium, all can realize same effect.
Embodiment 2
The catalyst using embodiment 1 preparation carries out being prepared tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, loads catalysis in round-bottomed flask
Agent, consumption are about 5% (accounting for furfuryl alcohol mass percent), and solvent (ethanol) thinner ratio is about 20:1 (ethanol: furfuryl alcohol, volume ratio),
Reaction temperature is 25 DEG C, reacts 1 hour, furfuryl alcohol conversion ratio 98%, tetrahydrofurfuryl alcohol under the conditions of hydrogen balloon (0.1MPa)
Selectivity 98%.
Embodiment 3
The catalyst using embodiment 1 preparation carries out being prepared tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, and the reaction in same embodiment 2 fills
Put with reaction temperature and pressure under conditions of, catalyst amount is about 5% (accounting for furfuryl alcohol mass percent), solvent (isopropanol)
Thinner ratio is about 20:1 (isopropanol: furfuryl alcohol, volume ratio), reacts 1 hour, furfuryl alcohol conversion ratio 70%, and tetrahydrofurfuryl alcohol selects
Property 99%.
Embodiment 4
The catalyst using embodiment 1 preparation carries out being prepared tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, and the reaction in same embodiment 2 fills
Put with reaction temperature and pressure under conditions of, catalyst amount is about 10% (accounting for furfuryl alcohol mass percent), solvent (1,2-bis-
Ethyl chloride) thinner ratio is about 20:1 (1,2-dichloroethanes: furfuryl alcohol, volume ratio), reacts 1 hour, furfuryl alcohol conversion ratio 89%,
Tetrahydrofurfuryl alcohol selectivity 95%.
Embodiment 5
The catalyst using embodiment 1 preparation carries out being prepared tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, loads and urge in autoclave
Agent consumption is about 5% (accounting for furfuryl alcohol mass percent), and solvent (ethanol) thinner ratio is about 20:1 (ethanol: furfuryl alcohol, volume ratio),
Reaction temperature is 25 DEG C, reacts half an hour, furfuryl alcohol conversion ratio 70%, tetrahydrofurfuryl alcohol selectivity 100% under the conditions of 0.5MPa.
In the present invention, described catalyst is used to carry out being prepared the reaction of tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, at 15-30 DEG C
Reaction temperature, 0.1-0.5MPa reaction pressure under, all can obtain close reaction result.
More than test result indicate that, utilize the catalyst of the present invention to achieve and directly prepared four by furfuryl alcohol under low temperature and lower pressure
Hydrogen furfuryl alcohol, and it is high to have furfuryl alcohol conversion ratio, the advantage that tetrahydrofurfuryl alcohol selectivity is high.The inventive method is applicable to water or major part
Organic solvent, is not limited in the solvent that above-described embodiment is mentioned.
Catalyst proposed by the invention and catalysis preparation method, the low-temp low-pressure condition of employing to reduce energy consumption reduce cost and
Simplify reaction process and there is great advantage.The boiling point being additionally, since furfuryl alcohol and tetrahydrofurfuryl alcohol differs less (7 DEG C), general rectification
It is difficult to separate, and the selectivity of the tetrahydrofurfuryl alcohol obtained prepared according to the methods of the invention is high, obtains high-purity four for commercial production
Hydrogen furfuryl alcohol is advantageous particularly.Load type palladium catalyst prepared by the present invention, is to be totally different from preparation method and chemical composition now
There is the catalyst of the conventional preparing tetrahydrofurfuryl alcohol by furfuralcohol hydrogenation of report.And, catalyst of the present invention also has catalysis activity height, furfuryl alcohol
Conversion ratio selectivity high, tetrahydrofurfuryl alcohol good, be applicable to the plurality of advantages such as major part common organic solvents.
The protection content of the present invention is not limited to above example.Under the spirit and scope without departing substantially from inventive concept, art technology
Personnel it is conceivable that change and advantage be all included in the present invention, and with appending claims as protection domain.
