CN100357286C - Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol - Google Patents
Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol Download PDFInfo
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- CN100357286C CN100357286C CNB2005101223101A CN200510122310A CN100357286C CN 100357286 C CN100357286 C CN 100357286C CN B2005101223101 A CNB2005101223101 A CN B2005101223101A CN 200510122310 A CN200510122310 A CN 200510122310A CN 100357286 C CN100357286 C CN 100357286C
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- furfuryl alcohol
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- furfuralcohol
- amorphous alloy
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Abstract
The present invention relates to a method for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol. The present invention prepares load type NiB and NiCobB amorphous alloy catalysts by adopting a metal induced chemical plating method, and furfuralcohol contact alcohol for a reaction in a High-pressure reaction vessel under the condition of the Hydrogenation technology of the furfuralcohol and the existence of an amorphous alloy catalyst. The catalyst is an amorphous alloy composed of an active component of NiB or NiCoB with inorganic oxide loading effective amount, and the effective active component NiB or NiCoB occupies 20 percent of the quality of the catalyst. The present invention is used for the hydrogenation reaction of the furfuralcohol, and has the advantages of favorable catalytic activity, high conversion rate of the furfuralcohol, good selectivity of the tetrahydrofurfuryl alcohol, moderate reaction conditions, simple technology, easy industrial amplifying production and no environmental pollution.
Description
Technical field
The present invention relates to catalytic hydrogenation reaction, particularly a kind of processing method of furfuryl alcohol hydrogenation preparing tetrahydrofurfuryl alcohol, the loading type NiB, NiCoB amorphous alloy catalyst that adopts the metal inducing chemical plating preparation prepares utilisation technology in the tetrahydrofurfuryl alcohol in the furfuryl alcohol hydrogenation reaction.
Background technology
Tetrahydrofurfuryl alcohol claims tetrahydrofuran-2-methanol again, is important organic solvent and fine chemical material.It on electronic chemical product and soldering flux a kind of good weldering solvent that helps, be that resin, coating, greasy good solvent also are to make dihydrofuran, tetrahydrofuran (THF), Methionin, the raw material of bentiamine, also can be used to produce polyamide-based plastics, in printing and dyeing, be used as lubricating oil, the decoloration and deodorization agent of dispersion agent and medicine.
At present, the processing method catalyst system therefor effect of industrial furfuryl alcohol hydrogenation reaction is preferably skeleton nickel, very easily catches fire but in a single day skeleton nickel is exposed in the air, brings great potential safety hazard to production.In addition, also there are unfavorable factors such as contaminate environment in skeletal nickel catalyst, thereby presses for and develop a kind of efficient and eco-friendly new catalyst.In recent years in document and the patent amorphous alloy catalyst to be used for the report of various hydrogenation reactions of common occurrence.For example, Chinese patent CN 1546229A discloses the catalyzer that the NiB amorphous alloy of carrying transition metal inductor and load significant quantity constitutes on the inorganic oxide, good dispersion degree, and the catalyst activity height, and safe in utilization, be suitable for catalytic hydrogenation reaction.But being used for the furfuryl alcohol hydrogenation reaction does not appear in the newspapers.
Summary of the invention
The purpose of this invention is to provide the processing method that a kind of furfuryl alcohol shortening prepares tetrahydrofurfuryl alcohol, can overcome the shortcoming of prior art, the present invention mainly is used for the catalyzer of furfuryl alcohol hydrogenation reaction with metal inducing chemical plating loading NiB, NiCoB amorphous alloy on inorganic oxide, show good catalytic activity, the reaction conditions gentleness, technology is simple, is easy to industry's enlarging production, and environmentally safe.
Furfuryl alcohol shortening provided by the invention prepares the processing method of tetrahydrofurfuryl alcohol, be under the furfuryl alcohol hydrogenation technique condition and in the presence of a kind of catalyzer with furfuryl alcohol and ethanol in intermittence tank reactor or in magnetically stabilized bed reactor contact reacts, described catalyzer is the amorphous alloy catalyst that contains Ni, this catalyzer consists of the active ingredient NiB of inorganic oxide supported significant quantity or the amorphous alloy of NiCoB, and described effective active component NiB or NiCoB account for 20% of catalyst quality.
The volume ratio of described ethanol and furfuryl alcohol is 1: 1.
Described catalyzer accounts for 5.3% of furfuryl alcohol volume, calculates by dry weight.
