CN115746923A - Method for preparing aviation fuel from lignin derivatives - Google Patents
Method for preparing aviation fuel from lignin derivatives Download PDFInfo
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- CN115746923A CN115746923A CN202211295572.8A CN202211295572A CN115746923A CN 115746923 A CN115746923 A CN 115746923A CN 202211295572 A CN202211295572 A CN 202211295572A CN 115746923 A CN115746923 A CN 115746923A
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- 229920005610 lignin Polymers 0.000 title claims abstract description 47
- 239000000446 fuel Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 23
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 150000002989 phenols Chemical class 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001299 aldehydes Chemical class 0.000 claims description 19
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 13
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical group O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 9
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 8
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- 229960001867 guaiacol Drugs 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 150000001335 aliphatic alkanes Chemical class 0.000 description 13
- -1 carbenium ion Chemical class 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- HWUPDMFSGDXFMI-UHFFFAOYSA-N C1CCCCC1.[C] Chemical compound C1CCCCC1.[C] HWUPDMFSGDXFMI-UHFFFAOYSA-N 0.000 description 8
- DXRZUVYXOONSEI-UHFFFAOYSA-N [C].C1(CCCCC1)C Chemical compound [C].C1(CCCCC1)C DXRZUVYXOONSEI-UHFFFAOYSA-N 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000029936 alkylation Effects 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DDFGTVSLZJLQEV-UHFFFAOYSA-N [C](C1CCCCC1)C1CCCCC1 Chemical compound [C](C1CCCCC1)C1CCCCC1 DDFGTVSLZJLQEV-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000002457 bidirectional effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical class C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical group CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- KNKXKITYRFJDNF-UHFFFAOYSA-N 2-methylphenol Chemical compound CC1=CC=CC=C1O.CC1=CC=CC=C1O KNKXKITYRFJDNF-UHFFFAOYSA-N 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 1
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing aviation fuel by using lignin derivatives. The method comprises the following steps: under the action of a first heteropoly acid catalyst, performing alkylation reaction on a lignin phenol derivative and a lignin aldehyde derivative under the condition of no solvent to obtain a tricyclic oxygen-containing fuel precursor; under the combined action of the second heteropoly acid catalyst and the hydrogenation metal catalyst, the tricyclic oxygen-containing fuel precursor is subjected to hydrodeoxygenation and isomerization reaction in a solvent to form a plurality of isomerized cycloalkanes. The invention can efficiently convert lignin phenolic derivatives with low carbon number and low calorific value into high-performance aviation fuel, and has better practical value.
Description
The technical field is as follows:
the invention relates to the technical field of organic matter preparation, in particular to a method for preparing aviation fuel from lignin derivatives.
Background art:
due to the non-renewable nature of fossil fuels and the adjustment of national energy strategies, renewable energy is an effective solution to the energy and carbon emissions problems. Biomass is widely considered to be sustainable, carbon dioxide neutral and the most abundant carbonaceous feedstock, and has become a fossil feedstock alternative source for the production of renewable fuels. Due to the particularities of the conditions of use of aircraft, carbon-based fuels remain irreplaceable. The preparation of high-performance aviation fuel by using renewable biomass-based raw materials accords with the national sustainable development strategy, and the source of the aviation fuel is also expanded.
Among them, increasing the carbon number by alkylation reaction has been widely studied. Alkylation is generally the coupling of an aromatic compound with a carbenium ion under acidic conditions, with the aim of increasing the number of carbons. Lignin, as a major component of biomass (15% -30%), is the most abundant source of aromatic compounds in nature. After hydrolysis, lignin generates a large amount of phenols and benzyl ether compounds, such as guaiacol, catechol, phenol, o-cresol, ethylphenol, and the like. Meanwhile, the aldehyde such as syringaldehyde, vanillin, p-tolualdehyde and the like can be formed, and the aldehyde is used as a substrate to carry out coupling of C-C bonds through alkylation reaction under an acidic condition, and then, the C-C bonds are subjected to hydrodeoxygenation to form an alkane product meeting the performance requirement of aviation fuel. There are many related technologies for producing aviation fuel from lignin derivatives. Most of the products are produced by taking phenols and benzyl ether compounds as substrates, alkylating the substrates under an acidic condition, and then hydrodeoxygenating the substrates under the catalysis of a commercially available metal supported catalyst and an acidic catalyst.
