CN108993495B - Method for preparing alkane compound by catalytic deoxidation of carbonyl or hydroxyl-containing compound - Google Patents

Method for preparing alkane compound by catalytic deoxidation of carbonyl or hydroxyl-containing compound Download PDF

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CN108993495B
CN108993495B CN201810869226.3A CN201810869226A CN108993495B CN 108993495 B CN108993495 B CN 108993495B CN 201810869226 A CN201810869226 A CN 201810869226A CN 108993495 B CN108993495 B CN 108993495B
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hydroxyl
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CN108993495A (en
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张颖
王昊
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University of Science and Technology of China USTC
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
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Abstract

The invention provides a method for preparing alkane compounds by catalytic deoxidation of compounds containing carbonyl or hydroxyl, which comprises the step of reacting compounds containing carbonyl or hydroxyl with H in the presence of a supported metal catalyst2Carrying out hydrodeoxygenation reaction to obtain alkane compounds, comprising the following steps: reacting compound containing carbonyl or hydroxyl with H under the catalysis of supported metal catalyst2Carrying out hydrodeoxygenation reaction to obtain alkane compounds, wherein the supported metal catalyst consists of a carrier and active metal loaded on the carrier, and the hydrodeoxygenation reaction is carried out at the temperature of 100-230 ℃ and the H of 0.1-10 MPa2Under pressure. The method can prepare the alkane compound by catalyzing and deoxidizing the compound containing carbonyl or hydroxyl under mild reaction conditions with high conversion rate and high selectivity, and the catalyst can be recycled, so the method has good industrial application prospect.

Description

Method for preparing alkane compound by catalytic deoxidation of carbonyl or hydroxyl-containing compound
Technical Field
The invention relates to the technical field of compound preparation, in particular to a method for preparing an alkane compound by catalytic deoxidation of a compound containing carbonyl or hydroxyl.
Background
The alkane compound has stable chemical property, is commonly used as a solvent, an organic synthesis raw material and a fuel, and has wide application in the fields of organic synthesis, chemical industry and energy. In industrial applications, hydrodeoxygenation of carbonyl-or hydroxyl-containing compounds such as aldehydes, ketones, acids, esters or alcohols to produce the corresponding alkanes is a common and important technique. For example, stearic acid as a raw material is a fatty acid widely existing in the nature, almost all the grease contains stearic acid with different contents, and heptadecane and octadecane are used as long-chain alkanes and are important chemical raw materials and energy materials, so that the efficient conversion of stearic acid into biodiesel has great energy strategic significance.
CN104722329A discloses a catalyst for preparing alkane by catalytic hydrogenation of biolipid, wherein the catalyst is prepared by loading 10-50 wt% of active metal Ni, Mo, Co or W on Al modified by alkali metal, alkaline earth metal and rare earth metal2O3Or a carrier consisting of a molecular sieve. However, the catalytic hydrogenation reaction in the application needs to be carried out at a high temperature (250-450 ℃) and a specific hydrogen-oil ratio and space velocity; although the active metal of the catalyst is non-noble metal, the rare earth metal such as Ce, La and the like is mainly used in the metal used for modifying the carrier of the catalyst, and the catalyst has poor reaction activity for preparing alkane, for example, the product selectivity is only about 80 percent, and the recycling performance is not mentioned at all.
In addition, CN107325835A discloses a method for converting oils and fats or their hydrolysates into higher fatty acids and long-chain alkanes by a hydrothermal method, wherein the catalyst used is metal powder, so that the catalyst after reaction cannot be recycled; meanwhile, the reaction needs to be carried out at a high temperature of about 300 ℃, and the reaction conditions are severe.
Disclosure of Invention
In view of the above, the present invention aims to provide a novel method for preparing alkane compounds by catalytic deoxygenation of carbonyl or hydroxyl-containing compounds, wherein the reaction conditions are mild, and the catalyst after the reaction can be recycled through simple post-treatment.
