CN102489315B - Ruthenium catalyst, preparation method and application in synthesizing tetrahydrofurfuryl alcohol - Google Patents
Ruthenium catalyst, preparation method and application in synthesizing tetrahydrofurfuryl alcohol Download PDFInfo
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Abstract
The invention provides a ruthenium catalyst for synthesizing tetrahydrofurfuryl alcohol in one-step hydrogenation of furfural. The expression of the ruthenium catalyst is Ru-M/TiO2, wherein Ru accounts for 0.5-15 wt% of the catalyst; and M is a metal auxiliary and accounts for 0-20 wt% of the catalyst. A preparation method of the ruthenium catalyst comprises the following steps of: adding a carrier TiO2 into a water solution containing ruthenium salt or a water solution containing ruthenium salt and metal auxiliary salt such that the weight ratio of ruthenium to carrier is 0.005-0.15:1; and then, adding 2-10 wt% of potassium borohydride or hydrazine hydrate solution to precipitate the solution. A nonionic surfactant is optimally added in the preparation method to improve the catalytic activity and selectivity. If the catalyst is subject to hydro-thermal treatment in a water solution of sodium sulfate, then the adsorption property of the catalyst can be changed, and the selectivity of catalyzing furfural to synthesize tetrahydrofurfuryl alcohol through one-step hydrogenation can be greatly improved. The catalyst has simple preparation method, good catalytic activity and high selectivity and is especially applicable to catalyzing the reaction of furfural to synthesize tetrahydrofurfuryl alcohol through one-step hydrogenation under the conditions of low temperature, low pressure and no solvent. Under certain reaction conditions, the yield of tetrahydrofurfuryl alcohol can reach more than 99%.
Description
Technical field
The present invention relates to a kind of ruthenium catalyst, its preparation method and the application in the tetrahydrobiopterin synthesis furfuryl alcohol thereof.
Background technology
Tetrahydrofurfuryl alcohol is a kind of important chemical material, and its purposes is wider, can be used to prepare lysine, oxolane, pyrans and pyridine etc., also can be used for preparing chemical substances such as herbicide, pesticide, antifreezing agent, plasticizer and decolorizer.At present industrial tetrahydrofurfuryl alcohol is mainly obtained by two step of furfural hydrogenation.Wherein the first step is the synthetic furfuryl alcohol of furfural hydrogenation, the main copper-based catalysts that uses is as the disclosed traditional copper chromium system of document US 2094975, CN1562477 and CN1978051 with as Chrome-free systems such as document CN1410161 and the disclosed copper zinc-aluminium of CN1256965 and copper magnesium; Its furfuryl alcohol yield can both reach more than 99%.In second step, furfuryl alcohol is hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol on Raney nickel, as is found in the report of CN1847234 and CN1830551.Yet two step hydrogenation method energy consumptions are big, seriously polluted; Especially copper and chromium all are easy to cause water resource pollution.
For shortening preparation technology, can obtain tetrahydrofurfuryl alcohol at traditional catalyst previous step hydrogenation such as nickel, cobalt, rutheniums by furfural.Yet in this course of reaction, if reaction temperature is low, hydrogenation activity is lower, just requires very high hydrogenation pressure; And the rising reaction temperature, furfural is coking in the catalyst surface polymerization easily again, and side reaction easily takes place simultaneously, generates 1,2-pentanediol or 1, open-loop products such as 5-pentanediol.Therefore, in order to obtain higher tetrahydrofurfuryl alcohol yield, one step of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is all adding under a large amount of pure equal solvent conditions usually, sacrifices the production capacity of hydrogenation reactor and uses condition of high voltage to carry out hydrogenation.As patent GB627293 report, use cobalt-alumina catalyst, make mixed solvent with 1: 1 furfural and tetrahydrofurfuryl alcohol, under 50 ℃ and 250 atmospheric condition of high voltage, the tetrahydrofurfuryl alcohol of acquisition more than 99%.
Thereby the ruthenium catalyst that the invention provides one step of a kind of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol with and preparation method thereof, this catalyst can be under low-temp low-pressure and solvent-free condition one step of catalysis furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol.