The invention content is as follows:
the invention solves the problems in the prior art and provides a method for preparing aviation fuel from lignin derivatives. The invention can efficiently convert lignin phenolic derivatives with low carbon number and low calorific value into high-performance aviation fuel, and has better practical value.
The invention aims to provide a method for preparing aviation fuel by using lignin derivatives, which comprises the following steps: under the action of a first heteropoly acid catalyst, performing alkylation reaction on a lignin phenol derivative and a lignin aldehyde derivative under the condition of no solvent to obtain a tricyclic oxygen-containing fuel precursor (alkylation reaction mixture/product); under the combined action of the second heteropolyacid catalyst and the hydrogenation metal catalyst, the tricyclic oxygen-containing fuel precursor is subjected to hydrodeoxygenation and isomerization reaction in a solvent to form a plurality of isomerized cycloalkanes (multi-component alkane products).
The tricyclic oxygen-containing fuel precursor prepared by the method does not need to be purified, and is subjected to hydrodeoxygenation and isomerization reaction under the synergistic action of the second heteropolyacid catalyst and the hydrogenation metal catalyst to form various isomerized cycloalkanes. The existing isomerization reactions are mostly isomerization of long-chain alkane, the method provided by the invention can be used for serially connecting a plurality of reactions of alkylation, hydrodeoxygenation and isomerization, the post-reaction treatment is not needed, the lignin ring structure is retained to the maximum extent, and the energy density of the fuel is improved.
The reaction equation for the above process, using phenol and benzaldehyde as reactants, is shown in formula I:
preferably, the method specifically comprises the following steps:
(1) Uniformly mixing a first heteropoly acid catalyst, a lignin phenol derivative and a lignin aldehyde derivative, and carrying out alkylation reaction for 0.5-6h at the temperature of 60-120 ℃ to obtain a tricyclic oxygen-containing fuel precursor (alkylation reaction mixture);
the tricyclic oxygen-containing fuel precursor has a structural formula shown in formula II:
wherein R is 1 Is OH, CH 3 Or OCH 3 ，R 2 Is OH, CH 3 Or OCH 3 ，R 3 Is OH, CH 3 Or OCH 3 ；
Taking phenol and benzaldehyde as reactants for example, the reaction equation in step (1) is shown in formula III:
(2) Putting a second heteropoly acid catalyst and a hydrogenation metal catalyst into a reaction vessel, then adding a solvent, and putting the tricyclic oxygen-containing fuel precursor obtained in the step (1) into the reaction vessel, wherein the hydrogen pressure is 2-5MPa, and the hydrogenation deoxidation and isomerization reaction are carried out at 180-230 ℃ for 6-24h to obtain a multi-component alkane product;
taking phenol and benzaldehyde as reactants for example, the reaction equation in step (2) is shown in formula IV:
the above process also isomerizes on the basis of hydrodeoxygenation, so that the high carbon number fuel precursor is fragmented to form the multi-component low carbon number alkanes. The carbon number and the property of the main alkane product in the multi-component alkane product meet the performance requirements of aviation fuel.
Preferably, the first heteropolyacid catalyst is phosphotungstic acid or silicotungstic acid, and the second heteropolyacid catalyst is phosphotungstic acid or silicotungstic acid.
Preferably, the molar ratio of the lignin phenolic derivative to the lignin aldehyde derivative is 1.5-2.5, and the molar ratio of the first heteropolyacid catalyst to the lignin aldehyde derivative is 0.009-0.037.
Preferably, the lignin phenolic derivative is selected from one of phenol, guaiacol, ethylphenol and o-cresol (o-methylphenol), and the lignin aldehyde derivative is selected from one of benzaldehyde, p-tolualdehyde and p-hydroxybenzaldehyde.
Preferably, the reaction temperature of the alkylation reaction is 60-100 ℃, and the reaction time is 2-4h.
Preferably, the hydrogenation metal catalyst in the step (2) is a platinum carbon catalyst or a palladium carbon catalyst, the mass ratio of the second heteropoly acid catalyst to the hydrogenation metal catalyst is 1:1, the solvent is a mixture of n-hexane and methanol or n-hexane, and the mass-to-volume ratio of the second heteropoly acid catalyst to the solvent is 0.002g/mL. Further preferably, the volume ratio of n-hexane to methanol in the mixed solvent of n-hexane and methanol is 17.
Preferably, the mass ratio of the tricyclic oxygen-containing fuel precursor to the second heteropolyacid catalyst is 36.75.
