CN108503515B - Method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin - Google Patents

Method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin Download PDF

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CN108503515B
CN108503515B CN201810193664.2A CN201810193664A CN108503515B CN 108503515 B CN108503515 B CN 108503515B CN 201810193664 A CN201810193664 A CN 201810193664A CN 108503515 B CN108503515 B CN 108503515B
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vanillin
hydrodeoxygenation
methanol
mixed solution
water
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CN108503515A (en
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胡勋
孙恺
杨成
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin. Active hydrogen generated by methanol-water gas phase reforming is directly used as a hydrogen source for vanillin hydrodeoxygenation reaction, so that the defects of an external hydrogen supply process in the processes of transportation, storage and use are avoided, and the speed and the efficiency of the vanillin hydrodeoxygenation reaction are improved. The method adopts Cu/ZnO-Al2O3The vanillin is subjected to in-situ hydrodeoxygenation by using hydrogen generated by methanol and water at high temperature in a fixed bed reactor under the nitrogen atmosphere. The method provided by the invention has the advantages of simple process, mild conditions, low cost and good industrial application prospect.

Description

Method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin
Technical Field
The invention belongs to the field of organic catalysis, and particularly relates to a method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin.
Background
With the increasingly prominent environmental and energy problems, the development and utilization of biomass resources are receiving more and more attention from people. The research on how to efficiently utilize biomass resources is carried out, 4-methyl guaiacol synthesized by hydrogenating and deoxidizing vanillin is often used as a model reaction for biomass degradation to research the conversion process, and the method has important theoretical guiding significance for researching the downstream reaction of biomass. Hydrogen in the hydrodeoxygenation reaction is a clean and environment-friendly energy source, and is used as a combustible gas to be stored and transported under pressure, so that higher requirements are put on hydrogen storage equipment and users.
With the development of modern chemical industry, the yield and the reserve of methanol at home and abroad are abundant, and various downstream reactions are developed vigorously by taking methanol as a raw material, wherein the methanol steam reforming has low cost, mild conditions, safety and reliability, and is one of important hydrogen production methods researched by scientists at present. As a liquid, methanol is easier to store handle. The invention provides a method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin, which is characterized in that exogenous hydrogen is not required to be provided, and active hydrogen generated by methanol steam reforming reaction is used for carrying out in-situ hydrodeoxygenation reaction on the vanillin.
The hydrogen production from methanol is an endothermic reaction, the reaction rate is improved by raising the temperature, the reaction rate is improved by hydrodeoxygenation from vanillin is an exothermic reaction, and the reaction rate is improved by lowering the temperature; in addition, the types and the action mechanisms of the catalysts for the hydrogen production reaction of methanol and the hydrodeoxygenation of vanillin are different, and the two reactions cannot be coupled by utilizing the prior art.
The invention relates to a method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin. Active hydrogen generated by methanol-water gas phase reforming is directly used as a hydrogen source for vanillin hydrodeoxygenation reaction, so that the defects of an external hydrogen supply process in the processes of transportation, storage and use are avoided. By using Cu/ZnO-Al2O3The vanillin is subjected to in-situ hydrodeoxygenation by using hydrogen generated by methanol and water at high temperature in a fixed bed reactor under the nitrogen atmosphere. The method provided by the invention has the advantages of simple process, mild conditions, low cost and good industrial application prospect.
Disclosure of Invention
The invention provides a method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin, aiming at the defects of the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing 4-methyl guaiacol by methanol steam hydrogen production and vanillin hydrodeoxygenation coupling reaction comprises the following steps:
(1) dropping a mixed solution of copper nitrate trihydrate, zinc nitrate hexahydrate, aluminum nitrate nonahydrate and deionized water into a sodium carbonate aqueous solution at a certain speed, carrying out water bath at 70 ℃, dropping for 2h, aging for 2h after dropping, filtering, washing, drying, calcining to obtain a catalyst, grinding, and sieving solid particles of 40-60 meshes for later use.
Wherein the mass ratio of the copper, the zinc, the alumina and the water is 0.25-0.40:0.10-0.20:1-2: 50-100.
(2) 0.5 g of the 40-60 mesh catalyst in the (1) is weighed and loaded into a fixed bed reactor, nitrogen and hydrogen with certain flow rate are introduced, and reduction is carried out at the temperature of 240 ℃ and 300 ℃ for 1 h to obtain Cu/ZnO-Al2O3A catalyst.
(3) Preparing 10-25 parts by mass of methanol and 20-45 parts by mass of water into a mixed solution a; preparing 10-25 parts by mass of methanol, 20-45 parts by mass of water and 0.2-1.2 parts by mass of vanillin into a mixed solution b.
(4) Under the nitrogen atmosphere, the mixed solution a is pumped into the container with Cu/ZnO-Al by a peristaltic pump2O3And (3) stopping after 30min of the fixed bed of the catalyst, introducing the mixed solution b, continuously reacting at the reaction temperature of 180-300 ℃ for 30min at the specified temperature, collecting the product, and calculating the conversion rate of the vanillin and the selectivity of the 4-methyl guaiacol.