The invention provides a method for preparing alkane compounds by catalytic deoxidation of compounds containing carbonyl or hydroxyl, which comprises the step of reacting compounds containing carbonyl or hydroxyl with H in the presence of a supported metal catalyst2Carrying out hydrodeoxygenation reaction to obtain alkane compounds,
wherein the supported metal catalyst consists of a carrier and an active metal supported on the carrier, and the carrier is selected from La2O3、ZrO2·Al2O3、ZrO2·La2O3、ZrO2·CeO2、ZrO2·Pr6O11、ZrO2·Nd2O3、ZrO2·Yb2O3、ZrO2·V2O5、ZrO2·ZnO2、ZrO2·Nb2O5、ZrO2·MoO3Or ZrO2MgO, the active metal is one or more selected from Ru, Rh, Pd, Os, Ir and Pt, and the hydrodeoxygenation reaction is carried out at a temperature of 100-230 ℃ and H of 0.1-10 MPa2Under pressure.
In a preferred embodiment, the supported metal catalyst is subjected to a pre-reduction treatment in a hydrogen atmosphere prior to use.
In a preferred embodiment, the carrier is La2O3、ZrO2·Al2O3Or ZrO2·La2O3。
In a preferred embodiment, the active metal is present in an amount of from 0.3% to 8.0% based on the weight of the supported metal catalyst.
In a preferred embodiment, the supported metal catalyst is prepared by:
a) mixing soluble salt containing carrier metal ions and a surfactant in water, adding an alkali solution to adjust the pH value to obtain a precipitate, and calcining the precipitate to obtain a catalyst carrier;
b) dispersing the obtained catalyst carrier in a solvent, adding salt containing active metal ions, stirring, mixing and drying to obtain the supported metal catalyst.
In a further preferred embodiment, in step a), the surfactant is cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, polyvinylpyrrolidone or sodium dodecylbenzenesulfonate.
In a further preferred embodiment, in step a), the alkali solution is sodium hydroxide, potassium hydroxide, sodium carbonate or an aqueous ammonia solution.
In a further preferred embodiment, in step a), the temperature of the calcination is from 400 to 800 ℃.
In a further preferred embodiment, in step b), the solvent is water, ethanol, acetone, diethyl ether, toluene or xylene.
In a further preferred embodiment, in step b), the salt containing an active metal ion is a nitrate, acetate or chloride salt.
In a preferred embodiment, the carbonyl-or hydroxyl-containing compound is an alcohol, aldehyde, ketone, acid, or ester compound.
In a preferred embodiment, the hydrodeoxygenation reaction is carried out at a temperature of 100 to 200 ℃ and a H of 1 to 8MPa2The reaction is carried out for 0.5 to 24 hours under pressure.
In a preferred embodiment, the hydrodeoxygenation reaction is carried out at a temperature of 120 to 180 ℃ and at a H of 2 to 6MPa2The reaction is carried out for 1-10 h under pressure.
In a preferred embodiment, the supported metal catalyst is recycled.
Compared with the prior art, the invention provides a novel method for preparing the alkane compound by catalytic deoxidation of the compound containing carbonyl or hydroxyl, which has mild reaction conditions and can recycle the catalyst after the reaction through simple post-treatment. The invention can prepare the alkane compound used as solvent, organic synthetic raw material and/or fuel and the like from the carbonyl or hydroxyl-containing compound by catalytic deoxidation with high conversion rate, high selectivity or product yield, mild reaction conditions, simple reaction device and equipment and the like by adopting the supported metal catalyst with specific composition, and has good industrial application prospect.
Detailed Description
The invention relates to a method for preparing alkane compounds by catalytic deoxidation of compounds containing carbonyl or hydroxyl, which comprises the step of reacting compounds containing carbonyl or hydroxyl with H in the presence of a supported metal catalyst2And carrying out hydrodeoxygenation reaction to obtain the alkane compound.
As used herein, the "carbonyl-or hydroxyl-containing compound" as a reaction raw material means any compound containing one or more carbonyl (-CO-) or one or more hydroxyl (-OH) functional groups, which may be a compound such as aldehyde, ketone, acid, ester, or alcohol, etc., which are commonly used in the field of organic chemistry, and the carbonyl-or hydroxyl-containing compound may be a compound containing both a carbonyl group and a hydroxyl group. In addition, the number of carbon atoms of the carbonyl group-or hydroxyl group-containing compound is not particularly limited, and may be usually 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 5 to 20 carbon atoms.