Preferably, the reaction temperature of the hydrodeoxygenation and isomerization reaction is 200-230 ℃, the reaction time is 12-24h, and the hydrogen pressure is 2-5MPa.
Compared with the prior art, the invention has the following advantages: the invention provides a method for converting lignin phenolic derivatives with low calorific value and low carbon number into alkane meeting the performance requirements of aviation fuel. The highly functionalized lignin phenol and aldehyde derivative have high alkylation reaction activity, can efficiently generate dialkyl products with tricyclic structures, and has the highest yield of 88.9%. The reaction path is simple, the reaction intermediate product can be directly subjected to hydrodeoxygenation and isomerization without treatment, and the carbon balance can reach 91.2 percent at most.
Description of the drawings:
FIG. 1 is a nuclear magnetic spectrum of a target product obtained in example 1 of the present invention;
FIG. 2 is a mass spectrum of dicyclohexylmethane, which is a main product obtained in example 16 of the present invention.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise specified, the experimental materials and reagents used herein are all conventional commercial products in the art.
A method for preparing aviation fuel from lignin derivatives comprises the following steps:
(1) Putting magnetons into a Schlenk tube, weighing a first heteropoly acid catalyst into the tube, uniformly mixing a lignin aldehyde derivative and a lignin phenol derivative, putting the mixture into the tube, installing the Schlenk tube, performing gas pumping and changing operation to enable the reaction to be performed in an argon atmosphere, reacting for 0.5-6h at the temperature of 60-120 ℃, and stirring at the speed of 700-900rpm to obtain an alkylation reaction mixture;
(2) Weighing a second heteropoly acid catalyst and a hydrogenation metal catalyst, adding the second heteropoly acid catalyst and the hydrogenation metal catalyst into a mechanical stirring kettle, adding a solvent into the mechanical stirring kettle, adding an alkylation reaction mixture into the mechanical stirring kettle, installing the mechanical stirring kettle, blowing the mechanical stirring kettle for a plurality of times by using hydrogen at normal temperature, then filling 2-5MPa hydrogen, and reacting for 6-24 hours at the temperature rising rate of 8-12 ℃/min and the temperature of 180-230 ℃ to obtain a multi-component alkane product.
In the following examples, the stirring speed in step (1) is preferably 700 to 900rpm, and the molar ratio of the lignin aldehyde derivative to the lignin phenol derivative is preferably 1.5 to 2.5, and more preferably 1:2. The molar ratio of the first heteropolyacid catalyst to the lignin aldehyde derivative is 0.009-0.037. The first heteropolyacid catalyst is phosphotungstic acid or silicotungstic acid. The lignin phenol derivative is selected from one of phenol, guaiacol, o-cresol and ethylphenol, and the lignin aldehyde derivative is selected from one of benzaldehyde, p-hydroxybenzaldehyde and p-tolualdehyde.
In the examples described below, step (2) preferably employs a phosphotungstic acid or a silicotungstic acid as the second heteropolyacid catalyst, a platinum carbon catalyst or a palladium carbon catalyst as the supported metal catalyst, and further preferably employs 5wt% of Pt/C as the supported metal catalyst. The reaction temperature is further preferably 200-230 ℃, the reaction time is further preferably 12-24h, the reaction solvent is n-hexane or a bidirectional system of n-hexane and methanol, and the bidirectional system of n-hexane and methanol with the volume ratio of 17.
The conversion rate and yield of the alkylation reaction are calculated as follows:
the conversion rate and the calculation mode of the hydrodeoxygenation and isomerization reaction are as follows:
example 1
Putting magnetons into a Schlenk tube, weighing 15mg phosphotungstic acid into the tube, weighing 5mmol benzaldehyde and 10mmol phenol, uniformly mixing, putting into the tube, installing the Schlenk tube, performing gas pumping and changing operation to enable the reaction to be performed under the argon atmosphere, reacting for 4 hours at 60 ℃, and stirring at the speed of 800rpm to obtain an alkylation reaction product (target product).
The target product was characterized as shown in fig. 1, and the conversion of benzaldehyde was 91.6%, the conversion of phenol was 71.1%, and the target product was 52.0%.
Example 2
Putting magnetons into a Schlenk tube, weighing 25mg phosphotungstic acid into the tube, weighing 5mmol benzaldehyde and 10mmol phenol, uniformly mixing, putting into the tube, installing the Schlenk tube, performing gas pumping and changing operation to enable the reaction to be performed under the argon atmosphere, reacting for 4 hours at 100 ℃, and stirring at the speed of 800rpm to obtain an alkylation reaction product (target product).
