CN102603681A - Method for preparing furfuryl alcohol through furfural liquid-phase catalytic hydrogenation - Google Patents
Method for preparing furfuryl alcohol through furfural liquid-phase catalytic hydrogenation Download PDFInfo
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Abstract
The invention discloses a method for preparing furfuryl alcohol through furfural liquid-phase catalytic hydrogenation, wherein Cr-free skeletal copper serves as a catalyst; right amount of Cr-free VIB or VIII group transition metal is contained in precursor copper aluminium alloy of the catalyst and used for increasing the activity and the selectivity of the skeletal copper catalyst; and the skeletal copper catalyst can be obtained through extracting and activating the copper aluminium alloy by utilizing an aqueous solution of caustic alkali or inorganic acid. According to the invention, right amount of skeletal copper catalyst and alkaline inorganic matter are added in a furfural liquid-phase hydrogenation system to serve as auxiliaries and the reaction is carried out at lower temperature and hydrogen pressure, therefore, excessive hydrogenation products i.e. 2- methyl furan and tetrahydrofurfuryl alcohol can be avoided from generating and the selectivity of the product furfuryl alcohol is increased. The method disclosed by the invention has the advantages of no chrome in the catalyst, low reaction and light-off temperatures, simpleness in process, high furfuryl alcohol yield and selectivity and capability of continuous indiscriminate application of the catalyst.
Description
Technical field:
The present invention relates to the method that a kind of Catalytical Hydrogenation of Furfural in Liquid Phase prepares furfuryl alcohol, especially adopt the skeletal copper catalyst that does not contain chromium to carry out Catalytical Hydrogenation of Furfural in Liquid Phase and prepare furfuryl alcohol.
Background technology:
Furfuryl alcohol is important Organic Chemicals, is used to produce furan type resin, furfuryl alcohol-urea-formaldehyde resin and the resol etc. of better performances; Also can produce fine chemical products such as medicine, agricultural chemicals, coating; Furfuryl alcohol is again the good solvent and the rocket fuel of varnish, pigment etc.In addition, furfuryl alcohol also is widely used in synthon, rubber and foundary industry.Furfuryl alcohol is generally prepared by furfural shortening method.
Furfural shortening system furfuryl alcohol has vapor phase process and two kinds of methods of liquid phase method usually.Gas phase hydrogenation generally is below 170 ℃, carries out under normal pressure or lower pressure (non-negative pressure) condition, adopts continuous flow reactor of fixed bed.Liquid-phase hydrogenatin generally is under 180-210 ℃, middle pressure (5-8MPa) or high pressure (more than the 10MPa), to carry out.
The catalyzer of hydrogenation of furfural system furfuryl alcohol is main with Cu-series catalyst mainly, adds various auxiliary agents and adopts different preparation to improve the performance of catalyzer, and also having with other metals such as nickel, cobalts is master's catalyzer.Since this century, because both at home and abroad to the environmental problem pay attention to day by day, therefore developing free of contamination chromium-free catalyst becomes main trend.
The vapor phase process hydrogenation catalyst of document and patent report can adopt coprecipitation method or immersion process for preparing, needs before using under certain temperature, to reduce earlier to handle, and having relatively high expectations to catalyst activity, selectivity and work-ing life.Liquid phase method adopts the copper chromium-based catalysts usually, generally exists hydrogenation activity low, and hydrogenation reaction needs higher temperature and hydrogen pressure, and the energy consumption problem of higher is like the CuO-Cr of German patent DE 3425758 reports
2O
3And Cu/SiO
2The liquid-phase hydrogenatin of two portions catalyst mix catalysis furfural, temperature of reaction 150-300 ℃, reaction pressure 2-10MPa, catalyzer is divided into two portions, has increased the difficulty of preparation process.Chinese patent ZL01141837.0 and ZL02140489.5 have reported the Cu-Cr catalyzer that adds group VIII metallic nickel or precious metals pt respectively, adopt the coprecipitation method preparation, and furfural liquid-phase hydrogenatin condition is 180-200 ℃ and 3.5-5.0MPa hydrogen pressure.Also there are patent report skeleton nickel or skeletal Co catalysts to be used for hydrogenation of furfural and prepare furfuryl alcohol, but, need carry out modification and handle in order to improve selectivity of catalyst.Reported with ammonium molybdate like U.S. Pat 4153578 and to have flooded modified skeletal nickel catalyst, reaction conditions is relatively gentleer, and the furfuryl alcohol yield is higher.Chinese patent ZL91103132.4 has reported the skeletal Co catalysts that the cobalt duraluminum extracting activation of adding chromium is obtained, and under the mitigation condition, has higher hydrogenation of furfural transformation efficiency.Chinese patent ZL97102713.7 has reported the skeletal nickel catalyst that adopts the modification of heteropolyacid salt dipping; Can improve activity of such catalysts and selectivity; The furfuryl alcohol selectivity is superior to the skeletal nickel catalyst of ammonium molybdate dipping modification, but adds ethanol in the reaction system as solvent.