The method adopts Cu/ZnO-Al2O3The method is characterized in that the catalyst is used, the reaction temperature is 200-450 ℃ in a fixed bed reactor under the nitrogen atmosphere, and the mixed solution of methanol, water and vanillin is used as a raw material to prepare the 4-methyl guaiacol.
The drying temperature in the step (1) is 80-110 ℃, the drying time is 6-12 h, the calcining temperature is 300-500 ℃, and the calcining time is 1-6 h.
The nitrogen flow rate in the step (2) is 20-60 mL/min, and the hydrogen flow rate is 20-60 mL/min.
In the step (4), the flow rate of nitrogen is 30-60 mL/min, the flow rate of the solution a is 0.05-0.50 mL/min, and the flow rate of the solution b is 0.05-0.50 mL/min.
The method for hydrogen production by methanol steam and hydrodeoxygenation of vanillin shows high activity and reaction rate.
Drawings
FIG. 1 results of example 1.
Figure 2 example 2 results.
Figure 3 example 3 results.
Figure 4 example 4 results.
FIG. 5 is a diagram of a reaction apparatus of the present invention.
1. A nitrogen gas cylinder; 2. a material tank for the solution a; 3. solution b material tank; 4. a pressure reducing valve; 5. a stop valve; 6. a peristaltic pump; 7. a fixed bed reactor; 8. a furnace; 9. a gas-liquid condenser; 10. a liquid collection bottle; 11. drying the bottle; 12. a pressure gauge; 13. an infrared gas analyzer.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
5.66 g of copper nitrate trihydrate, 4.13 g of zinc nitrate hexahydrate, 36.78 g of aluminum nitrate nonahydrate and 270.55 g of deionized water are prepared into a mixed solution A. Dissolving 19.07 g of sodium carbonate in 368.75 g of deionized water, placing in 70 ℃ water bath and stirring, slowly dripping the mixed solution A for 2h, aging at 70 ℃ for 2h after dripping, filtering and washing, drying at 100 ℃ for 8 h, calcining at 350 ℃ for 4 h to obtain the catalyst, grinding, and sieving to obtain solid particles with 40-60 meshes. Weighing 0.5 g of 40-60 mesh catalyst, loading into a fixed bed reactor, reducing at 300 ℃ for 1 h under the conditions of nitrogen flow rate of 30 mL/min and hydrogen flow rate of 30 mL/min to obtain Cu/ZnO-Al2O3A catalyst.
The reaction atmosphere is nitrogen, 30 mL/min, 16 g of methanol and 27 g of water are prepared into a mixed solution a, 16 g of methanol, 27 g of water and 0.84 g of vanillin are prepared into a mixed solution b, and the mixed solution a is introduced into a reaction chamber filled with Cu/ZnO-Al by a peristaltic pump2O3And (3) introducing a fixed bed of the catalyst, stopping introducing after 30min, introducing a mixed solution b, wherein the flow rates of a and b are both 0.1 mL/min, the reaction temperature is 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, and 300 ℃, continuously reacting for 30min respectively, recording the gas content, collecting liquid-phase products, and analyzing and calculating the conversion rate of vanillin and the selectivity of 4-methyl guaiacol by GC-MS (gas chromatography-mass spectrometry), wherein the results are shown in figure 1, and the reaction device is shown in figure 5.
Example 2
6.5 g of copper nitrate trihydrate, 3.43 g of zinc nitrate hexahydrate, 36.78 g of aluminum nitrate nonahydrate and 310.00 g of deionized water are prepared into a mixed solution A. Dissolving 11.01 g of sodium carbonate in 340.75 g of deionized water, placing in 70 ℃ water bath and stirring, slowly dripping the mixed solution A for 2h, aging at 70 ℃ for 2h after dripping, filtering and washing, drying at 110 ℃ for 6 h, calcining at 300 ℃ for 3 h to obtain the catalyst, grinding and sieving solid particles with 40-60 meshes. Weighing 0.5 g of 40-60 mesh catalyst, loading into a fixed bed reactor, reducing at 300 ℃ for 1 h under the conditions of nitrogen flow rate of 30 mL/min and hydrogen flow rate of 30 mL/min to obtain Cu/ZnO-Al2O3A catalyst.
The reaction atmosphere is nitrogen, 30 mL/min, 16 g of methanol and 27 g of water are prepared into a mixed solution a, 16 g of methanol, 27 g of water and 0.84 g of vanillin are prepared into a mixed solution b, and the mixed solution a is introduced into a reaction chamber filled with Cu/ZnO-Al by a peristaltic pump2O3And (3) stopping introducing the fixed bed of the catalyst after 30min, introducing the mixed solution b, wherein the flow rates of a and b are both 0.1 mL/min, the reaction temperature is 260 ℃, the reaction is 30min, 60 min, 90 min, 120 min, 150 min and 180 min, recording the gas content, collecting liquid-phase products, and calculating the conversion rate of vanillin and the selectivity of 4-methyl guaiacol by GC-MS analysis, wherein the result is shown in figure 2.
Example 3
The catalyst was prepared in the same manner as in example 1.
The reaction atmosphere is 30 mL/min of nitrogen and 60 mL/min of hydrogen, 1 g of vanillin and 50 g of water are prepared into a mixed solution c, the mixed solution c is kept at the temperature of 45 ℃ and is filled with Cu/ZnO-Al2O3The fixed bed of the catalyst, the flow rate is 0.1 mL/min, the reaction temperature is 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃ and the reaction is continuously carried out for 30min respectively, the gas content is recorded, the liquid phase product is collected and analyzed by GC-MS to calculate the conversion rate of the vanillin and the selectivity of the 4-methyl guaiacol, and the result is shown in figure 3.
Example 4
The catalyst was prepared in the same manner as in example 1.
The reaction atmosphere is 30 mL/min nitrogen and 60 mL/min hydrogen, 1 g vanillin and 50 g water are prepared into a mixed solution c, the mixed solution c is kept at the temperature of 45 ℃ and is filled with Cu/ZnO-Al2O3A fixed bed of catalyst, flow rate 0.1 mL/min, reaction temperature 260 ℃, reaction for 30min, 60 min, 90 min, 120 min, 150 min, 180 min, recording gas content, collecting liquid phase product, calculating conversion rate of vanillin and selectivity of 4-methyl guaiacol by GC-MS analysis, and the result is shown in figure 4.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (5)