Summary of the invention
The present invention at first provides a kind of ruthenium catalyst of one step of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol, and its expression formula is Ru-M/TiO
2, wherein Ru accounts for the 0.5-15% of total catalyst weight; M is one or more among metal promoter Fe, Co, Ni, Mn, Cu, Zn and the Al, and it accounts for the 0-20% of total catalyst weight.
Preferably, metal promoter M accounts for the 1-10% of total catalyst weight.The interpolation of a certain amount of metal promoter can be stablized and further be disperseed ruthenium catalyst, so make one step of ruthenium catalyst catalysis furfural during hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol feed stock conversion and selectivity of product all be improved to some extent.
The present invention also provides a kind of preparation method of aforesaid ruthenium catalyst, comprises the steps: steps A, adds carrier TiO in the aqueous solution that contains ruthenium salt or in the aqueous solution that contains ruthenium salt and metal promoter salt
2, the weight ratio that makes ruthenium and carrier is 0.005-0.15: 1; With step B, the potassium borohydride or the hydrazine hydrate solution that add concentration in the above-mentioned mixed liquor and be 2-10wt% make its precipitation, and washing precipitation is to neutral.
In ruthenium catalyst preparation method of the present invention, adding carrier TiO among the preferred steps A
2Also add non-ionic surface active agent in the aqueous solution before, it accounts for total solution weight is 0.5-2wt%, and preferred described non-ionic surface active agent is to be selected from NPE, polyvinylpyrrolidone and the sorbitan ester one or more.During Preparation of Catalyst, under the effect of non-ionic surface active agent micella, obtain component than homogeneous, the less precipitation of active component particle diameter, improve the decentralization of active component on carrier, and then improve catalyst activity and selective.
In a ruthenium catalyst preparation method's of the present invention specific embodiments, also be included in the step C behind the step B, namely add aqueous sodium persulfate solution in the precipitation and make solvent, and in hydrogen hydrothermal treatment step B gained precipitation.In this scheme, aqueous sodium persulfate solution concentration is 1～30wt% among the preferred steps C; The hydrothermal treatment consists temperature is 100～150 ℃, and Hydrogen Vapor Pressure is 0.3～5MPa, and the processing time is 0.5～10 hour.More preferably, aqueous sodium persulfate solution concentration is 10wt% among the step C; The hydrothermal treatment consists temperature is 120 ℃, and Hydrogen Vapor Pressure is 1MPa, and the precipitation process time is 3 hours.Under nitrogen atmosphere, can change the catalyst absorption property through the aqueous sodium persulfate solution processing, reduce the active sites quantity that may cause side reactions such as hydrogenolysis on the catalyst, thereby significantly improve the selective of one step of catalyst furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol.
In preparation method of the present invention, preferred described ruthenium salt is ruthenium trichloride, nitrate or chloride that described metal promoter salt is Fe, Co, Ni, Mn, Cu, Zn or Al.
The application of ruthenium catalyst in one step of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol that the present invention also provides a kind of above-mentioned ruthenium catalyst or prepares as above-mentioned preparation method.According to this Application of Catalyst, preferably, the temperature of hydrogenation reaction is that 50-110 ℃, pressure are 0.5-3MPa, and is reflected at not have under the condition of adding solvent and carries out.
The ruthenium catalyst that uses the inventive method to prepare is applied to one step of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol, can obtain the high selectivity of high conversion and the product of raw material under low temperature, low pressure and solvent-free condition.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described in further detail; but it only is preferred embodiment of the present invention; protection scope of the present invention is not limited thereto; any those skilled in the art can be easy to the change of carrying out or change be encompassed within protection scope of the present invention in technical scope disclosed by the invention.
In the following example and Comparative Examples, conversion ratio reaches and optionally is defined as follows; And its analytical instrument is the Agilent7890 gas chromatograph.The furfural (mol) * 100% that the furfural of conversion ratio=reaction consumes (mol)/reaction drops into; Selectively=furfural (mol) * 100% of tetrahydrofurfuryl alcohol (mol)/reaction consumes that reaction generates.
