CN116836740A - Novel alpha-pinene-based biomass high-energy density fuel - Google Patents
Novel alpha-pinene-based biomass high-energy density fuel Download PDFInfo
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- pinene
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- hydrodeoxygenation
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- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 title claims abstract description 93
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 title claims abstract description 52
- 239000000446 fuel Substances 0.000 title claims abstract description 52
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002028 Biomass Substances 0.000 title claims abstract description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 6
- 230000008014 freezing Effects 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract 3
- 238000003442 catalytic alkylation reaction Methods 0.000 claims abstract 2
- 239000000047 product Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000005804 alkylation reaction Methods 0.000 claims description 15
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound 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 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 4
- 239000003377 acid catalyst Substances 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000006471 dimerization reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229930003658 monoterpene Natural products 0.000 description 2
- 235000002577 monoterpenes Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
- -1 polycyclic alkane Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/60—Controlling or regulating the processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2270/00—Specifically adapted fuels
- C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an alpha-pinene-based synthesized high-energy density fuel and a preparation method thereof. The method is characterized in that alpha-pinene and phenol are used as raw materials, and the molecular formula C with the content higher than 88% is obtained through acid catalytic alkylation, catalytic hydrodeoxygenation and distillation purification 16 H 28 Hydrodeoxygenation product of a monoalkylated product of (2) having a heating value of 40.1MJ/L,Density 0.93g/mL, viscosity 200mm at 15 DEG C ‑2 Excellent comprehensive performance of/s and freezing point-65 ℃ and meets the performance requirement of high-energy density fuel. The method opens up a feasible new way for preparing biomass-based high-energy density fuel and high-added-value deep processing of biomass resources such as alpha-pinene, phenol and the like at low cost.
Description
Technical Field
The invention relates to a novel alpha-pinene-based biomass high-energy density fuel and a preparation method thereof, in particular to a method for preparing a fuel component by alkylation of alpha-pinene and phenol under the catalysis of phosphotungstic acid and catalytic hydrodeoxygenation, belonging to the technical field of biomass high-energy density fuel preparation.
Background
High Energy Density Fuels (HEDF), which generally refer to single or multi-component mixed fuels having a density greater than 0.80g/mL, are used primarily in aerospace vehicles including aircraft, missiles, rockets, spacecraft, and satellites. The performance of the aircraft is greatly dependent on the performances such as the volumetric combustion heat value and the density of the fuel used by the aircraft, and the liquid hydrocarbon fuel with high density and high volumetric heat value can effectively improve the range, the navigational speed, the load and the like of the aerospace aircraft. Therefore, the molecular design and preparation technology of the high-density aviation fuel has great significance to the aerospace field.
The fuel used in the aerospace field at present is mainly prepared from petroleum through processes of rectification, cracking, reforming and the like, and contains C 6 ～C 16 Saturated straight chain, branched chain paraffins and naphthenes. Among them, chain hydrocarbons are the most common jet fuel component, but have lower volumetric heating value, and are difficult to meet the use requirements of high-performance aerospace vehicles. The adoption of cycloparaffin or polycyclic alkane can realize higher volume density, for example, the JP-10 density of the fuel with the main component of hanging tetrahydrodicyclopentadiene is 0.94g/mL, which is more than 15 percent higher than that of the traditional aviation kerosene. At present, high-energy density hydrocarbon fuels with the density of 0.93-1.21 g/mL can be synthesized in various countries. However, these high energy density jet fuels are still derived from non-renewable fossil feedstocks. With the continuous growth of world population and the increase of global energy consumption, development of novel high-energy-density fuel by taking renewable biomass resources as raw materials is urgently needed, so that dependence on fossil raw materials is reduced, and the aims of carbon neutralization and carbon peak reaching are fulfilled.
