CN104610199A - Method for preparing tetrahydrofurfuryl alcohol by liquid phase hydrogenation and catalyst used by method - Google Patents
Method for preparing tetrahydrofurfuryl alcohol by liquid phase hydrogenation and catalyst used by method Download PDFInfo
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- CN104610199A CN104610199A CN201510036166.3A CN201510036166A CN104610199A CN 104610199 A CN104610199 A CN 104610199A CN 201510036166 A CN201510036166 A CN 201510036166A CN 104610199 A CN104610199 A CN 104610199A
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- palladium catalyst
- load type
- tetrahydrofurfuryl alcohol
- carrier
- furfuryl 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
- B01J23/44—Palladium
Abstract
The invention discloses a method for preparing tetrahydrofurfuryl alcohol by liquid phase hydrogenation. According to the method disclosed by the invention, the tetrahydrofurfuryl alcohol is prepared through the following steps: applying a loaded palladium catalyst for performing high-selective hydrogenation on furfuryl alcohol under the conditions of a low temperature and low pressure, and performing a reaction. The carrier of the loaded palladium catalyst is a titania material, and palladium nanometer metal ions are loaded on the carrier. The invention further discloses a preparation method of the loaded palladium catalyst. The method disclosed by the invention has the characteristics of mild reaction condition, high catalytic activity, high selectivity of the tetrahydrofurfuryl alcohol and the like.
Description
Technical field
The present invention relates to a kind of directly from the liquid phase hydrogenating method of furfuryl alcohol production high purity tetrahydrofurfuryl alcohol, and the load type palladium catalyst used in this process.
Background technology
Tetrahydrofurfuryl alcohol, also known as tetrahydrofurfuryl carbinol, is green solvent and important organic intermediate, has a wide range of applications in agricultural and industry.It can be used for manufacturing dihydrofuran, tetrahydrofuran (THF), Methionin and bentiamine; May be used for producing amides plastics, frostproofer, weedicide and sterilant; Printing and dyeing are used as the decoloration and deodorization agent of lubricating oil dispersant and medicine.
Industrially generally carry out tetrahydrobiopterin synthesis furfuryl alcohol by the method for the continuous two-step catalyzing hydrogenation of furfural, primary process is, furfural first on Cu-Cr catalyst hydrogenation generate furfuryl alcohol, furfuryl alcohol generates tetrahydrofurfuryl alcohol by the final shortening of noble metal catalyst again.According to reported in literature, preparing tetrahydrofurfuryl alcohol by furfuralcohol hydrogenation catalyzer used can be alloy, metal oxide, skeleton nickel and load type metal catalyst.Wherein, the catalytic activity of alloy and metal oxide catalyst and selectivity are far below skeletal nickel catalyst; Although skeletal nickel catalyst relative reactivity is higher, reaction needed is carried 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 catalyzer selectivity is very high, the temperature of reaction needed is still higher.The furfuryl alcohol Hydrogenation reported in prior art comprises following for tetrahydrofurfuryl alcohol reaction process condition and catalyzer situation:
US Patent No. 2838523 describes the preparation method of a kind of load nickel catalyzator over celite and the application at Hydrogenation tetrahydrofurfuryl alcohol thereof.Prepare in the application of tetrahydrofurfuryl alcohol in furfuryl alcohol liquid-phase hydrogenatin, hydrogen-oil ratio 27110: 1, temperature be 81-84 DEG C, under pressure is the condition of normal pressure, the yield of tetrahydrofurfuryl alcohol is 99%.
Patent US3652458 describes the preparation method of the nickel catalyzator of a kind of load on aerosil and the application in hydrogenation reaction thereof.Prepare in the application of tetrahydrofurfuryl alcohol in furfuryl alcohol liquid-phase hydrogenatin, hydrogen-oil ratio 22500: 1, temperature be 150 DEG C, under pressure is the condition of normal pressure, the transformation efficiency of furfuryl alcohol is 99.8%, and the yield of tetrahydrofurfuryl alcohol is 89%.
The preparation method of a kind of load ruthenium catalyst over a molecular sieve and the application in hydrogenation reaction thereof is described in patent US4459419.Prepare in the application of tetrahydrofurfuryl alcohol in furfuryl alcohol liquid-phase hydrogenatin, in methanol solvate, catalyst levels is about 10% (accounting for the mass percent of furfuryl alcohol), and temperature is 45 DEG C, and pressure is 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 nickel catalyzator on alumina and the application in Hydrogenation tetrahydrofurfuryl alcohol thereof.Prepare in the application of tetrahydrofurfuryl alcohol in furfuryl alcohol liquid-phase hydrogenatin, air speed be 0.25, under temperature is 120 DEG C, reaction pressure is the condition of 4MPa, the transformation efficiency of furfuryl alcohol is 99.8%, and the selectivity of tetrahydrofurfuryl alcohol is 97%.
