GB2598654A - A catalyst for furfural selective hydrogenation - Google Patents

A catalyst for furfural selective hydrogenation Download PDF

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GB2598654A
GB2598654A GB2105536.3A GB202105536A GB2598654A GB 2598654 A GB2598654 A GB 2598654A GB 202105536 A GB202105536 A GB 202105536A GB 2598654 A GB2598654 A GB 2598654A
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catalyst
selective hydrogenation
dicarboxylic acid
oxygen
mixed solvent
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Chen Hua
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Hangzhou Jingshu New Mat Co Ltd
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Hangzhou Jingshu New Mat Co Ltd
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Abstract

Preparation of a catalyst for selective hydrogenation of biomass, comprising: S1: 9-(3,5-dicarboxylic acid-benzyl)-9H-carbazole-3,6-dicarboxylic acid (H4DCDC) is dissolved in a mixed solvent of DMA/EtOH/H2O to obtain a solution; S2: cupric nitrate is dissolved in the mixed solvent and then the solution obtained in S1 is added slowly, after ultrasonication for 5-10mins the temperature is raised to 120-160ºC, reacted for 24-48h and then cooled to room temperature; S3: solids are filtered and washed with ethanol, and naturally dried for 12-20h at room temperature to obtain a Cu-MOF. An additional step, S4, can also be performed, wherein the solid obtained in S3 is calcined under an oxygen atmosphere, such as an oxygen-nitrogen mixture with an oxygen content of 0.5-20% and flow velocity of 80-120mL/min, to obtain the catalyst. Preferably the molar ratio of the H4DCDC and cupric nitrate is 1-2:1.5-2 and volume ratio of the mixed solvent of DMA/EtOH/H2O is 1:1:1. The calcination heating rate may be 2-10ºC/min up to 100-350ºC, where this temperature is maintained for 1-3h. When used in furfural selective hydrogenation reactions, preferably for the preparation of furfuryl alcohol or tetrahydrofurfuryl alcohol, the catalyst can have a particle size of 8-30microns and provide a high conversion rate and high selectivity.

Description

A CATALYST FOR FURFURAL SELECTIVE HYDROGENATION
TECHNICAL FIELD
[0001] The present invention relates to the technical field of catalyst, in particular to a catalyst for furfural selective hydrogenation.
BACKGROUND OF THE INVENTION
[0002] Catalytic hydrogenation is important reactions in pharmacy, fine chemical engineering and energy conversion, for industrial engineering, the catalytic hydrogenation is usually applying hydrogenides with specific stoichiometric ratios, like lithium aluminium hydride, sodiumborohydride, borane -morpholine and etc., and reactive hydrogen species produced by decomposition of hydrides are applied to hydrogenate reactants; although a hydrogenation activity of the hydrogenides is relative high, when there are multiple functional groups in the substrate molecule, this non-selective hydrogenation causes the reaction to produce many byproducts, which will cause the waste of chemical resources and energy; moreover, some inorganic salt ions are produced in decomposition of the hydrogenides, and filtering and cleaning of waste inorganic salt ions will pollute environment; another commercial hydrogenation catalyst like platinum carbon, palladium on carbon and rhodium carbon will reduce a cost of filtering catalyst to some extent, however, when a multiple of reducible groups exists in the reactant at the same time, to obtain a production with a high selectivity is pretty difficult.
[0003] In recent years, due to the massive use of fossil energy has brought various problems to human daily life, various natural disasters occur frequently, environmental pollution problems are becoming more and more serious, and traditional fossil energy can no longer meet the growing needs of human beings. Therefore, the development of new energy sources to replace the traditional fossil energy has become a hot topic of research in various countries. At present, the widely used renewable energy sources mainly include wind energy, solar energy, tidal energy, geothermal energy, etc. However, these energy sources have their own limitations and there are still great problems in the sustainable development and utilization. With the development of science and technology to develop and utilize biomass to produce biomass oil and fine chemicals, it can effectively reduce the dependence on traditional fossil energy.
[0004] The hydrodeoxygenation of biomass aldehydes to produce high density biomass oil and liquid fuels is very promising, and it is very difficult to reduce the hydrogen consumption and carbon loss by only reducing the aldehyde group without affecting other structures in this reaction. However, their expensive price limits their widespread use, and the noble metals tend to lead to some by-products from excessive hydrogenation. In general, non-precious metal catalysts cannot achieve the desired catalytic effect, and the catalyst fabrication is often accompanied by a complex modification process.