Embodiment 1
Preparation of catalysts: with 1.5g FeCl
3.6H
2O, 0.75g ruthenium metal concentration are 10% RuCl
3The aqueous solution and 50ml distilled water add in the there-necked flask, and mechanical agitation 30min fully dissolves.Add non-ionic surface active agent NPE 0.5g again, stir adding 2.1g titania support after 5 minutes, and stir 1h.Take by weighing 0.8g KBH
4Be made into the 30ml aqueous solution.Under stirring condition, begin to drip KBH
4The aqueous solution, control dropwises in 10-15min and continues to stir 0.5h.Above-mentioned solution centrifugal is separated, extremely neutral with the distilled water washing precipitation.In 100ml concentration was 10% aqueous sodium persulfate solution, activation was 3 hours under 120 ℃ and 1MPa Hydrogen Vapor Pressure with above-mentioned sediment.Centrifugation and with after the ethanol washing 3 times obtains the target catalyst in the present embodiment.
One step of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol: the above-mentioned catalyst for preparing is added in the 500ml reactor together with the 300ml furfural, nitrogen replacement 5 times, be warming up to target temperature, begin to charge into hydrogen and pick up counting, hydrogenation reaction is carried out under the condition of the mixing speed of 1MPa, 600rpm and 80 ℃, and hydrogenation is lower than 0.5% or stop reaction when stopping to inhale hydrogen substantially until furfural content.Reaction result is as shown in table 1.
Comparative Examples 1
Do not prepare catalyst, and directly use the 3g ruthenium content of market purchase to be the Ru/Al of 5wt%
2O
3As one step of catalyst furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Comparative Examples 2
Do not prepare catalyst, and the 5g Raney's nickel that directly uses market to buy goes on foot hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol as catalyst furfural one.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 2
Preparation of catalysts is substantially the same manner as Example 1, but does not use surfactant.Namely compare with embodiment 1 and lack " adding non-ionic surface active agent NPE 0.5g again " this step.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 3
Preparation of catalysts is substantially the same manner as Example 1, but does not use any metal promoter, simultaneously with 10%RuCl
3The consumption of the aqueous solution changes 0.30g into.Also namely " 1.5g FeCl among the embodiment 1
3.6H
2O, 0.75g ruthenium metal concentration are 10% RuCl
3The aqueous solution " " 0.30g ruthenium metal concentration is 10% RuCl to change use into
3The aqueous solution ".One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 4
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change use " 0.5gFeCl into
3.6H
2O ".One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 5
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change use " 2.0gFeCl into
3.6H
2O ".One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 6
Preparation of catalysts is substantially the same manner as Example 1, but does not carry out " with above-mentioned sediment in 100ml concentration is 10% aqueous sodium persulfate solution, activation is 3 hours under 120 ℃ and 1MPa Hydrogen Vapor Pressure " this step.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 7
Preparation of catalysts is substantially the same manner as Example 1, but " with above-mentioned sediment in 100ml concentration is 10% aqueous sodium persulfate solution; activation is 3 hours under 120 ℃ and 1MPa Hydrogen Vapor Pressure " among the embodiment 1 changed into " with above-mentioned sediment in the 100ml deionized water, activation is 3 hours under 120 ℃ and 1MPa Hydrogen Vapor Pressure ".One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 8
Preparation of catalysts is substantially the same manner as Example 1, but " NPE 0.5g " among the embodiment 1 changed into " polyvinylpyrrolidone 0.5g ".One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 9
Preparation of catalysts is substantially the same manner as Example 1, but " NPE 0.5g " among the embodiment 1 changed into " sorbester p17 is 0.5g ".One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 10
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change " 1.5g ferric nitrate " into, and " taking by weighing 0.8g KBH
4Be made into the 30ml aqueous solution " change " use 4g 50% hydrazine hydrate be made into the 30ml aqueous solution " into.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 11
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change " 1.0g cobalt chloride " into.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 12
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change " 1.0g nickel chloride " into.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 13
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change " 1.0g zinc chloride " into.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 14
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change " 1.0g aluminium chloride " into.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 15
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change " 1.0g copper nitrate " into.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 16
Preparation of catalysts is substantially the same manner as Example 1, but " 1.5g FeCl among the embodiment 1
3.6H
2O " change " 1.0g manganese nitrate " into.One step of the furfural process of hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol is identical with embodiment 1.Reaction result is as shown in table 1.