Adopt the Cu-series catalyst of the precipitator method or immersion process for preparing; Generally must reduce processing under 200 ℃ the temperature in advance being higher than before using; The hydrogenation of furfural temperature of reaction then is lower than the reduction temperature of copper catalyst, and this will certainly cause puzzlement to processing unit Material Selection aspect.In addition, be difficult in the copper chromium-based catalysts use that furfural liquid-phase hydrogenatin is used always reclaim, have comparatively serious environmental pollution problem.
Summary of the invention:
The purpose of this invention is to provide the method that a kind of Catalytical Hydrogenation of Furfural in Liquid Phase prepares furfuryl alcohol, it is low to have a cost, and technology is simple, the characteristics that product furfuryl alcohol yield and selectivity are high.
The objective of the invention is to realize like this: adopt the skeleton copper that does not contain chromium as catalyzer; And contain the group vib or the group VIII transition metal that do not comprise chromium in right amount in the precursor xaloy of catalyzer; In order to improve the activity and the selectivity of skeletal copper catalyst, xaloy can obtain skeletal copper catalyst through caustic alkali or inorganic acid aqueous solution extracting activation.In furfural liquid-phase hydrogenatin system, add an amount of skeletal copper catalyst and alkaline inorganics as auxiliary agent, can under temperature of reaction that is starkly lower than the copper chromium-based catalysts and pressure, react, specifically realize according to the following steps:
(1) xaloy activation: the mass content of xaloy consists of group vib or the group VIII transition metal 0.1-10% beyond metallic aluminium 40-58%, metallic copper 40-50%, the dechromisation; Group vib transition metal beyond the dechromisation is meant molybdenum, tungsten; Group VIII transition metal is meant iron, cobalt or nickel; Choose one or more, preferred molybdenum or nickel.Go out the metallic aluminium in the xaloy with caustic-alkali aqueous solution or inorganic acid aqueous solution extracting, the preferred NaOH of caustic alkali, the preferred hydrochloric acid of mineral acid.If use the caustic-alkali aqueous solution extracting, the alkali consumption is 1-3 a times of copper-aluminium alloy powder weight, and preferred 1-2 times, it is mixed with mass concentration is 5.0%-40%, the alkali aqueous solution of preferred 10-25%, and extraction temperature is 40-100 ℃; If use the inorganic acid aqueous solution extracting, the mineral acid consumption is 1-4 a times of copper-aluminium alloy powder weight, and preferred 1.5-3.0 doubly; It is mixed with volumetric molar concentration is the 1-6 mol, the inorganic acid aqueous solution of preferred 2-4 mol, and extraction temperature is 30-80 ℃; Preferred 40-60 ℃; The extracting time is 0.5-3.0 hour, preferred 1-2 hour, promptly gets skeletal copper catalyst.
(2) washing of catalyzer and preservation: the skeletal copper catalyst after above-mentioned steps is handled uses 40-80 ℃ deoxygenation deionized water wash to be 7-9 to washing lotion pH; Preferred 7-8, and skeleton copper is kept in the NaOH solution of deionized water or absolute ethyl alcohol or 0.1mol/L.
(3) furfural liquid-phase hydrogenatin reaction: the technical grade furfural is handled through underpressure distillation and is removed oxidative condensation product wherein; Furfural, skeletal copper catalyst and auxiliary agent are added in the autoclave, are 90-160 ℃ in temperature, and preferred 120-140 ℃, hydrogen pressure are 1.0-8.0MPa; The condition of preferred 2.0-5.0MPa is carried out furfural liquid-phase hydrogenatin reaction; Wherein, the consumption of skeletal copper catalyst accounts for the 1-10% of furfural amount, preferred 2-8%; Auxiliary agent is selected from NaOH, KOH or Na
2CO
3Deng metal hydroxides or basic metal carbonate, preferred NaOH, the consumption of auxiliary agent accounts for the 0.05-0.40% of furfural amount, preferred 0.1-0.2%, above-mentioned consumption is mass percent.
The skeletal copper catalyst that the invention has the beneficial effects as follows the catalysis furfural liquid-phase hydrogenatin that is proposed does not contain chromium, and can apply mechanically continuously, can reduce environmental pollution; In addition; Skeletal copper catalyst has the good low-temperature hydrogenation activity; Can realize that furfural transforms basically fully being starkly lower than under the hydrogenation reaction temperature and pressure of Cu-Cr catalyst, thereby can cut down the consumption of energy, and avoid the generation of excessive hydrogenation product 2-methyl furan and tetrahydrofurfuryl alcohol; With the selectivity of raising product furfuryl alcohol, thus the energy consumption of reduction product fractionation by distillation.