BRIEF SUMMARY OF THE INVENTION
[0005] The present invention provide a catalyst for selective hydrogenation of biomass so as to overcome the existing technical problems.
[0006] Another purpose of the present invention is providing an application of the above-stated catalyst in a furfural selective hydrogenation reaction.
[0007] To achieve the objectives, the embodiments of the present invention adopt the following technical solutions: [0008] A catalyst for selective hydrogenation of biomass, wherein the catalyst is prepared by the following methods: [0009] 51: 9-(3,5-dicarboxylic acid-benzyI)-9H-indazole3,6-dicarboxylic acid (H4DCDC) s dissolved in a mixed solvent of DIVIA/Et0H/H20, thereby a solvent is obtained to be used [0010] 52: Cupric nitrate is dissolved in the mixed solvent of DIVIA/Et0H/H20, and then the solvent obtained in Si is added slowly, after ultrasonic processing for 5-10 min, the temperature is raised to 120-160t to be reacted for 24-48h, and then cooled to room temperature.
[0011] 53: solids are filtered and washed with ethanol, and then being naturally dried for 12- 20h at the room temperature, and then Cu-MOF are obtained.
[0012] Or after the 53, the preparation methods further comprises a 54, specifically as follows: [0013] 51: 9-(3,5-dicarboxylic acid-benzyI)-9H-indazole3,6-dicarboxylic acid (H4DCDC) is dissolved in a mixed solvent of DMA/Et0H/H20, thereby a solvent is obtained to be used.
[0014] 52: Cupric nitrate is dissolved in the mixed solvent of DIVIA/Et0H/H20, and then the solvent obtained in Si is added slowly, after ultrasonic processing for 5-10 mm, the temperature is raised to 120-160°C to be reacted for 24-48h, and then cooled to room temperature.
[0015] S3 solids are filtered and washed with ethanol, and then being naturally dried for 1220h at the room temperature, and then Cu-MOF are obtained.
[0016] 54:the solid obtained in S3 is calcined under an oxygen atmosphere, thereby the catalyst is obtained.
[0017] Preferably, a molar ratio of the 9-(3,5-dicarboxylic acid-benzyI)-9H-indazole3,6-dicarboxylic acid (H4DCDC) and the cupric nitrate is 1-2:1.5-2.
[0018] Preferably, a volume ratio of the mixed solvent of DMAJEt0H/H20 is 1:1:1.
[0019] Preferably, the atmosphere containing oxygen in S4 is one of oxygen-nitrogen mixture, oxygen-argon mixture and oxygen-helium mixture; more preferably, the atmosphere containing oxygen in S4 is the oxygen-nitrogen mixture [0020] Preferably, an oxygen content in the atmosphere in S4 is 0.5%-20% and a flow velocity is 80-120mL/min.
[0021] Preferably, a heating rate in calcining of S4 is heating to 100-350°C under temperature of 2--10°C/min,and then maintain at the temperature for 1-3h.
[0022] Particle size of the catalyst prepared in terms of the above-stated methods is 8-30micron when in a furfural selective hydrogenation reaction [0023] The catalyst is used in the furfural selective hydrogenation reaction, especially in preparing furfuryl alcohol or tetrahydrofurfuryl alcohol in the furfural selective hydrogenation reaction.
[0024] Compared with the existing arts, the benefits of the invention are as follows: (1) compared with traditional Cu-catalyst, the present catalyst has a high catalytic hydrogenation activity, Cu-ions active species have obvious activation function to C-0 bonding, which overcomes a poor activity of the traditional Cu-catalyst in catalyze C-0 bonding; (2) the catalyst disclosed in the present invention is metal-organic framework Cu-catalyst, by coating with carbon, agglomeration and a leaching of the active component is effectively suppressed under a reaction condition of Cu-catalyst, which also maintains a highly-dispersing of Cu-component; (3) by controlling oxygen content in heat processing, the catalyst disclosed in the present invention is able to directionally adjust and control a content of Cu20, thereby the product of the furfural selective hydrogenation reaction is selectively to be tetrahydrofurfuryl alcohol or furfuryl alcohol, thereby different processes are made to catalyst to meet production requirements in terms of the practical demands; (4) when preparing the tetrahydrofurfuryl alcohol or the furfuryl alcohol with the furfural selective hydrogenation reaction, the catalyst provided by the present invention has a high conversion rate and high selectivity under a relative moderate condition; moreover, the catalyst is simple in preparing, convenient in operation, low in equipment requirement and cost, which has a bright prospect
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 s a PXRD diagram of catalyst prepared in embodiment 1 of the present invention
DETAILED DESCRIPTION OF THE INVENTION
[0026] Detailed descriptions of the present invention are further described below with reference to the embodiments and figures, however, the embodiments of the present invention are not limited to this.