Document Green Chem.2012, has reported a kind of load at MnO in 14,3402-3409
xon with precious metal Ru, Rh, Pd and Pt are the catalyzer in active centre and the application in furfuryl alcohol liquid-phase hydrogenatin and hydrogenolysis thereof.Wherein prepare in the application of tetrahydrofurfuryl alcohol in furfuryl alcohol liquid-phase hydrogenatin, active the highest be Ru catalyzer, 120 DEG C, 6MPa, reaction 4 hours under aqueous conditions, furfuryl alcohol transformation efficiency 99.9%, the selectivity 78.7% of tetrahydrofurfuryl alcohol.
In the method that above-mentioned prior art proposes, be that the catalyzed reaction technique that starting raw material produces tetrahydrofurfuryl alcohol all needs to carry out under High Temperature High Pressure etc. requires higher condition with furfuryl alcohol, energy consumption is large.And the high hydrogen-oil ratio in existing method, means and the hydrogen participation reaction that reaction needed is a large amount of makes production cost higher.
Summary of the invention
In order to overcome the deficiency that above-mentioned prior art exists, the invention provides a kind of palladium catalyst that can realize directly using from the liquid phase hydrogenating method and this process of furfuryl alcohol production high purity tetrahydrofurfuryl alcohol under low-temp low-pressure.The method that the present invention proposes, carries out high selectivity hydrogenation to furfuryl alcohol, prepares the tetrahydrofurfuryl alcohol of purity under low-temp low-pressure.In load type palladium catalyst of the present invention, support of the catalyst is titania meterial.
The present invention is used for being directly loaded catalyst from furfuryl alcohol Hydrogenation for the catalyzer of tetrahydrofurfuryl alcohol, and its carrier is titania meterial, is further titanium oxide nanotubes.In this loaded catalyst, metal active centres is palladium.Particularly, in this loaded catalyst, on the carrier, palladium nano metal ion is uniformly dispersed palladium nano metal ion load, and size is 2-10nm.
In loaded catalyst of the present invention, the charge capacity of metal active centres is 1-10wt.%.
The invention allows for the application of described loaded catalyst, utilize this loaded catalyst to prepare tetrahydrofurfuryl alcohol by the method for liquid-phase hydrogenatin from furfuryl alcohol.
In the present invention, the preparation of load type palladium catalyst can adopt deposition sedimentation method of reducing to prepare.Wherein, the carrier of catalyzer can adopt hydrothermal synthesis method to prepare.The preparation of described load type palladium catalyst comprises the following steps:
(1) preparation of support of the catalyst: by TiO
2powder adds in NaOH strong solution, is cooled to room temperature after reacting 2-3 days under the condition of 100-150 DEG C, and after filtering washing, drying obtains support of the catalyst.In an embodiment, described support of the catalyst is TiOx nano tube material.
(2) deposition sedimentation process: be dispersed in by metal-salt in carrier aqueous solution, adds the rear filtration drying of reductive 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), metal-salt can be muriate, nitrate or carbonate; Particularly, metal-salt can be PdCl
2, Pd (NO
3)
2or Pd (Ac)
2.Preferably, metal-salt is PdCl
2.
In the present invention, in described step (2), reductive agent can be sodium borohydride, hydrazine hydrate, formaldehyde or Trisodium Citrate; Preferably, reductive agent is sodium borohydride.
The present invention applies this load type palladium catalyst directly by the method for furfuryl alcohol Hydrogenation for tetrahydrofurfuryl alcohol, and be the process adopting liquid-phase hydrogenatin, carry out high selectivity hydrogenation to furfuryl alcohol, catalysis prepares tetrahydrofurfuryl alcohol.
The present invention directly prepares the method for high purity tetrahydrofurfuryl alcohol from furfuryl alcohol liquid-phase hydrogenatin, under the condition of low-temp low-pressure, carry out high selectivity Hydrogenation for tetrahydrofurfuryl alcohol to furfuryl alcohol.The catalyzer adopted is load type palladium catalyst, and wherein, support of the catalyst is titania meterial.Further, described titania meterial is titanium oxide nanotubes, and it can be prepared by water heat transfer.In described load type palladium catalysis, palladium nano metal ion load on the carrier.
In the present invention, in described load type palladium catalyst, palladium nano metal ion 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 the 1-10% of furfuryl alcohol mass percent.
The present invention prepares in the method for high purity tetrahydrofurfuryl alcohol, can realize directly preparing tetrahydrofurfuryl alcohol by furfuryl alcohol under the condition of the temperature and pressure lower than existing preparation method.Preferably, in the present invention, temperature of reaction is at 15-30 DEG C, and reaction pressure is 0.1-0.5MPa.