Cyclic monoterpenes present in nature are an important class of cycloalkanes that can be used as ideal biomass sources for advanced jet fuels [ Energy ]&Fuels,2020,34(5):5929–5937]Wherein, the Chinese is rich in yieldThe turpentine resource takes alpha-pinene as the main component, and can provide C for the construction of high-energy density fuel due to the advantages of compact molecular structure, polycyclic structure, double bonds between the inner ring and the outer ring and the like 10 A molecular skeleton. However, the saturated hydrocarbon obtained by directly hydrogenating monoterpenes such as alpha-pinene has low energy density, low flash point and insufficient safety, and is difficult to meet the requirements of modern high-performance aircrafts. In the prior art, C is obtained by acid catalysis of pinene dimerization reaction 20 The carburetion product has higher density and combustion heat, but the low-temperature viscosity is too high, the freezing point is too high, and the carburetion product is difficult to be directly applied to high-altitude low-temperature environments. Although the carbureted product obtained by cyclopropanization of pinene has better Fuel performance, the preparation process involves an organic solvent, a Zn carbene catalyst which is difficult to recycle and a diiodimethane carbureted module with poor atomic economy [ Fuel,2022,307:121906]Likewise, C is used 4 The problems of petroleum-based raw materials, complex components of reaction products and the like [ ZL2021112247490 ] still exist in the preparation of fuel by carburating alpha-pinene by mixed hydrocarbon]. If the raw materials from biomass can be used as carburetion modules, the novel pinene-based high-density fuel molecules can be constructed, and the novel pinene-based high-density fuel molecules have more important sustainable development significance. However, the carburetion reaction of the alpha-pinene has great difficulty due to the self structure and the reaction performance characteristics of the alpha-pinene, and particularly, a reaction module derived from biomass is adopted to carburetze the alpha-pinene to construct novel molecules, and a fuel product with good performance is prepared, which is more recently reported.
The invention is proposed for this purpose.
According to the invention, on the basis of screening the reaction performance of lignin derived phenols such as phenol, anisole, guaiacol, 4-methyl guaiacol and alpha-pinene under the promotion of various catalysts, the alkylation reaction of the alpha-pinene and phenol under the catalysis of phosphotungstic acid is realized for the first time, and the high-density product with excellent comprehensive performance is obtained after further hydrodeoxygenation and purification, and can be used as a novel biomass-based high-energy density fuel or fuel additive. So far, no relevant report is found at home and abroad.
Disclosure of Invention
The invention aims to provide a novel biomass high-energy density fuel and a preparation method thereof: alpha-pinene and lignin depolymerized monomer phenol are used as raw materials, phosphotungstic acid is used for catalyzing alkylation reaction, and a product mixture is subjected to catalytic hydrodeoxygenation and distillation to obtain the novel alpha-pinene-based biomass high-energy density fuel.
The invention is realized by the following technical scheme:
adding a certain amount of phenol into a normal pressure batch reactor provided with a reflux and stirring device, heating to 160 ℃, adding 10wt% of phosphotungstic acid which is roasted for 3 hours at 250 ℃ in a muffle furnace as a catalyst based on the amount of the phenol, and then dropwise adding 0.5 times of the molar amount of alpha-pinene for reacting for 4 hours, wherein the reaction process is schematically as follows:
separating and removing phosphotungstic acid after alkylation reaction, transferring the liquid mixture into a stainless steel high-pressure reaction kettle, adding 10wt% of Pd/C and HZSM-5 zeolite according to the proportion of 5wt% and 10wt% of phenol respectively, adding deionized water according to the proportion of 10mL per gram of phenol, sealing, and respectively using N 2 And H 2 Replacing the atmosphere in the kettle, and filling 4MPa H 2 Stirring and reacting for 48 hours at 200 ℃, wherein the reaction process is schematically shown as follows:
and separating out an organic phase product after the hydrodeoxygenation reaction is finished, and performing reduced pressure distillation to obtain the alpha-pinene-based biomass high-density fuel product.