Table 1
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectively (%) |
| Embodiment 1 | 3.1 | ＞99.9 | 99.2 |
| Comparative Examples 1 | 6.7 | 95.4 | 92.3 |
| Comparative Examples 2 | 9.2 | 92.1 | 78.4 |
| Embodiment 2 | 4.5 | 98.0 | 99.0 |
| Embodiment 3 | 8.2 | 98.5 | 87.5 |
| Embodiment 4 | 4.5 | 97.3 | 87.1 |
| Embodiment 5 | 3.4 | 98.9 | 97.8 |
| Embodiment 6 | 3.7 | 98.5 | 85.0 |
| Embodiment 7 | 2.5 | 99.2 | 84.5 |
| Embodiment 8 | 3.8 | 99.1 | 99.5 |
| Embodiment 9 | 2.8 | 99.4 | 99.0 |
| Embodiment 10 | 5.1 | 99.2 | 97.0 |
| Embodiment 11 | 3.0 | 99.1 | 98.4 |
| Embodiment 12 | 4.6 | 99.1 | 95.7 |
| Embodiment 13 | 3.8 | 99.5 | 92.3 |
| Embodiment 14 | 2.7 | 99.2 | 97.8 |
| Embodiment 15 | 5.4 | 99.4 | 98.9 |
| Embodiment 16 | 4.3 | 99.3 | 98.8 |
By table 1 as seen, under preferred embodiment of the present invention, furfural one step hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol can be when feed stock conversion be very high selectivity of product fine, thereby the tetrahydrofurfuryl alcohol yield can be greater than 99%.
Claims (10)
1. the preparation method of the ruthenium catalyst of one step of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol, the expression formula of described ruthenium catalyst is Ru-M/TiO
2, wherein Ru accounts for the 0.5-15% of total catalyst weight; M is one or more among metal promoter Fe, Co, Ni, Mn, Cu, Zn and the Al, and it accounts for the 0-20% of total catalyst weight, and the content of M is non-vanishing; Described preparation method comprises the steps: steps A, in the aqueous solution that contains ruthenium salt and metal promoter salt, adds non-ionic surface active agent earlier, and making it account for total solution weight is 0.5-2wt%; Add carrier TiO again
2, the weight ratio that makes ruthenium and carrier is 0.005-0.15:1; Step B, the potassium borohydride or the hydrazine hydrate solution that add concentration in the above-mentioned mixed liquor and be 2-10wt% make its precipitation, and washing precipitation is to neutral.
2. preparation method according to claim 1 is characterized in that, metal promoter M accounts for the 1-10% of total catalyst weight.
3. preparation method according to claim 1 is characterized in that, described non-ionic surface active agent is to be selected from NPE, polyvinylpyrrolidone and the sorbitan ester one or more.
4. the preparation method of the ruthenium catalyst of one step of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol, the expression formula of described ruthenium catalyst is Ru-M/TiO
2, wherein Ru accounts for the 0.5-15% of total catalyst weight; M is one or more among metal promoter Fe, Co, Ni, Mn, Cu, Zn and the Al, and it accounts for the 0-20% of total catalyst weight, and the content of M is non-vanishing; Described preparation method comprises the steps: steps A, adds carrier TiO in the aqueous solution that contains ruthenium salt and metal promoter salt
2, the weight ratio that makes ruthenium and carrier is 0.005-0.15:1; Step B, the potassium borohydride or the hydrazine hydrate solution that add concentration in the above-mentioned mixed liquor and be 2-10wt% make its precipitation, and washing precipitation is to neutral; Step C adds aqueous sodium persulfate solution in the precipitation and makes solvent, and in hydrogen hydrothermal treatment step B gained precipitation.