The catalyzer of the inventive method and employing is applicable to water or majority of organic solvent.In the present invention, reaction solvent is water, common alcoholic and halogenated hydrocarbon solvent.Preferably, reaction solvent is alcohols.More specifically, alcoholic solvent comprises ethanol, Virahol etc.; Halogenated hydrocarbon solvent comprises 1,2-ethylene dichloride, chloroform etc.
Compared with prior art, the inventive method has reaction conditions gentleness, and catalytic activity is high, and tetrahydrofurfuryl alcohol selectivity height waits the feature of marked improvement, and this reaction process is simple to operate, and energy consumption is low.
Accompanying drawing explanation
Figure 1 shows that the XRD figure of titanium nano-tube material;
Fig. 2 (a) is depicted as the SEM figure of titanium nano-tube material;
Fig. 2 (b) is depicted as the TEM figure of palladium catalyst.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The preparation of embodiment 1 catalyzer:
By TiO
2powder adds in 5-15M NaOH strong solution, is cooled to room temperature after reacting 2-3 days under the condition of 100-150 DEG C, and after filtering washing, drying obtains titanium nano-tube material, and its XRD figure as shown in Figure 1.From the SEM figure shown in Fig. 2 (a), titanium nano-tube material prepared by the present invention is very even, and has good nanotube pattern.
Get appropriate PdCl
2solution adds in the titanium oxide nanotubes aqueous solution, regulates pH to pd after stirring
2+completely, add filtration drying after sodium borohydride reduction, prepare load type palladium catalyst, its specific surface area is 95-120m to precipitation
2/ g, from the TEM figure shown in Fig. 2 (b), metallic palladium nanoparticle is uniformly distributed on carrier, and its size is at 2-10nm, and mean sizes is 5.3nm substantially.
PdCl is adopted in the present embodiment
2, can also be Pd (NO
3)
2or Pd (Ac)
2, all can realize same effect.
Sodium borohydride is adopted to be reductive agent in the present embodiment.In the inventive method, reductive agent can also be hydrazine hydrate, formaldehyde or Trisodium Citrate, all can realize same effect.
Embodiment 2
The catalyzer using embodiment 1 to prepare carries out preparing tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, in round-bottomed flask, load catalyzer, consumption is about 5% (accounting for furfuryl alcohol mass percent), solvent (ethanol) thinning ratio is about 20: 1 (ethanol: furfuryl alcohol, volume ratio), temperature of reaction is 25 DEG C, react 1 hour under hydrogen balloon (0.1MPa) condition, furfuryl alcohol transformation efficiency 98%, tetrahydrofurfuryl alcohol selectivity 98%.
Embodiment 3
The catalyzer using embodiment 1 to prepare carries out preparing tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, under the reaction unit of same embodiment 2 and the condition of temperature of reaction and pressure, catalyst levels is about 5% (accounting for furfuryl alcohol mass percent), solvent (Virahol) thinning ratio is about 20: 1 (Virahols: furfuryl alcohol, volume ratio), react 1 hour, furfuryl alcohol transformation efficiency 70%, tetrahydrofurfuryl alcohol selectivity 99%.
Embodiment 4
The catalyzer using embodiment 1 to prepare carries out preparing tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, under the reaction unit of same embodiment 2 and the condition of temperature of reaction and pressure, catalyst levels is about 10% (accounting for furfuryl alcohol mass percent), solvent (1,2-ethylene dichloride) thinning ratio is about 20: 1 (1,2-ethylene dichloride: furfuryl alcohol, volume ratio), react 1 hour, furfuryl alcohol transformation efficiency 89%, tetrahydrofurfuryl alcohol selectivity 95%.
Embodiment 5
The catalyzer using embodiment 1 to prepare carries out preparing tetrahydrofurfuryl alcohol by furfuryl alcohol liquid-phase hydrogenatin, in autoclave, load catalyst levels be about 5% (accounting for furfuryl alcohol mass percent), solvent (ethanol) thinning ratio is about 20: 1 (ethanol: furfuryl alcohol, volume ratio), temperature of reaction is 25 DEG C, half hour is reacted, furfuryl alcohol transformation efficiency 70%, tetrahydrofurfuryl alcohol selectivity 100% under 0.5MPa condition.
In the present invention, use described catalyzer to carry out being prepared by furfuryl alcohol liquid-phase hydrogenatin the reaction of tetrahydrofurfuryl alcohol, under the reaction pressure of the temperature of reaction of 15-30 DEG C, 0.1-0.5MPa, all can obtain close reaction result.