100271 All reagents applied in the owin embodiments are commercially available without otherwise specified [0028] A preparation method of the 9-(3,5-dicarboxylic acid-benzy1)-9H-indazole3,6-dicarboxylic acid (H4DCDC) is listed as follows: [0029] Under an inert atmosphere, 16.7g of carbazole are dissolved in dichloromethane, and then cooling down to 0 °C to add 1.3g of aluminum chloride, after stirring for 15 min, 18.0g of acetyl chloride is added under 0 °C, after reacting for 1 hour at 0 °C, the reaction was then warmed to room temperature and reacted for 2 hours, after the reaction finishes, water is added to quench the acetyl chloride, and then 24.6g of 3,6-diacetyl carbazole is obtained to be used through purifying by column chromatography.
[0030] 24.6g of 3,6-diacetyl carbazole is dissolved in acetone, and then 4g of sodium hydroxide and 13.8g of potassium carbonate are added to be stirred for 10 min, and then 31.5g of 5-bromomethy1-1,3-ethyl isophthalic acid is added, and the temperature is elevated to 60°C for allowing the reaction for 4 hours, and then 43.7g of (3,5-dicarboxylate-benzy1)-91-1-3,6-biacetyl carbazole is obtained by recrystallization [0031] 43.7g of (3,5-dicarboxylate-benzy1)-9H-3,6-biacetyl carbazole is dissolved in 1,4-Dioxane, and then 28.8g of bromine is added to be stirred for 15min, and then 7.2g of the sodium hydroxide is added, and then the temperature is elevated to 80°C to be reacted for 8hours, and after the reaction finishes, 34.7g of the 9-(3,5-dicarboxylic acid-benzy1)-9Hindazole3,6-dicarboxylic acid (H4DCDC) is obtained by reciystal I i zati on.
[0032] Embodiment 1 [0033] A catalyst for selective hydrogenation of biomass, wherein the catalyst is prepared by the following methods: [0034] Si: 4.3g of the 9-(3,5-dicarboxylic acid-benzy1)-9H-indazole3,6-dicarboxylic acid (H4DCDC) is dissolved in 5m1 mixed solvent of DIVIA/Et0H/H20, thereby the solvent is obtained to be used; [0035] 52. 1.9g of cupric nitrate is dissolved in the 5m1 mixed solvent of DMA/Et0H/H20, and then the solvent obtained in S1 is added slowly, after ultrasonic processing for 5 min, the temperature is raised to 120°C to be reacted for 48h, and then cooled to room temperature; [0036] 53: solids are filtered and washed with ethanol, and then being naturally dried for 12h at the room temperature, and then Cu-MOF with a particle size of 8 microns are obtained, and then a X-ray powder diffraction is characterized to the catalyst.
[0037] Wherein a volume ratio of the mixed solvent of DNIA/Et0H/H20 is 1:1:1.
[0038] Embodiment 2 [0039] The catalyst for selective hydrogenation of biomass, wherein the catalyst is prepared by the following methods: [0040] Sl: 6.5g of the 9-(3,5-dicarboxylic acid-benzy1)-9H-indazole3,6-dicarboxylic acid (H4DCDC) is dissolved in 5m1 the mixed solvent of DIVIA/Et0H/1-120, thereby a solvent is obtained to be used; [0041] S2: 2.2g of the cupric nitrate is dissolved in the 5m1 the mixed solvent of DMA/Et0H/H20, and then the solvent obtained in Si is added slowly, after ultrasonic processing for 7 mm, the temperature is raised to 140°C to be reacted for 36h, and then cooled to room temperature; [0042] S3 solids are filtered and washed with the ethanol, and then being naturally dried for 16h at the room temperature, and then the Cu-MOF with a particle size of 15 microns are obtained [0043] Wherein the volume ratio of the mixed solvent of DISTA/Et0H/1120 is 1:1:1; [0044] Embodiment 3 [0045] The catalyst for selective hydrogenation of biomass, wherein the catalyst is prepared by the following methods: [0046] Si: 8.6g of the 9-(3,5-dicarboxylic acid-benzy1)-9H-indazole3,6-dicarboxylic acid (H4DCDC) is dissolved in 10m1 the mixed solvent of DMA/Et0H/H20, thereby a solvent is obtained to be used; [0047] 52: 3.8g of cupric nitrate is dissolved in the 5m1 the mixed solvent of DMA/Et0H/FL0, and then the solvent obtained in SI is added slowly, after ultrasonic processing for 10 min, the temperature is raised to 160°C to be reacted for 24h, and then cooled to room temperature; [0048] S3: solids are filtered and washed with the ethanol, and then being naturally dried for 20h at the room temperature, and then the Cu-MOF with a particle size of 30 microns are obtained.