As used herein, "alkane compound" as a reaction product encompasses all reaction products obtained by the catalytic hydrodeoxygenation reaction of the present invention of the above-described carbonyl-or hydroxyl-containing compounds, including alkanes (straight or branched chain), cycloalkanes (with or without substituents such as C) obtained by the catalytic hydrodeoxygenation reaction of the present invention1-10Alkyl, halogen, etc.), and alkanes or cycloalkanes containing one or more heteroatoms selected from O, S or N in the molecule, such as furans, which may be a single alkane compound or a mixture of alkanes. When the obtained alkane compound is a mixture, it may be separated as needed by a method commonly used in the art, or may be used directly as a mixture as needed, for example, as a solvent or a fuel, etc. In the present invention, the carbon number of the alkane compound as the reaction product is determined by the carbonyl group-or hydroxyl group-containing compound as the reaction raw material, that is, the carbon number may be in the range of usually 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 5 to 20 carbon atoms.
In the process of the present invention, the supported metal catalyst is composed of a carrier and an active metal supported on the carrier.
The carrier in the catalyst used in the present invention may be lanthanum oxide (La)2O3) Alumina-modified zirconia (ZrO)2·Al2O3) Lanthanide metal oxide modified zirconia (e.g., ZrO)2·La2O3、ZrO2·CeO2、ZrO2·Pr6O11、ZrO2·Nd2O3、ZrO2·Yb2O3) A fourth period transition metal oxide-modified zirconia (e.g., ZrO)2·V2O5、ZrO2·ZnO2) A fifth period transition metal oxide modified zirconia (e.g., ZrO)2·Nb2O5、ZrO2·MoO3) Or alkaline earth metal oxide-modified zirconia (e.g. ZrO)2MgO). Preferably, the carrier is La2O3、ZrO2·Al2O3Or ZrO2·La2O3More preferably ZrO2·Al2O3。
The active metal in the catalyst used in the present invention is one or more selected from Ru, Rh, Pd, Os, Ir and Pt.
Preferably, in certain embodiments of the invention, the catalyst used is Ru/La2O3、Ru/ZrO2·Al2O3、Ru/ZrO2·La2O3、Ru/ZrO2·CeO2、Ru/ZrO2·Pr6O11、Ru/ZrO2·Nd2O3、Ru/ZrO2·Yb2O3、Ru/ZrO2·V2O5、Ru/ZrO2·ZnO2、Ru/ZrO2·Nb2O5、Ru/ZrO2·MoO3、Ru/ZrO2·MgO、Ru/ZrO2·Al2O3、Rh/ZrO2·Al2O3、Pd/ZrO2·Al2O3、Os/ZrO2·Al2O3、Ir/ZrO2·Al2O3Or Pt/ZrO2·Al2O3。
Preferably, in the process of the present invention, the active metal is present in an amount of from 0.3% to 8.0%, preferably from 1.0% to 5.0%, most preferably about 2.0%, based on the total weight of the supported metal catalyst. If the content of the active metal is less than 0.3%, the catalytic activity of the catalyst for the hydrodeoxygenation reaction of a carbonyl-or hydroxyl-containing compound is insufficient, resulting in that the reaction cannot be performed with high conversion and high selectivity or yield under the mild reaction conditions of the present invention, and also possibly causing incomplete hydrodeoxygenation reaction, particularly incomplete hydrodeoxygenation reaction of an alcohol compound; if the content of the active metal exceeds 8.0 percent, the catalytic activity of the catalyst is not obviously increased, but the production cost of the catalyst is obviously increased, so that the overall cost of the method is increased, and the industrial application prospect of the method is influenced.
The catalyst of the present invention may be prepared by impregnation or coprecipitation methods which are conventional in the art. Preferably, the supported metal catalyst used in the process of the present invention is prepared according to the following method:
a) mixing soluble salt containing carrier metal ions and a surfactant in water, adding an alkali solution to adjust the pH value to obtain a precipitate, and calcining the precipitate to obtain a catalyst carrier;
b) dispersing the obtained catalyst carrier in a solvent, adding salt containing active metal ions, stirring, mixing and drying to obtain the supported metal catalyst.
The soluble salt containing a carrier metal ion in the method of the present invention is not particularly limited, and any soluble salt known to those skilled in the art may be used. Preferably, the soluble salt containing the carrier metal ion used in step a) is a nitrate or chloride salt.
Preferably, the surfactant used in step a) may be cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, polyvinylpyrrolidone or sodium dodecylbenzenesulfonate.
Preferably, the alkaline solution used in step a) is also referred to as co-precipitant and may be sodium hydroxide, potassium hydroxide, sodium carbonate or aqueous ammonia solution.