The conversion of benzaldehyde was 100%, the conversion of phenol was 80.7%, and the target product was 38.3%.
Examples 3 to 13
Reference is made to examples 1 and 2, with the difference that the reaction temperature, the amount of catalyst used and the time are different, see in particular table 1.
TABLE 1
Example 14
The same as example 1, except that: the first heteropolyacid catalyst is silicotungstic acid, the lignin phenol derivative is guaiacol, the lignin aldehyde derivative is benzaldehyde, the molar ratio of guaiacol to benzaldehyde is 1.5, the molar ratio of silicotungstic acid to benzaldehyde is 0.037, the reaction temperature of the alkylation reaction is 60 ℃, and the reaction time is 6 hours.
The yield of the alkylated product of example 14 was measured according to the test method of example 1, and the results were: the alkylation product of example 14 was obtained in a 70% yield.
Example 15
The same as example 1, except that: the first heteropolyacid catalyst is silicotungstic acid, the lignin phenol derivative is p-methylphenol, the lignin aldehyde derivative is p-methylbenzaldehyde, the molar ratio of p-methylphenol to p-methylbenzaldehyde is 1.
The yield of the alkylated product obtained in example 15 was measured according to the test method of example 1, and the results were: the alkylation product of example 15 was obtained in 80% yield.
Example 16
Weighing 40mg of phosphotungstic acid, adding 40mg of Pt/C5 wt% into a mechanical stirring kettle, adding 17mL of n-hexane into the kettle, dissolving 0.294g of the alkylation product prepared in example 13 into 3mL of methanol, adding into the mechanical stirring kettle, installing the mechanical stirring kettle, purging for 7 times by using hydrogen at normal temperature, filling 3MPa of hydrogen, increasing the temperature rate at 10 ℃/min, and reacting for 20 hours at 230 ℃ to obtain the multi-component alkane product. The mass spectrum of dicyclohexylmethane, the main product of the multi-component alkane product, is shown in fig. 2, the conversion of the substance in the multi-component alkane product is 92.0%, the yield of cyclohexane carbon is 29.4%, the yield of methylcyclohexane carbon is 5.4%, and the yield of dicyclohexyl carbon is 3.1% and the yield of dicyclohexyl methane carbon is 32.8%.
The density of dicyclohexylmethane obtained by the reaction is detected to be 0.876g/cm 3 The energy density was 37.0MJ/L. In contrast, the density of the commercially available long-chain tridecane was 0.756g/cm 3 The energy density is 34.0MJ/L.
Example 17
The same as in example 16, except that: the reaction temperature of the hydrodeoxygenation and isomerization reaction is 230 ℃, the reaction time is 6 hours, and the hydrogen pressure is 2MPa. The yield of cyclohexane carbon was 30%, that of methylcyclohexane carbon was 2.4%, that of bicyclohexane carbon was 4.98%, and that of dicyclohexylmethane carbon was 24%.
Example 18
The same as in example 16, except that: the reaction temperature of the hydrodeoxygenation and isomerization reaction is 180 ℃, the reaction time is 24 hours, and the hydrogen pressure is 5MPa. The yield of cyclohexane carbon was 16.1%, that of methylcyclohexane carbon was 5.1%, and that of dicyclohexylmethane carbon was 4.0% and 17.1%.
Example 19
The same as in example 16, except that: the reaction temperature of the hydrodeoxygenation and isomerization reaction is 200 ℃, the reaction time is 20h, and the hydrogen pressure is 5MPa. The yield of cyclohexane carbon was 23.5%, the yield of methylcyclohexane carbon was 4.7%, the yield of dicyclohexyl carbon was 3.0%, and the yield of dicyclohexyl methane carbon was 25%.
Example 20
The same as in example 16, except that: 5wt% of Pt/C40 mg to 5wt% Pd/C40 mg, cyclohexane carbon yield 24.0%, methylcyclohexane carbon yield 4.0%, dicyclohexylmethane carbon yield 2.0%, dicyclohexylmethane carbon yield 32.5%.
Example 21
The same as in example 16, except that: 5wt% of Pt/C40 mg to 5wt% of Ru/C40 mg, a cyclohexane carbon yield of 20.0%, a methylcyclohexane carbon yield of 2.5%, a dicyclohexylmethane carbon yield of 1.0%, and a dicyclohexylmethane carbon yield of 30.5%.