Embodiment:
Further specify the present invention through embodiment below, but invention is not limited.
Embodiment 1: sieve 200 order copper-aluminium alloy powders, 15 grams; Nickeliferous 5.5% (quality %) in the alloy; 25 gram NaOH are dissolved in wiring solution-forming in 100 ml deionized water, under the whipped state copper-aluminium alloy powder are slowly joined in the NaOH solution, be warmed up to 70 ℃ of activation 1 hour then.Use 500 milliliters 60 ℃ deionized water wash to pH be 7, replace deionized water with absolute ethyl alcohol again.Whole skeletal copper catalysts that above-mentioned activation is good and 200 milliliters of furfurals add in the autoclave simultaneously, add NaOH 0.4 gram again.Control still interior reaction temperature is that 130-140 ℃, hydrogen pressure are 3.0MPa, and the furfural transformation efficiency is 99.5%, furfuryl alcohol selectivity 97.6%.
Embodiment 2: sieve 200 order copper-aluminium alloy powders 15 gram, contain molybdenum 2.0% (quality %) in the alloy, under the whipped state copper-aluminium alloy powder is slowly joined in 250 milliliters the hydrochloric acid soln of 2.5 mol, be warmed up to 40 ℃ of activation 1 hour then.Use 500 milliliters 60 ℃ deionized water wash to pH be 7, replace deionized water with absolute ethyl alcohol again.Whole skeletal copper catalysts that above-mentioned activation is good and 200 milliliters of furfurals add in the autoclave simultaneously, add NaOH 0.4 gram again.Control still interior reaction temperature is that 130-140 ℃, hydrogen pressure are 3.0MPa, and the furfural transformation efficiency is 99.4%, furfuryl alcohol selectivity 97.3%.
Embodiment 3: sieve 200 order copper-aluminium alloy powders, 20 grams; Iron content 3.5% (quality %) in the alloy; 30 gram NaOH are dissolved in wiring solution-forming in 125 ml deionized water, while stirring copper-aluminium alloy powder are slowly joined in the NaOH solution, be warmed up to 60 ℃ of activation 1.5 hours then.Use 500 milliliters 50 ℃ deionized water wash to pH be 8, replace deionized water with absolute ethyl alcohol again.Whole skeletal copper catalysts that above-mentioned activation is good and 200 milliliters of furfurals add in the autoclave simultaneously, add KOH 0.2 gram again.Control still interior reaction temperature is that 120-130 ℃, hydrogen pressure are 4.0MPa, and the furfural transformation efficiency is 99.8%, furfuryl alcohol selectivity 96.8%.
Embodiment 4: sieve 200 order copper-aluminium alloy powders, 16 grams; Contain cobalt 4.0% (quality %) in the alloy; 26 gram NaOH are dissolved in wiring solution-forming in 110 ml deionized water, under stirring copper-aluminium alloy powder are slowly joined in the NaOH solution, be warmed up to 80 ℃ of activation 1 hour then.Use 500 milliliters 60 ℃ deionized water wash to pH be 7, replace deionized water with absolute ethyl alcohol again.Whole skeletal copper catalysts that above-mentioned activation is good and 200 milliliters of furfurals add in the autoclave simultaneously, add Na again
2CO
30.4 gram.Control still interior reaction temperature is that 130-140 ℃, hydrogen pressure are 4.0MPa, and the furfural transformation efficiency is 99.6%, furfuryl alcohol selectivity 96.3%.
Embodiment 5: reacted catalyzer among the embodiment 1 is reclaimed through spinning; Through absolute ethanol washing, and replenish, repeat the hydrogenation of furfural process among the embodiment 1 according to the fresh skeletal copper catalyst 1g of embodiment 1 method activatory; The furfural transformation efficiency is 99.3%, furfuryl alcohol selectivity 96.9%.
The contrast experiment: adopting coprecipitation method to prepare the CuO mass content is 55% Cu-Cr
2O
3-Al
2O
3Catalyzer 15g, before using earlier 300 ℃ of hydrogen reducings 8 hours.Whole Cu-Cr catalysts and furfural that reduction is good add in the autoclave for 200 milliliters simultaneously, and control hydrogenation reaction temperature is 170-180 ℃, and hydrogen pressure 5.0MPa, furfural transformation efficiency are 99.2%, furfuryl alcohol selectivity 92.6%.
Visible by above embodiment, skeletal copper catalyst of the present invention has greater activity and selectivity, and under relatively low reaction pressure and temperature of reaction, furfural also can transform fully, and obtains higher furfuryl alcohol productive rate and selectivity.Catalyzer can be applied mechanically continuously, replenishes a small amount of live catalyst and can reach similar hydrogenation performance.