Preferably, in step a), after the pH of the mixed solution is adjusted to a desired value, stirring is stopped for aging. Preferably, the aging is carried out at 60-98 ℃ for 5-15 h.
Preferably, the calcination is carried out in step a) at a temperature of 400 to 800 ℃, for example about 550 ℃.
Preferably, the solvent used in step b) is water, ethanol, acetone, diethyl ether, toluene or xylene, preferably acetone.
Preferably, the salt containing active metal ions used in step b) is a nitrate, acetate, or chloride salt.
The temperature and equipment for the drying in step b) of the process of the present invention are not particularly limited as long as the final catalyst solid can be obtained. For example, before drying, the mixture can be evaporated to dryness by a rotary evaporator and then dried in a drying box at 20-80 ℃.
In certain preferred embodiments of the present invention, the catalyst of the present invention may be prepared as follows:
dissolving surfactant such as cetyl trimethyl ammonium bromide in distilled water, and adding soluble salt containing carrier metal ion such as La (NO)3)3Or ZrOCl2And Al (NO)3)3The pH of the obtained mixed solution is adjusted to about 9 to 10 by dropping an alkali solution such as an aqueous solution of sodium hydroxide to precipitate the carrier metal ions (i.e., the carrier metal salt solution is converted into a precipitate), and the precipitate is aged, then a solid precipitate is obtained by filtration and washed with, for example, distilled water, dried with, for example, anhydrous magnesium sulfate, and calcined in, for example, a muffle furnace at, for example, 500 to 600 ℃.
Dispersing the obtained catalyst carrier in a solvent such as acetone, dissolving a soluble salt compound of the active metal in the same solvent, and then adding the dissolved salt compound of the active metal into the carrier solution, or directly adding the soluble salt compound of the active metal into the carrier solution, and stirring for more than 4 hours at a constant temperature such as 20-60 ℃. And then, distilling under reduced pressure by using a rotary evaporator to remove the solvent, and drying overnight in a drying box at 20-80 ℃ to obtain the supported metal catalyst.
Preferably, the catalyst prepared by the above method is subjected to a pre-reduction treatment in a hydrogen atmosphere before use to be further activated, thereby improving its catalytic activity.
In the process of the present invention, the hydrodeoxygenation reaction is carried out at a temperature of 100 to 230 ℃, preferably 100 to 200 ℃, more preferably 120 to 180 ℃, for example at a temperature of about 160 ℃.
In the process of the invention, the hydrodeoxygenation reaction is at H of 0.1 to 10MPa, preferably 1 to 8MPa, more preferably 2 to 6MPa, for example at about 4MPa2Under pressure.
In the method of the present invention, the time of the hydrodeoxygenation reaction is preferably 0.5 to 24 hours, more preferably 0.5 to 16 hours, and most preferably 1 to 10 hours.
The present invention does not require special equipment for the catalytic hydrodeoxygenation reaction, for example, the catalytic hydrodeoxygenation reaction of the present invention can be carried out in an autoclave, a fixed bed or a trickle bed as is common in the art.
The catalytic hydrodeoxygenation reaction of the invention adopts a solid-phase catalytic system, and can efficiently hydrodeoxygenate compounds containing carbonyl or hydroxyl in a liquid phase to generate corresponding alkane products under a mild temperature condition. The method has the characteristics of simple catalyst preparation process, high activity, high selectivity, mild reaction conditions, good stability and the like, and after the reaction is finished, the reaction liquid and the catalyst can be separated by simple filtration; the separated catalyst can be recycled, and the catalytic activity and the selectivity are not reduced. In addition, the catalyst after repeated use can be reused after simple post-treatment such as heating and hydrogen reduction treatment.
The inventor of the invention has proved through experiments that the conversion rate of the raw material of the method for preparing the alkane compound can reach 99.9%, and the yield of the product alkane compound can reach 975%.
Examples
In order to further illustrate the present invention, the following detailed description is given with reference to examples. Those skilled in the art will appreciate that these examples are not intended to limit the scope of the present invention.
In the following examples, unless otherwise specified, the methods used are all conventional in the art, and the materials, reagents and the like used are commercially available.