Described inorganic oxide is: Al
2O
3, white carbon black, nanometer SiO
2Or Fe
2O
3
Ni and B mol ratio are 3: 7 among the described amorphous alloy NiB, and Ni, Co, B mol ratio are 3: 0.6: 7 among the NiCoB.
Described catalyst pack containing metal inductor Ag, charge capacity accounts for 0.2% of carrier quality.
Described furfuryl alcohol hydrogenation technique condition is: temperature 95-130 ℃, hydrogen pressure 2.0-3.0MPa is under the stirring velocity 250-650rpm, till being reacted to hydrogen pressure and not descending.
Furfuryl alcohol shortening provided by the invention prepares the processing method of tetrahydrofurfuryl alcohol, can overcome the shortcoming of prior art.The present invention mainly is used for the catalyzer of furfuryl alcohol hydrogenation reaction with metal inducing chemical plating loading NiB amorphous alloy on inorganic oxide, show good catalytic activity, furfuryl alcohol transformation efficiency height, the tetrahydrofurfuryl alcohol selectivity is good, the reaction conditions gentleness, technology is simple, is easy to industry's enlarging production, and environmentally safe.
Substantive distinguishing features that the present invention gives prominence to and unusual effect can be embodied from following embodiment, but they impose any restrictions the present invention.
Embodiment
Embodiment 1
Adopt metal inducing chemical plating to prepare NiCoB/Al
2O
3Amorphous alloy catalyst.
With main salt NiSO
46H
2O 4.8g, complexing agent quadrol 4.9ml are dissolved in the 213.3ml water, add to contain 1.95gKBH
4With the aqueous solution 133.3ml of 11.3g NaOH, be made into stable NiB plating bath.With main salt CoCl
26H
2O 0.83g, complexing agent and auxiliary complex-former sodium tartrate 16g, borax 1.9g, NH
4Cl 0.33g is soluble in water respectively, is mixed into 198.3ml solution, adds and contains 0.37g KBH
4With the aqueous solution 50ml of 2.1g NaOH, be made into stable CoB plating bath.NiB and CoB plating bath are mixed, promptly make stable NiCoB plating bath.
Under 45 ℃ of water bath condition, in plating bath, add 5.0g Ag/Al
2O
3Precursor, reaction is to there not being bubble to generate.The catalyzer of preparing is through being washed to neutrality, again with absolute ethanol washing and be kept in the dehydrated alcohol standby.
Adopt the 250ml autoclave to carry out the furfuryl alcohol hydrogenation reaction.Reaction conditions: 60ml water, 60ml furfuryl alcohol, 3.18gNiCoB/Al
2O
3Amorphous alloy catalyst (amounting to into dry weight); Hydrogen pressure 2.8-3.0MPa; Stirring velocity 650rpm; 110 ℃ of temperature of reaction; Reaction times and evaluation result are listed in the table 1.
Embodiment 2
With the Al among the embodiment 1
2O
3Carrier changes Fe into
2O
3, other are all with embodiment 1.The results are shown in Table 1.
Embodiment 3
Temperature of reaction among the embodiment 2 is elevated to 150 ℃, and other are all with embodiment 2.The results are shown in Table 1.
Embodiment 4
Temperature of reaction among the embodiment 2 is elevated to 150 ℃, and rotating speed is transferred to 700rpm, and other are all with embodiment 2.The results are shown in Table 1.
Embodiment 5
Adopt metal inducing chemical plating to prepare the white carbon black amorphous alloy catalyst of NiB/.
With main salt NiSO
46H
2O 4.8g is dissolved in the 53.3ml water, and complexing agent quadrol 4.9ml is dissolved in the 213.3ml water, adds to contain 1.95g KBH
4With the aqueous solution 133.3ml of 11.3g NaOH, be made into stable NiB plating bath.
Under 45 ℃ of water bath condition, in plating bath, add the white carbon black precursor of 5.0g Ag/, reaction is to there not being bubble to generate.The catalyzer of preparing is through being washed to neutrality, again with absolute ethanol washing and be kept in the dehydrated alcohol standby.
Adopt the 250ml autoclave to carry out the furfuryl alcohol hydrogenation reaction.Reaction conditions: 60ml water, 60ml furfuryl alcohol, the white carbon black amorphous alloy catalyst of 3.18g NiB/ (amounting to into dry weight); Hydrogen pressure 2.8-3.0MPa; Stirring velocity 650rpm; 110 ℃ of temperature of reaction; Reaction times and evaluation result are listed in the table 1.
Embodiment 6
Adopt metal inducing chemical plating to prepare NiB/SiO
2Amorphous alloy catalyst.