Above experimental result shows, utilize catalyzer of the present invention to achieve and directly prepare tetrahydrofurfuryl alcohol by furfuryl alcohol under low temperature and lower pressure, and it is high to have furfuryl alcohol transformation efficiency, the advantage that tetrahydrofurfuryl alcohol selectivity is high.The inventive method is applicable to water or majority of organic solvent, is not limited in the solvent that above-described embodiment is mentioned.
Catalyzer proposed by the invention and catalysis preparation method thereof, the low-temp low-pressure condition of employing reduces costs minimizing energy consumption and simplifies reaction process has great advantage.And because the boiling point of furfuryl alcohol and tetrahydrofurfuryl alcohol differs less (7 DEG C), general rectifying is difficult to be separated, and the selectivity of the tetrahydrofurfuryl alcohol obtained prepared according to the methods of the invention is high, obtains high purity tetrahydrofurfuryl alcohol advantageous particularly for industrial production.Load type palladium catalyst prepared by the present invention is the catalyzer of the conventional preparing tetrahydrofurfuryl alcohol by furfuralcohol hydrogenation being different from existing report in preparation method and chemical constitution completely.And catalyzer of the present invention also has that catalytic activity is high, the transformation efficiency of furfuryl alcohol is high, the selectivity of tetrahydrofurfuryl alcohol is good, be applicable to the plurality of advantages such as most of common organic solvents.
Protection content of the present invention is not limited to above embodiment.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.
Claims (10)
1. directly prepare a method for tetrahydrofurfuryl alcohol from furfuryl alcohol liquid-phase hydrogenatin, it is characterized in that, under low-temp low-pressure, adopt load type palladium catalyst to carry out high selectivity hydrogenation to furfuryl alcohol, reaction prepares described tetrahydrofurfuryl alcohol; Wherein, the carrier of described load type palladium catalyst is titania meterial, and palladium nano metal ion load on the carrier; In described load type palladium catalyst, palladium nano metal ion is dispersed;
Wherein, in described method, the consumption of load type palladium catalyst is the 1-10% accounting for furfuryl alcohol mass percent.
2. method according to claim 1, is characterized in that, temperature of reaction is 15-30 DEG C, and reaction pressure is 0.1-0.5MPa.
3. method according to claim 1, is characterized in that, reaction solvent is water, alcohols or halogenated hydrocarbon.
4. for the load type palladium catalyst of furfuryl alcohol Hydrogenation for tetrahydrofurfuryl alcohol, it is characterized in that, the carrier of described load type palladium catalyst is titania meterial, and palladium nano metal ion load on the carrier; In described load type palladium catalyst, palladium nano metal ion is dispersed, and the size of palladium nano metal ion is 2-10nm.
5. according to claim 4ly it is characterized in that for the load type palladium catalyst of furfuryl alcohol Hydrogenation for tetrahydrofurfuryl alcohol, described titania meterial is titanium oxide nanotubes.
6. according to described in claim 4 or 5 for the preparation method of furfuryl alcohol Hydrogenation for the load type palladium catalyst of tetrahydrofurfuryl alcohol, it is characterized in that, described carrier is prepared by hydrothermal synthesis method, metal-salt is loaded on described carrier by deposition sedimentation by recycling reductive agent, prepares described load type palladium catalyst.
7. preparation method according to claim 6, is characterized in that, comprises following:
(1) carrier preparation: by TiO
2powder adds in NaOH strong solution, reacts 2-3 days, be cooled to room temperature under the condition of 100-150 DEG C, and after filtration, washing, drying obtains described carrier;
(2) deposition sedimentation process: metal-salt is dispersed in the aqueous solution containing described carrier, adds reductive agent after reduction reaction, filtration drying, obtain described load type palladium catalyst.
8. the preparation method according to claim 6 or 7, is characterized in that, described metal-salt is muriate, nitrate or carbonate.
9. the preparation method according to claim 6 or 7, is characterized in that, described reductive agent is sodium borohydride, hydrazine hydrate, formaldehyde or Trisodium Citrate.
10. preparing the application in tetrahydrofurfuryl alcohol from furfuryl alcohol liquid-phase hydrogenatin according to the load type palladium catalyst described in claim 4 or 5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786962A (en) * | 2019-02-21 | 2019-05-21 | 成都形水科技有限公司 | The preparation method of frequency selection antenna house |
| 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 |
| CN111229218A (en) * | 2020-01-10 | 2020-06-05 | 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109786962A (en) * | 2019-02-21 | 2019-05-21 | 成都形水科技有限公司 | The preparation method of frequency selection antenna house |
| 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 |
| CN111229218A (en) * | 2020-01-10 | 2020-06-05 | 清华大学 | Monoatomic palladium composite catalyst and preparation method and application thereof |
| 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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