Example 22
The same as in example 16, except that: 5wt% of Pt/C40 mg to 5wt% Rh/C40 mg, cyclohexane carbon yield 22.5%, methylcyclohexane carbon yield 3.5%, dicyclohexylmethane carbon yield 1.5% 31.5%.
Comparative example 1
The same as in example 16, except that: the catalyst was 5wt% Pt/C40 mg and H-ZSM-5 40mg.
The reaction product obtained in comparative example 1 was examined according to the examination method of example 16, and as a result, the reaction product obtained in comparative example 1 was examined for a yield of 19.0% of cyclohexane carbon, 1.5% of methylcyclohexane carbon, 0% of dicyclohexylmethane carbon and 20.0% of dicyclohexylmethane carbon.
Comparative example 2
The same as in example 16, except that: the catalyst was 60mg of phosphotungstic acid (HPW) only.
The reaction product obtained in comparative example 2 was examined according to the examination method of example 16, and as a result of the examination, the yield of bicycloalkane in the reaction product obtained in comparative example 2 was 0%, and only the phenomenon of carbon-carbon bond cleavage occurred.
Comparative example 3
The same as in example 16, except that: the catalyst was only 5wt% Pt/C80 mg.
The reaction product obtained in comparative example 3 was examined according to the examination method of example 16, and as a result, the alkane yield in the reaction product obtained in comparative example 3 was 4%.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (9)
1. A method for preparing aviation fuel by using lignin derivatives is characterized by comprising the following steps: under the action of a first heteropoly acid catalyst, performing alkylation reaction on a lignin phenol derivative and a lignin aldehyde derivative under the condition of no solvent to obtain a tricyclic oxygen-containing fuel precursor; under the synergistic action of the second heteropolyacid catalyst and the hydrogenation metal catalyst, the tricyclic oxygen-containing fuel precursor is subjected to hydrodeoxygenation and isomerization reaction in a solvent to form a plurality of isomerized cycloalkanes.
2. The method according to claim 1, characterized in that it comprises in particular the steps of:
(1) Uniformly mixing a first heteropoly acid catalyst, a lignin phenol derivative and a lignin aldehyde derivative, and carrying out alkylation reaction for 0.5-6h at 60-100 ℃ to obtain a tricyclic oxygen-containing fuel precursor;
(2) And (2) putting a second heteropoly acid catalyst and a hydrogenation metal catalyst into a reaction vessel, then adding a solvent, and putting the tricyclic oxygen-containing fuel precursor obtained in the step (1) into the reaction vessel, wherein the hydrogen pressure is 2-5MPa, and the hydrogen pressure is 180-230 ℃ to perform hydrodeoxygenation and isomerization reaction for 6-24h to obtain various isomerized cyclanes.
3. A process according to claim 1 or 2, wherein the first heteropolyacid catalyst is a phosphotungstic acid or a silicotungstic acid and the second heteropolyacid catalyst is a phosphotungstic acid or a silicotungstic acid.
4. The method according to claim 1 or 2, wherein the molar ratio of the lignin phenolic derivative to the lignin aldehyde derivative is 1.5-2.5, and the molar ratio of the first heteropolyacid catalyst to the lignin aldehyde derivative is 0.009-0.037.
5. The method according to claim 1 or 4, wherein the lignin phenol derivative is selected from one of phenol, guaiacol, ethylphenol and o-cresol, and the lignin aldehyde derivative is selected from one of benzaldehyde, p-tolualdehyde and p-hydroxybenzaldehyde.
6. The process according to claim 1 or 2, wherein the alkylation reaction is carried out at a reaction temperature of 60 ℃ to 100 ℃ for a reaction time of 2 to 4 hours.
7. The method as claimed in claim 2, wherein the hydrogenation metal catalyst in step (2) is a platinum-carbon catalyst or a palladium-carbon catalyst, the mass ratio of the second heteropolyacid catalyst to the hydrogenation metal catalyst is 1:1, the solvent is a mixture of n-hexane and methanol or n-hexane, and the mass-to-volume ratio of the second heteropolyacid catalyst to the solvent is 0.002g/mL.
8. The process of claim 2 wherein the mass ratio of tricyclic oxygenate precursor to second heteropolyacid catalyst is 36.75.
9. The method according to claim 2, wherein the reaction temperature of the hydrodeoxygenation and isomerization reaction is 200-230 ℃, the reaction time is 12-24h, and the hydrogen pressure is 2-5MPa.
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