1. A method for hydrogen production by methanol steam and hydrodeoxygenation coupling of vanillin is characterized by comprising the following steps:
(1) dropping a mixed solution of copper nitrate trihydrate, zinc nitrate hexahydrate, aluminum nitrate nonahydrate and deionized water into a sodium carbonate aqueous solution at a certain speed, carrying out water bath at 70 ℃, dropping for 2h, aging for 2h after dropping, filtering, washing, drying and calcining to obtain a catalyst, grinding and screening solid particles of 40-60 meshes for later use, wherein the mass ratio of copper, zinc and aluminum oxide to water is 0.25-0.40:0.10-0.20:1-2: 50-100;
(2) 0.5 g of the 40-60 mesh catalyst in the (1) is weighed and loaded into a fixed bed reactor, nitrogen and hydrogen with certain flow rate are introduced, and reduction is carried out at the temperature of 240 ℃ and 300 ℃ for 1 h to obtain Cu/ZnO-Al2O3A catalyst;
(3) preparing 10-25 parts by mass of methanol and 20-45 parts by mass of water into a mixed solution a; preparing 10-25 parts by mass of methanol, 20-45 parts by mass of water and 0.2-1.2 parts by mass of vanillin into a mixed solution b;
(4) under the nitrogen atmosphere, the mixed solution a is pumped into the container with Cu/ZnO-Al by a peristaltic pump2O3And (3) stopping after 30min, introducing the mixed solution b, continuously reacting at the reaction temperature of 180-300 ℃ for 30min at the specified temperature, collecting the product, analyzing by GC-MS, and calculating the conversion rate of the vanillin and the selectivity of the 4-methyl guaiacol.
2. The method of claim 1, wherein the hydrogen production by methanol steam and the hydrodeoxygenation by vanillin are coupled by Cu/ZnO-Al2O3Taking a mixed solution of methanol, water and vanillin as a raw material to perform coupling reaction in a fixed bed reactor in nitrogen atmosphere to generate the 4-methyl guaiacol.
3. The method as claimed in claim 1, wherein the drying temperature in step (1) is 80-110 ℃, the drying time is 6-12 h, the calcination temperature is 300-500 ℃, and the calcination time is 1-6 h.
4. The method for coupling hydrogen production from methanol steam and hydrodeoxygenation of vanillin of claim 1, wherein the flow rate of nitrogen in the step (2) is 20-60 mL/min, and the flow rate of hydrogen is 20-60 mL/min.
5. The method for coupling hydrogen production from methanol steam and hydrodeoxygenation of vanillin of claim 1, wherein the flow rate of nitrogen in the step (4) is 30-60 mL/min, the flow rate of the solution a is 0.05-0.50 mL/min, and the flow rate of the solution b is 0.05-0.50 mL/min.
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CN1785513A (en) * 2005-09-30 2006-06-14 复旦大学 Nano-copper base catalyst used for methanol aqueous vapour reforming hydrogen producing and its preparation method
CN105435800A (en) * 2015-11-19 2016-03-30 中科合成油技术有限公司 Catalyst used for preparing 2,5-methyl furan and preparation method thereof
WO2016066835A1 (en) * 2014-10-30 2016-05-06 Córdova Armando A mild catalytic reduction of c-o bonds and c=o bonds using a recyclable catalyst system

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Publication number Priority date Publication date Assignee Title
CN1785513A (en) * 2005-09-30 2006-06-14 复旦大学 Nano-copper base catalyst used for methanol aqueous vapour reforming hydrogen producing and its preparation method
WO2016066835A1 (en) * 2014-10-30 2016-05-06 Córdova Armando A mild catalytic reduction of c-o bonds and c=o bonds using a recyclable catalyst system
CN105435800A (en) * 2015-11-19 2016-03-30 中科合成油技术有限公司 Catalyst used for preparing 2,5-methyl furan and preparation method thereof

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