5. preparation method according to claim 4 is characterized in that, metal promoter M accounts for the 1-10% of total catalyst weight.
6. preparation method according to claim 4 is characterized in that, is adding carrier TiO in the steps A
2Also add non-ionic surface active agent in the aqueous solution before, it accounts for total solution weight is 0.5-2wt%, and described non-ionic surface active agent is to be selected from NPE, polyvinylpyrrolidone and the sorbitan ester one or more.
7. according to any described preparation method in the claim 4 ~ 6, it is characterized in that aqueous sodium persulfate solution concentration is 1 ~ 30wt% among the described step C; The hydrothermal treatment consists temperature is 100 ~ 150 ℃, and Hydrogen Vapor Pressure is 0.3 ~ 5MPa, and the processing time is 0.5 ~ 10 hour.
8. preparation method according to claim 7 is characterized in that, aqueous sodium persulfate solution concentration is 10wt% among the described step C; The hydrothermal treatment consists temperature is 120 ℃, and Hydrogen Vapor Pressure is 1MPa, and the precipitation process time is 3 hours.
9. preparation method according to claim 4 is characterized in that, described ruthenium salt is ruthenium trichloride, nitrate or chloride that described metal promoter salt is Fe, Co, Ni, Mn, Cu, Zn or Al.
10. the application of ruthenium catalyst in one step of furfural hydrogenation tetrahydrobiopterin synthesis furfuryl alcohol for preparing as any described preparation method in the claim 4 ~ 9, wherein, the temperature of hydrogenation reaction is that 50-110 ℃, pressure are 0.5-3MPa, is reflected at not have under the condition of adding solvent to carry out.
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| US9045381B2 (en) | 2010-10-19 | 2015-06-02 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN102921415B (en) * | 2012-10-31 | 2015-03-11 | 江苏清泉化学股份有限公司 | Hydrogenation catalyst, preparation method of hydrogenation catalyst and application of hydrogenation catalyst to 2-methyltetrahydrofuran synthesis |
| IL234479A0 (en) | 2014-09-04 | 2014-12-02 | Yeda Res & Dev | Liquid-organic hydrogen carrier system based on catalytic peptide formation and hydrogenation using 2-aminoethanol and 2-(methylamino)ethanol |
| IL234478A0 (en) | 2014-09-04 | 2014-12-02 | Yeda Res & Dev | Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN105418551A (en) * | 2015-12-15 | 2016-03-23 | 林康艺 | Method for preparing furfuryl alcohol by catalyzing furfural |
| CN106083529B (en) * | 2016-06-03 | 2018-09-25 | 江苏清泉化学股份有限公司 | A kind of preparation method and bisphenol-A catalyst for hydrogenation of hydrogenated bisphenol A |
| CN106622219B (en) * | 2016-10-28 | 2019-11-08 | 南京工业大学 | A kind of catalyst, preparation method and the application of furfuryl alcohol liquid-phase hydrogenatin tetrahydrofurfuryl alcohol |
| CN109647388B (en) * | 2017-10-11 | 2021-08-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method thereof and preparation method of tetrahydrofurfuryl alcohol |
| CN109796427A (en) * | 2017-11-17 | 2019-05-24 | 华东师范大学 | A kind of preparation method of tetrahydrofurfuryl alcohol |
| CN108607598A (en) * | 2018-06-12 | 2018-10-02 | 中科合成油技术有限公司 | A kind of Pd bases catalyst and the preparation method and application thereof |
| CN109603852B (en) * | 2019-01-23 | 2020-06-12 | 云南大学 | Preparation method of ruthenium-cobalt magnetic catalyst and application of ruthenium-cobalt magnetic catalyst in selective hydrogenation |
| CN110193370A (en) * | 2019-04-23 | 2019-09-03 | 江西理工大学 | The bimetallic catalyst and preparation method, application of furfural selective hydrogenation furfuryl alcohol |
| CN114192165A (en) * | 2021-12-28 | 2022-03-18 | 浙江微通催化新材料有限公司 | Ruthenium-based catalyst and preparation method and application thereof |
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