Claims (8)
1. the method directly preparing tetrahydrofurfuryl alcohol from furfuryl alcohol liquid-phase hydrogenatin, it is characterised in that under low-temp low-pressure, uses load
Type palladium catalyst carries out selective hydrogenation to furfuryl alcohol, and reaction prepares described tetrahydrofurfuryl alcohol；Wherein, described load type palladium
The carrier of catalyst is titanium oxide nanotubes, and palladium nano metal particles loads on the carrier；Described load type palladium is catalyzed
In agent, palladium nano metal particles is dispersed；
Wherein, in described method, the consumption of load type palladium catalyst is the 1-10% accounting for furfuryl alcohol mass percent；
The preparation method of described titanium oxide nanotubes is: by TiO2Powder adds in the NaOH concentrated solution that concentration is 5-15M,
It is cooled to room temperature after reacting 2-3 days under conditions of 100-150 DEG C, after filtering washing, is dried to obtain catalyst carrier.
Method the most according to claim 1, it is characterised in that reaction temperature is 15-30 DEG C, reaction pressure is 0.1-0.5MPa.
Method the most according to claim 1, it is characterised in that reaction dissolvent is water, alcohols or halogenated hydrocarbon.
4. one kind is used for the furfuryl alcohol Hydrogenation load type palladium catalyst for tetrahydrofurfuryl alcohol, it is characterised in that described load type palladium catalyst
Carrier be titanium oxide nanotubes, palladium nano metal particles load on the carrier；In described load type palladium catalyst,
Palladium nano metal particles is dispersed, and the size of palladium nano metal particles is 2-10nm；
The preparation method of described titanium oxide nanotubes is: by TiO2Powder adds in the NaOH concentrated solution that concentration is 5-15M,
It is cooled to room temperature after reacting 2-3 days under conditions of 100-150 DEG C, after filtering washing, is dried to obtain catalyst carrier.
The most according to claim 4 for furfuryl alcohol Hydrogenation for the preparation method of the load type palladium catalyst of tetrahydrofurfuryl alcohol, it is special
Levying and be, prepare described carrier by hydrothermal synthesis method, slaine is loaded to institute by deposition sedimentation by recycling reducing agent
State on carrier, prepare described load type palladium catalyst；
Wherein, described slaine is chloride, nitrate or carbonate.
Preparation method the most according to claim 5, it is characterised in that include following:
(1) prepared by carrier: by TiO2Powder adds in the NaOH concentrated solution that concentration is 5-15M, at the bar of 100-150 DEG C
React 2-3 days under part, be cooled to room temperature, through filtering, wash, be dried to obtain described carrier；
(2) deposition sedimentation processes: be dispersed in by slaine in the aqueous solution containing described carrier, adds reducing agent through reduction
After reaction, filtration drying, obtain described load type palladium catalyst.
7. according to the preparation method described in claim 5 or 6, it is characterised in that described reducing agent be sodium borohydride, hydrazine hydrate,
Formaldehyde or sodium citrate.
Load type palladium catalyst the most according to claim 4 is preparing the application in tetrahydrofurfuryl alcohol from furfuryl alcohol liquid-phase hydrogenatin.
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| CN109796427A (en) * | 2017-11-17 | 2019-05-24 | 华东师范大学 | A kind of preparation method of tetrahydrofurfuryl alcohol |
| CN110240578A (en) * | 2018-03-08 | 2019-09-17 | 华东师范大学 | A kind of plus hydrogen prepares the method for tetrahydrofurfuryl alcohol and nickel catalyst carried |
| CN109786962B (en) * | 2019-02-21 | 2021-02-23 | 成都形水科技有限公司 | Preparation method of frequency selection antenna housing |
| CN111229218B (en) * | 2020-01-10 | 2021-01-01 | 清华大学 | Monoatomic palladium composite catalyst and preparation method and application thereof |
| CN114591271A (en) * | 2022-03-22 | 2022-06-07 | 大连理工大学 | Method for preparing tetrahydrofurfuryl alcohol by furfural one-step hydrogenation under low-temperature condition |
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| CN102078810A (en) * | 2009-11-30 | 2011-06-01 | 葛昌华 | Oxide supported palladium hydrogenation catalyst and preparation method thereof |
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| JP6037209B2 (en) * | 2012-08-30 | 2016-12-07 | 国立大学法人東北大学 | Method for producing tetrahydrofuran compound, hydrogenation catalyst and method for producing the same |
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| CN102078810A (en) * | 2009-11-30 | 2011-06-01 | 葛昌华 | Oxide supported palladium hydrogenation catalyst and preparation method thereof |
| CN104059035A (en) * | 2014-07-01 | 2014-09-24 | 浙江大学 | Furfural catalytic hydrogenation method under supercritical carbon dioxide and method for preparing catalysts |
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