Example 1: Ru/La2O3Preparation of the catalyst
5.47g of hexadecyltrimethylammonium bromide was weighed into a 500mL three-necked flask (equipped with a heating device, a magnetic stirring device, a thermometer, and a dropping funnel), 30mL of deionized water was added, and heated to 60 ℃ under magnetic stirring. Then, 12.99g of La (NO) was weighed out3)3·6H2O and was added to 50mL of deionized water and dissolved with stirring by a stirring bar, and then dropwise added to the flask through a dropping funnel with stirring, followed by addition of a 1mol/L NaOH solution to adjust the pH of the mixed solution to 9. Then, the stirring is closed, the mixture is aged for 10 hours at the temperature of 90 ℃, filtered, washed for 3 times by 30mL of deionized water and ethanol respectively, dried in a drying box at the temperature of 60 ℃, and then placed in a muffle furnace to be calcined for 4 hours at the temperature of 550 ℃, so that the carrier La is obtained2O3。
1.00g of the obtained carrier La was weighed2O3Placed in a 500mL three-necked flask equipped with a heating device, a magnetic stirring device, a thermometer and a dropping funnel, 40mL of acetone was added, and heated to 45 ℃ under magnetic stirring. 0.0519g of RuCl were weighed out3·xH2Adding 10mL of acetone into the mixture, stirring the mixture by a stirring rod to dissolve the acetone, dropwise adding the mixture into the flask through a dropping funnel while stirring, continuously stirring the mixture for 24 hours, evaporating the mixture to dryness under reduced pressure by a rotary evaporator, and drying the mixture in a drying oven at 80 ℃ to obtain Ru/La2O3Catalyst, wherein the Ru content is 2.0 wt% based on the total weight of the catalyst.
Example 2: Ru/ZrO2·Al2O3Preparation of the catalyst
Except that the raw materials for preparing the carrier are differentThe procedure was essentially the same as in example 1. 5.47g of cetyltrimethyl ammonium bromide was weighed into a flask, 30mL of deionized water was added, and heated to 60 ℃ with magnetic stirring. Then 8.06g ZrOCl is weighed2·8H2O and 1.88gAl (NO)3)3·9H2O and adding the mixture into deionized water to dissolve, dropwise adding the mixture into a flask, then adjusting the pH of the mixed solution to 6 by using 1mol/L NaOH solution, then closing stirring, aging for 10h at 90 ℃, filtering, respectively washing for 3 times by using 30mL of deionized water and ethanol, drying in a drying box at 60 ℃, then putting the dried product into a muffle furnace to calcine for 4h at 550 ℃, thereby obtaining the carrier ZrO2·Al2O3。
1.00g of the resulting support ZrO was weighed2·Al2O3Placed in a flask, acetone was added and heated to 45 ℃ with magnetic stirring. 0.0519g of RuCl were weighed out3·xH2O is added into acetone to be dissolved, then the mixture is dripped into the flask drop by drop and is continuously stirred for 24 hours, and the mixture is decompressed, steamed and dried to obtain the catalyst Ru/ZrO2·Al2O3Wherein the Ru content is 20 wt% based on the total weight of the catalyst.
Example 3: preparation of other catalysts
The following catalysts having active metal contents of 2.0%, respectively (based on the total weight of the catalyst) were also prepared by the present invention through the same preparation process as in example 1 or 2: Ru/ZrO2·La2O3、Ru/ZrO2·CeO2、Ru/ZrO2·Pr6O11、Ru/ZrO2·Nd2O3、Ru/ZrO2·Yb2O3、Ru/ZrO2·V2O5、Ru/ZrO2·ZnO2、Ru/ZrO2·Nb2O5、Ru/ZrO2·MoO3、Ru/ZrO2·MgO、Ru/ZrO2·Al2O3、Rh/ZrO2·Al2O3、Pd/ZrO2·Al2O3、Os/ZrO2·Al2O3、Ir/ZrO2·Al2O3And Pt/ZrO2·Al2O3。
Example 4: preparation of alkane compounds (mixture of heptadecane and octadecane) by catalytic hydrodeoxygenation of stearic acid
The catalysts in table 1 below, prepared in examples 1 to 3, were subjected to a pre-reduction treatment in a hydrogen atmosphere for 2 hours for activation.
Adding 025mmol of stearic acid, 50mg of any one of the catalysts subjected to pre-reduction treatment and 10mL of deionized water into a 25mL high-pressure reaction kettle, then sealing the reaction kettle, replacing the reaction kettle with hydrogen, introducing 4MPa of hydrogen, heating to 160 ℃, reacting for 4 hours under magnetic stirring, cooling to room temperature, discharging gas and reducing pressure, opening the reaction kettle, collecting reaction liquid, extracting with ethyl acetate, centrifuging through a centrifuge, separating the catalyst from the reaction liquid, and analyzing the obtained reaction liquid by gas chromatography.