[0049] Embodiment 4 [0050] The catalyst for selective hydrogenation of biomass, wherein the catalyst is prepared by the following methods: [0051] Si: 4.3g of the 9-(3,5-dicarboxylic acid-benzy1)-9H4ndazole3,6-dicarboxylic acid (H4DCDC) is dissolved in the 5m1 mixed solvent of DMAJEt0H/H20, thereby a solvent is obtained to be used.
[0052] S2: 1.9g of the cupric nitrate is dissolved in the 5m1 mixed solvent of DMA/Et0H/F120, and then the solvent obtained in SI is added slowly, after ultrasonic processing for 5 mm, the temperature is raised to 120°C to be reacted for 48h, and then cooled to room temperature; [0053] S3: solids are filtered and washed with the ethanol, and then being naturally dried for 12h at the room temperature, and then the Cu-MOF is obtained; [0054] 54: the solid obtained in 83 is placed in oxygen-nitrogen mixture with an oxygen content of 0.5% and a flow velocity of 80mL/minfor being calcined after the temperature is heated to 100 °C at a heating rate of 2°C/min and maintained for 1-3 hours, thereby the catalyst with the particle size of 8 microns is obtained.
[0055] Wherein the volume ratio of the mixed solvent of DMA/Et0H/1120 is 1:1:1.
[0056] Embodiment 5 [0057] The catalyst for selective hydrogenation of biomass, wherein the catalyst is prepared by the following methods: [0058] S 1: 8.6g of the 9-(3,5-dicarb oxyl i c acid-benzy1)-9H4ndazole3,6-dicarboxylic acid (H4DCDC) is dissolved in the 10m1 mixed solvent of DMA/Et0H/H20, thereby a solvent is obtained to be used.
[0059] S2: 3.8g of the cupric nitrate is dissolved in the 5m1 mixed solvent of DMA/Et0H/H20, and then the solvent obtained in S1 is added slowly, after ultrasonic processing for 10 min, the temperature is raised to 160°C to be reacted for 24h, and then cooled to room temperature; [0060] 53: solids are filtered and washed with the ethanol, and then being naturally dried for 20h at the room temperature, and then the Cu-MOF is obtained; [0061] S4: the solid obtained in S3 is placed in oxygen-nitrogen mixture with an oxygen content of 20% and a flow velocity of 120mL/min,for being calcined after the temperature is heated to 350°C at a heating rate of 10°C/min and maintained for 3 hours, thereby the catalyst with the particle size of 30 microns is obtained.
[0062] Wherein the volume ratio of the mixed solvent of DMA/Et0H/1120 is 1:1:1.
[0063] Embodiment 6 [0064] A selective catalytic hydrogenation is performed to the catalysts prepared in embodiments 1-5, specifically, 50mg of catalyst and 100mg of 2-Furaldehyde are dissolved in 30mL isopropanol, and then reaction is performed in a high-temperature and high-pressure reaction kettle with a hydrogen pressure of 3MPa, wherein reaction systems of the catalysts added in the embodiments 1 and 2 are reacted for 4 hours at a temperature of 140°C while the reaction systems of the catalysts added in the embodiments 3,4 and 5 are reacted for 4 hours at a temperature of 180°C; the obtained product are analyzed by gas chromatography and the specific activity data are shown in Form I. [0065] Form 1 Reactivity Data of the catalysts prepared in embodiments 1-5 Conversion of furfurala/% Furfuryl alcohol 1% Tetrahydrofurfuryl alcohoU% Embodiment 1 100 90 2 Embodiment 2 100 93 5 Embodiment 3 100 8 85 Embodiment 4 100 3 88 Embodiment 5 100 2 90 [0066] From Form 1, the catalysts prepared in embodiments 1-5 are high in conversion of furfurala, and the furfuryl alcohol are completely conversed under the reaction; selectivity of the furfuryl alcohol in the catalysts prepared in embodiments 1-2 reach to 90% and 93% while content of the tetrahydrofurfuryl alcohol are merely 2% and 5%, as the catalysts 1 and 2 are not oxidized and content of Cu20 is relative low; meanwhile, as the catalysts prepared in embodiments 3,4 and 5 are oxidized, so the content of Cu20 increases and a hydrogenation activity of the catalysts enhanced, thereby the hydrogenation depth is deepen, and main product of the reaction is converted into the tetrahydrofurfuryl alcohol from the furfuryl alcohol, wherein the oxygen content of the embodiments 3,4 and 5 when in oxidization is gradually increased, correspondingly, the content of the Cu20 is also increased, thereby selectivity of the tetrahydrofurfuryl alcohol respectively ascend to 85%, 88% and 90%.