Claims (8)
1. a Catalytical Hydrogenation of Furfural in Liquid Phase prepares the method for furfuryl alcohol; It is characterized in that: adopt skeleton copper as catalyzer; And contain group vib transition metal or group VIII transition metal beyond the dechromisation in the precursor xaloy of catalyzer, specifically realize according to the following steps:
(1) xaloy activation: the mass content of xaloy consists of metallic aluminium 40-58%, metallic copper 40-50%, the group vib that does not comprise chromium or group VIII transition metal 0.1-10%, promptly gets skeletal copper catalyst after going out the metallic aluminium in the xaloy with caustic-alkali aqueous solution or inorganic acid aqueous solution extracting; If use the caustic-alkali aqueous solution extracting, the alkali consumption is 1-3 a times of copper-aluminium alloy powder weight, and it is mixed with the alkali aqueous solution that mass concentration is 5.0%-40%, and extraction temperature is 40-100 ℃; If use the inorganic acid aqueous solution extracting, the mineral acid consumption is 1-4 a times of copper-aluminium alloy powder weight, and it is mixed with the inorganic acid aqueous solution that volumetric molar concentration is the 1-6 mol, and extraction temperature is 30-80 ℃, and the extracting time is 0.5-3 hour;
(2) washing of catalyzer and preservation: the skeletal copper catalyst after above-mentioned steps is handled uses 40-80 ℃ deoxygenation deionized water wash to be 7-9 to washing lotion pH, and skeleton copper is kept in the NaOH solution of deionized water or absolute ethyl alcohol or 0.1mol/L;
(3) furfural liquid-phase hydrogenatin reaction: the technical grade furfural is handled through underpressure distillation and is removed oxidative condensation product wherein; Furfural, skeletal copper catalyst and auxiliary agent are added in the autoclave; In temperature is that 90-160 ℃, hydrogen pressure are that the condition of 1.0-8.0MPa is carried out furfural liquid-phase hydrogenatin reaction, and wherein, the consumption of skeletal copper catalyst accounts for the 1-10% of furfural amount; The consumption of auxiliary agent accounts for the 0.05-0.40% of furfural amount, and above-mentioned consumption is mass percent.
2. the method for preparing furfuryl alcohol according to the described Catalytical Hydrogenation of Furfural in Liquid Phase of claim 1; Group vib beyond the dechromisation that it is characterized in that in the xaloy being contained or group VIII transition metal are one or more in molybdenum, tungsten, iron, cobalt and the nickel, preferred molybdenum or nickel.
3. the method for preparing furfuryl alcohol according to the described Catalytical Hydrogenation of Furfural in Liquid Phase of claim 1; It is characterized in that; The preferred NaOH of caustic alkali that is used for the extracting xaloy, consumption are preferably 1-2 times of copper-aluminium alloy powder quality, and the aqueous solution mass concentration that is made into is preferably 10-25%; Temperature is preferably 60-80 ℃, and the extracting time is preferably 1-2 hour.
4. the method for preparing furfuryl alcohol according to the described Catalytical Hydrogenation of Furfural in Liquid Phase of claim 1; It is characterized in that; The mineral acid that is used for the extracting xaloy is preferably hydrochloric acid, and consumption is preferably 1.5-3.0 times of copper-aluminium alloy powder quality, and the aqueous solution volumetric molar concentration that is made into is preferably the 2-4 mol; Temperature is preferably 40-60 ℃, and the extracting time is preferably 1-2 hour.
5. prepare the method for furfuryl alcohol according to the described Catalytical Hydrogenation of Furfural in Liquid Phase of claim 1, it is characterized in that, the skeletal copper catalyst that extracting obtains needs to be preferably 7-8 with 40-80 ℃ of deoxygenation deionized water wash to washing lotion pH value.
6. prepare the method for furfuryl alcohol according to the described Catalytical Hydrogenation of Furfural in Liquid Phase of claim 1, it is characterized in that, the preferred mass per-cent consumption of skeletal copper catalyst is the 2-8% of furfural amount.
7. prepare the method for furfuryl alcohol according to the described Catalytical Hydrogenation of Furfural in Liquid Phase of claim 1, it is characterized in that auxiliary agent is selected from NaOH, KOH or Na
2CO
3, its preferred mass per-cent consumption is the 0.1-0.2% of furfural amount,
8. prepare the method for furfuryl alcohol according to the described Catalytical Hydrogenation of Furfural in Liquid Phase of claim 1, it is characterized in that, the preferred 120-140 of hydrogenation reaction temperature ℃, the preferred 2.0-5.0MPa of hydrogen pressure.
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| CN105348234A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for converting furfural into furfuryl alcohol by catalysis |
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| CN116459836A (en) * | 2023-03-17 | 2023-07-21 | 大连理工大学 | Preparation of Ni-Cu-B catalyst and application thereof in selective hydrogenation of furfural |
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