The gas chromatography conditions were as follows: GC1690 gas chromatography, FID detector, capillary chromatography column (HP-5, 30m × 0.250mm × 0.25 μm), programmed temperature ramp was used, starting at a column temperature of 200 deg.C and ramping up to 250 deg.C at a ramp rate of 5 deg.C/min for 3 minutes. The carrier gas was 99.99% high purity nitrogen at a flow rate of 1 mL/min.
The results of the catalyst and gas chromatography are shown in Table 1, and these reactions all give paraffinic compounds as a mixture of heptadecane and octadecane, and such products can be used directly as solvents or fuels without isolation.
Table 1: the catalyst used and the corresponding conversion (%) of the starting material (stearic acid) and the overall yield (%) of the paraffinic products (heptadecane and octadecane)
Catalyst and process for preparing same Stearic acid conversion (%) Total yield of alkane (%)
Ru/La2O3 95.1 93.7
Ru/ZrO2·Al2O3 99.9 95.3
Ru/ZrO2·La2O3 98.7 92.2
Ru/ZrO2·CeO2 98.1 96.0
Ru/ZrO2·Pr6O11 97.7 89.5
Ru/ZrO2·Nd2O3 96.6 94.8
Ru/ZrO2·Yb2O3 97.0 90.2
Ru/ZrO2·V2O5 98.8 95.3
Ru/ZrO2·ZnO2 96.1 92.9
Ru/ZrO2·Nb2O5 97.0 90.1
Ru/ZrO2·MoO3 97.5 90.6
Ru/ZrO2·MgO 95.8 89.8
Rh/ZrO2·Al2O3 97.0 91..9
Pd/ZrO2·Al2O3 91.1 88.2
Os/ZrO2·Al2O3 95.6 91.6
Ir/ZrO2·Al2O3 91.9 88.1
Pt/ZrO2·Al2O3 96.6 92.1
Example 5: preparation of corresponding alkane compound by catalytic hydrodeoxygenation of different reactants
The procedure is as in example 4, except that 0.25mmol of the different carbonyl-or hydroxy-containing reactants indicated in Table 2 are used and only 50mg of the Ru/ZrO prepared in example 2 are used2·Al2O3The catalyst, the reaction materials and the results of gas chromatography are shown in Table 2.
Table 2: different reaction raw materials and corresponding conversion rate, corresponding product and yield result thereof
Figure BDA0001749612090000091
Figure BDA0001749612090000101
Example 6: preparation of alkane compounds (mixture of heptadecane and octadecane) by catalytic hydrodeoxygenation of stearic acid under different reaction conditions
The reaction procedure was the same as in example 4, except that only the Ru/ZrO prepared in example 2 was used2·Al2O3Catalysts were reacted at various temperatures, hydrogen pressures and times as shown in table 3 below.
These reactions all gave paraffinic compounds as a mixture of heptadecane and octadecane, and the results of gas chromatography are shown in Table 3.
Table 3: results of different reaction conditions and corresponding feedstock conversion and yield of paraffinic products
Figure BDA0001749612090000102
Example 7: preparation of alkane compounds (mixture of heptadecane and octadecane) by catalytic hydrodeoxygenation of stearic acid in different solvents
The reaction procedure was the same as in example 4, except that only 50mgRu/ZrO prepared in example 2 was used2·Al2O3The catalyst was added to 10mL of each of the different solvents shown in Table 4 below to carry out the reaction.
These reactions all gave paraffinic compounds as a mixture of heptadecane and octadecane and the results of gas chromatography are shown in Table 4.
Table 4: results for different reaction solvents and corresponding feedstock conversion and yield of paraffinic products
Figure BDA0001749612090000111
Example 8: evaluation of catalyst recycle Performance
The procedure is as in example 4, except that only 50mg of Ru/ZrO isolated after the end of the reaction in example 4 are used2·Al2O3The catalyst is hydrodeoxygenated with stearic acid to produce paraffinic compounds and the process is repeated five more times, i.e. the catalyst is separated again after the reaction and reused.
These reactions were all able to give paraffinic compounds as a mixture of heptadecane and octadecane and the results of gas chromatography are shown in table 5. From the results of table 5, it can be seen that the catalyst of the present invention has good stability and recyclability.