With main salt NiSO
46H
2O 3.76g is dissolved in the 100ml water, adds complexing agent and PH conditioning agent NH
3H
2O20ml adds and contains 1.53g KBH
4Aqueous solution 22.5ml, be made into stable NiB plating bath.
Under 45 ℃ of water bath condition, in plating bath, add 4.5gAg/SiO
2Precursor, reaction is to there not being bubble to generate stopped reaction.The catalyzer of preparing is through being washed to neutrality, again with absolute ethanol washing and be kept in the dehydrated alcohol standby.
Adopt the 250ml autoclave to carry out the furfuryl alcohol hydrogenation reaction.Reaction conditions: 60ml water, 60ml furfuryl alcohol, 3.18g NiB/SiO
2Amorphous alloy catalyst (amounting to into dry weight); Hydrogen pressure 2.8-3.0MPa; Stirring velocity 650rpm; 110 ℃ of temperature of reaction; Reaction times and evaluation result are listed in the table 1.
Embodiment 7
Hydrogen pressure among the embodiment 6 and stirring velocity is constant, change temperature of reaction, other are all with embodiment 6.Evaluation result sees Table 2.
Embodiment 8
Temperature of reaction among the embodiment 6 and stirring velocity is constant, change hydrogen pressure, other are all with embodiment 6.Evaluation result sees Table 3.
Embodiment 9
Temperature of reaction among the embodiment 6 is transferred to 120 ℃, and hydrogen pressure is constant, changes stirring velocity, and other are all with embodiment 6.Evaluation result sees Table 4.
Product detection method: product is separated, analyze with gas chromatograph.Detector is a hydrogen flame detector, and chromatographic column is polyoxyethylene glycol-20000 capillary column, testing conditions: temperature of vaporization chamber-220 ℃, sensing chamber's temperature-180 ℃, column compartment temperature-130 ℃, sample size 0.4ul.
Table 1 different catalysts under the differential responses condition to the hydrogenation effect of furfuryl alcohol
| Embodiment | Temperature (℃)/hydrogen pressure (MPa)/rotating speed (rpm) | Reaction times (h) | Furfuryl alcohol transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
| 1 | 110/2.8-3.0/650 | 2.7 | 97.9 | 99.8 |
| 2 | 110/2.8-3.0/650 | 5 | 0.2 | 19.3 |
| 3 | 150/2.8-3.0/650 | 5 | 14.0 | 100.0 |
| 4 | 150/2.8-3.0/700 | 7 | 18.1 | 100.0 |
| 5 | 110/2.8-3.0/650 | 4.3 | 92.4 | 100.0 |
| 6 | 110/2.8-3.0/650 | 1.5 | 99.1 | 100.0 |
Table 2 NiB/SiO
2Catalyzer when changing temperature of reaction to the hydrogenation effect of furfuryl alcohol
| Embodiment | Temperature (℃)/hydrogen pressure (MPa)/rotating speed (rpm) | Reaction times (min) | Furfuryl alcohol transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
| 7 | 95/2.8-3.0/650 | 1.8 | 98.1 | 99.8 |
| 100/2.8-3.0/650 | 1.7 | 99.1 | 100.0 | |
| 110/2.8-3.0/650 | 1.5 | 99.1 | 100.0 | |
| 120/2.8-3.0/650 | 1.5 | 99.3 | 100.0 | |
| 130/2.8-3.0/650 | 1.3 | 99.5 | 100.0 |
Table 3 NiB/SiO
2Catalyzer when changing hydrogen pressure to the hydrogenation effect of furfuryl alcohol
| Embodiment | Temperature (℃)/hydrogen pressure (MPa)/rotating speed (rpm) | Furfuryl alcohol transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
| 8 | 110/2.0-2.2/650 | 99.8 | 99.6 |
| 110/2.2-2.4/650 | 98.8 | 99.6 | |
| 110/2.6-2.8/650 | 99.5 | 99.6 | |
| 110/2.8-3.0/650 | 99.3 | 100.0 |
Table 4 NiB/SiO
2Catalyzer when changing stirring velocity to the hydrogenation effect of furfuryl alcohol
| Embodiment | Temperature (℃)/hydrogen pressure (MPa)/rotating speed (rpm) | Furfuryl alcohol transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
| 9 | 120/2.8-3.0/250 | 42.0 | 98.5 |
| 120/2.8-3.0/450 | 84.1 | 99.5 | |
| 120/2.8-3.0/550 | 100.0 | 99.8 | |
| 120/2.8-3.0/650 | 99.3 | 100.0 |
Claims (6)
1, a kind of furfuryl alcohol shortening prepares the processing method of tetrahydrofurfuryl alcohol, be under the furfuryl alcohol hydrogenation technique condition and in the presence of a kind of catalyzer with furfuryl alcohol and ethanol in intermittence tank reactor or in magnetically stabilized bed reactor contact reacts,
It is characterized in that described catalyzer is the amorphous alloy catalyst that contains Ni, this catalyzer consists of the active ingredient NiB of inorganic oxide supported metal inducement agent Ag and significant quantity or the amorphous alloy of NiCoB, and described effective active component NiB or NiCoB account for 20% of catalyst quality;
Described metal inducement agent Ag charge capacity accounts for 0.2% of inorganic oxide carrier quality.