[0067] The above embodiments are preferred application modes of the present invention, but application modes of the present invention are not limited thereof, and any other changes modification, substitution, combination, simplification within the spirit and principle of the present invention should be regarded as an equivalent displacement of the present invention, and are included within the protection scope of the present invention.

Claims (8)

  1. CLAIMS1. A catalyst for selective hydrogenation of biomass, wherein the catalyst is prepared by the following methods: Si: 9-(3,5-dicarboxylic acid-benzyI)-9H-indazole3,6-dicarboxylic acid (H4DCDC) is dissolved in a mixed solvent of DMA/Et0H/H20, thereby a solvent is obtained to be used; 52: Cupric nitrate is dissolved in the mixed solvent of DNIA/Et0H/H20, and then the solvent obtained in St is added slowly, after ultrasonic processing for 5-10 min, the temperature is raised to 120-160°C to be reacted for 24-48h, and then cooled to room temperature; S3: solids are filtered and washed with ethanol, and then being naturally dried for 12-20h at the room temperature, and then Cu-MOF are obtained; or after the S3, the preparation methods further comprises a S4, specifically as follows: Si: 9-(3,5-dicarboxylic acid-benzy1)-9H-indazolc3,6-dicarboxylic acid (H4DCDC) is dissolved in a mixed solvent of DMA/Et0H/H20, thereby a solvent is obtained to be used; S2: Cupric nitrate is dissolved in the mixed solvent of DNIA/Et0H/H20, and then the solvent obtained in Si is added slowly, after ultrasonic processing for 5-10 min, the temperature is raised to 120-160°C to be reacted for 24-48h, and then cooled to room temperature; S3: solids are filtered and washed with ethanol, and then being naturally dried for 12-20h at the room temperature, and then Cu-MOF are obtained; S4:the solid obtained in S3 is calcined under an oxygen atmosphere, thereby the catalyst is obtained.
  2. 2. The catalyst for selective hydrogenation of biomass defined in claim 1, wherein a molar ratio of the 9-(3,5-dicarboxylic acid-benzy1)-9H-indazole3,6-dicarboxylic acid (H4DCDC) and the cupric nitrate is 1-2:1.5-2.
  3. 3. The catalyst for selective hydrogenation of biomass defined in claim t, wherein a volume ratio of the mixed solvent of DMA/Et0H/H20 is 1:1:1
  4. 4. The catalyst for selective hydrogenation of biomass defined in claim I, wherein the atmosphere containing oxygen in S4 is one of oxygen-nitrogen mixture, oxygen-argon mixture and oxygen-helium mixture, more preferably, the atmosphere containing oxygen in S4 is the oxygen-nitrogen mixture.
  5. 5. The catalyst for selective hydrogenation of biomass defined in claim 1, wherein an oxygen content in the atmosphere in S4 is 0.5%-20% and a flow velocity is 80--120mL/min.
  6. 6. The catalyst for selective hydrogenation of biomass defined in claim 1, wherein a heating rate in calcining of S4 is heating to 100-350°C under temperature of 2-10°C/min,and then maintain at the temperature for 1-3h.
  7. 7. The catalyst for selective hydrogenation of biomass defined in claim 1, wherein particle size of the catalyst prepared in terms of the above-stated methods is 8-30micron when in a furfural selective hydrogenation reaction.
  8. 8. The catalyst for selective hydrogenation of biomass defined in claim 1, wherein the catalyst is used in the furfural selective hydrogenation reaction, especially in preparing furfuryl alcohol or tetrahydrofurfuryl alcohol in the furfural selective hydrogenation reaction.
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CN107376997A (en) * 2017-07-04 2017-11-24 常州大学 A kind of catalyst preparation and its application for Oxybenzene methyl alcohol producing benzaldehyde
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CN111905830A (en) * 2020-09-08 2020-11-10 陈华 Catalyst for selective hydrogenation of furfural

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CN109369689A (en) * 2018-12-10 2019-02-22 中原工学院 A kind of copper metal organic frame (Cu-MOF) catalysis material, preparation method and application
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