Table 5: the number of times of catalyst recycling and the corresponding results of feedstock conversion and yield of paraffinic products
Figure BDA0001749612090000112
Other embodiments
By the same preparation process as in example 1 or 2The following catalysts were also prepared according to the invention with active metal contents of 0.3%, 1.0%, 3.0%, 5.0%, 6.5% and 8.0%, respectively (based on the total weight of the catalyst): Ru/ZrO2·Al2O3、Ru/ZrO2·La2O3、Rh/ZrO2·Al2O3、Pd/ZrO2·Al2O3、Os/ZrO2·Al2O3、Ir/ZrO2·Al2O3And Pt/ZrO2·Al2O3And their performance for catalytic deoxygenation of carbonyl-or hydroxyl-containing compounds to produce paraffinic compounds was evaluated in the same reaction procedure as in example 4, showing that these catalysts all exhibit similar performance in the reaction as in example 4.
As shown in the above examples, the present invention provides a new method for preparing alkane compounds by catalytic deoxygenation of carbonyl or hydroxyl-containing compounds, which has mild reaction conditions and can recycle the catalyst after the reaction through simple separation. The invention can prepare alkane compounds used as solvent, organic synthetic raw material and/or fuel and the like from carbonyl or hydroxyl-containing compounds through catalytic deoxidation with high conversion rate, high selectivity, mild reaction conditions, simple reaction device and equipment and the like by adopting the supported metal catalyst with specific composition, and has good industrial application prospect.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (9)

1. A process for the catalytic deoxygenation of a carbonyl-or hydroxyl-containing compound to produce an alkane compound, said process comprising reacting the carbonyl-or hydroxyl-containing compound with H in the presence of a supported metal catalyst2Carrying out hydrodeoxygenation reaction to obtain alkane compounds,
whereinThe supported metal catalyst consists of a carrier and an active metal loaded on the carrier, wherein the carrier is selected from ZrO2·La2O3、ZrO2·Pr6O11、ZrO2·Nd2O3、ZrO2·Yb2O3、ZrO2·V2O5、ZrO2·ZnO、ZrO2·Nb2O5Or ZrO2MgO, the active metal being one or more selected from Ru, Rh, Pd, Os, Ir and Pt; and the hydrodeoxygenation reaction is carried out at the temperature of 100-230 ℃ and the H of 0.1-10 MPa2The reaction is carried out under pressure, and the reaction is carried out,
and the supported metal catalyst is prepared as follows:
a) mixing soluble salt containing carrier metal ions and a surfactant in water, adding an alkali solution to adjust the pH value to obtain a precipitate, and calcining the precipitate to obtain a catalyst carrier;
b) dispersing the obtained catalyst carrier in a solvent, adding salt containing active metal ions, stirring, mixing and drying to obtain the supported metal catalyst.
2. The method according to claim 1, wherein the supported metal catalyst is subjected to a pre-reduction treatment in a hydrogen atmosphere before use.
3. A method according to claim 1, characterized in that the carrier is ZrO2·La2O3。
4. The method of claim 1, wherein the active metal is present in an amount of 0.3 wt% to 8.0 wt%, based on the weight of the supported metal catalyst.
5. The method according to claim 1, characterized in that in step a), the surfactant is cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, polyvinylpyrrolidone or sodium dodecylbenzenesulfonate; the alkali solution is sodium hydroxide, potassium hydroxide, sodium carbonate or ammonia water solution; the calcining temperature is 400-800 ℃; in step b), the solvent is water, ethanol, acetone, diethyl ether, toluene or xylene; the salt containing active metal ions is nitrate, acetate or chloride salt.
6. The method of claim 1, wherein the carbonyl-or hydroxyl-containing compound is an alcohol, aldehyde, ketone, acid, or ester compound.
7. The method according to claim 1, wherein the hydrodeoxygenation reaction is carried out at a temperature of 100 to 200 ℃ and at a H of 1 to 8MPa2The reaction is carried out for 0.5 to 24 hours under pressure.
8. The method of claim 1, wherein the hydrodeoxygenation reaction is carried out at a temperature of 120 to 180 ℃ and a H of 2 to 6MPa2The reaction is carried out for 1-10 h under pressure.
9. The method of claim 1, wherein the supported metal catalyst is recycled.
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