2, prepare the processing method of tetrahydrofurfuryl alcohol according to the described furfuryl alcohol shortening of claim 1, the volume ratio that it is characterized in that described ethanol and furfuryl alcohol is 1: 1.
3, the processing method for preparing tetrahydrofurfuryl alcohol according to the described furfuryl alcohol shortening of claim 1 is characterized in that described catalyzer accounts for 5.3% of furfuryl alcohol volume, calculates by dry weight, and wherein catalyst quality unit is gram, and the furfuryl alcohol volume unit is a milliliter.
4, the processing method for preparing tetrahydrofurfuryl alcohol according to the described furfuryl alcohol shortening of claim 1 is characterized in that described inorganic oxide is: Al
2O
3, white carbon black, nanometer SiO
2Or Fe
2O
3
5, the processing method for preparing tetrahydrofurfuryl alcohol according to the described furfuryl alcohol shortening of claim 1 is characterized in that Ni and B mol ratio are 3: 7 among the described amorphous alloy NiB, and Ni, Co, B mol ratio are 3: 0.6: 7 among the NiCoB.
6, the processing method for preparing tetrahydrofurfuryl alcohol according to the described furfuryl alcohol shortening of claim 1, it is characterized in that described furfuryl alcohol hydrogenation technique condition is temperature 95-130 ℃, hydrogen pressure 2.0-3.0MPa is under the stirring velocity 250-650rpm, till being reacted to hydrogen pressure and not descending.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101223101A CN100357286C (en) | 2005-12-13 | 2005-12-13 | Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol |
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|---|---|---|---|
| CNB2005101223101A CN100357286C (en) | 2005-12-13 | 2005-12-13 | Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol |
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|---|---|
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| CN100357286C true CN100357286C (en) | 2007-12-26 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829574B (en) * | 2010-05-17 | 2012-10-10 | 天津市安凯特催化剂有限公司 | Preparation method and application of load type nanometer nickel-cobalt catalyst |
| CN102068986B (en) * | 2011-01-06 | 2012-11-21 | 华东理工大学 | Catalyst used in ring-opening hydrogenation reaction of furan derivative |
| JP2015003892A (en) * | 2013-06-24 | 2015-01-08 | 宇部興産株式会社 | Method for producing polyol compound |
| CN112316945B (en) * | 2020-11-03 | 2021-09-03 | 吉林大学 | Heterogeneous nano composite material, preparation method thereof, nitro reduction catalyst and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179358A (en) * | 1996-10-15 | 1998-04-22 | 中国石油化工总公司 | Ni-B amorphous alloy catalyst, its preparing process and application |
| CN1262147A (en) * | 2000-03-02 | 2000-08-09 | 南开大学 | Hydrogenation catalyst with TiO2 as carrier of non-crystal NiB alloy |
| CN1546229A (en) * | 2003-12-15 | 2004-11-17 | 南开大学 | Catalyst for porous support carried NiB amorphous alloy and preparation method thereof |
-
2005
- 2005-12-13 CN CNB2005101223101A patent/CN100357286C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179358A (en) * | 1996-10-15 | 1998-04-22 | 中国石油化工总公司 | Ni-B amorphous alloy catalyst, its preparing process and application |
| CN1262147A (en) * | 2000-03-02 | 2000-08-09 | 南开大学 | Hydrogenation catalyst with TiO2 as carrier of non-crystal NiB alloy |
| CN1546229A (en) * | 2003-12-15 | 2004-11-17 | 南开大学 | Catalyst for porous support carried NiB amorphous alloy and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 超细Ni-B非晶态合金催化糠醛液相加氢制备糠醇 骆红山等.分子催化，第16卷第1期 2002 * |
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