The method adopts alpha-pinene and lignin depolymerized monomer phenol as raw materials, and the novel biomass-based mixed high-density fuel product is obtained through alkylation reaction and hydrodeoxygenation reaction, and the density and the heat value of the product are similar to those of an alpha-pinene dimerization hydrogenation product, but the low-temperature performances such as freezing point and viscosity are far better than those of the alpha-pinene dimerization hydrogenation product. The invention provides a new method for obtaining the pine-pitch oil-based high-energy-density fuel with low cost and excellent performance.
Drawings
FIG. 1 is a gas chromatogram of the reaction product of alkylation of phenol and α -pinene obtained in example 1.
FIG. 2 is a gas chromatogram of the hydrodeoxygenation product obtained in example 2.
FIG. 3 is a gas chromatogram of the high energy density fuel product obtained in example 3.
FIG. 4 is a gas chromatogram of the distilled substrate described in example 4.
Detailed Description
The process of the present invention is further illustrated, but is not intended to be limiting, by the following examples.
Example 1
5g of phenol is added into a three-neck flask provided with a reflux condenser and a stirring device, the temperature is raised to 160 ℃,0.5g of phosphotungstic acid which is roasted for 3 hours at 250 ℃ in a muffle furnace is added, 4.3mL of alpha-pinene is added dropwise, the reaction is carried out for 4 hours, cooling separation is carried out, and the phosphotungstic acid is removed, thus the gas chromatogram of the obtained alkylation reaction mixture is shown in figure 1. Through gas chromatography-mass spectrometry analysis, the main component in the mixed solution is C 16 H 22 O, a mono-alkylated product of alpha-pinene and phenol, and in addition, contains a small amount of alpha-pinene (C 10 H 16 ) Phenol (C) 6 H 6 O), p-cymene (C) produced by isomerism of alpha-pinene 10 H 14 ) Alpha-pinene autodimerization product (C) 20 H 32 ) And the product of dialkylation of alpha-pinene with phenol (C 26 H 38 O)。
Example 2
The alkylation reaction mixture obtained in example 1 was transferred to a stainless steel autoclave, 50mL of deionized water was added, 0.5g of 10wt% Pd/C and 1g of HZSM-5 zeolite having a silica-alumina ratio of 27, and after sealing, the mixture was treated with N 2 4 times with H 2 3 times of replacement and 4MPa H recharging 2 The reaction was stirred at 200℃for 48h. Cooling and exhausting after the reaction is finished, and removing low-boiling-point components by rotary evaporation of an upper organic phase, wherein a gas chromatogram is shown in figure 2. Through gas chromatography-mass spectrometry analysis, the main component in the mixed solution is C 16 H 28 Mono-alkyl of (2)Hydrodeoxygenation products of the product, in addition, hydrogenation products (C) comprising alpha-pinene and isomers thereof 10 H 20 ) Dicyclohexyl (C) obtained by hydrodeoxygenation of phenol 12 H 22 ) Hydrogenation product of alpha-pinene dimer (C 20 H 34 ) Hydrodeoxygenation product of dialkylated product (C) 26 H 44 ). The composition and fuel properties of the mixture are shown in Table 1.
Example 3
The liquid product obtained in example 2 was distilled under reduced pressure at a vacuum degree of-0.1 MPa, and the fraction at 140.+ -. 2 ℃ was taken to obtain a gas chromatogram of the fuel product shown in FIG. 3, whose composition and fuel properties are shown in Table 1.
Example 4
The distilled substrate obtained in example 3 was collected, the gas chromatogram thereof was shown in FIG. 4, and the composition and fuel properties thereof were shown in Table 1.
Comparative example 1
The fuel properties of the commercial pinane were measured and are shown in Table 1.
Comparative example 2
20mL of toluene and 2g of phosphotungstic acid baked for 3 hours at 250 ℃ in a muffle furnace are added into a three-neck flask provided with a reflux condenser and a stirring device, 20mL of alpha-pinene is dripped when the temperature is heated to 90 ℃, the reaction is carried out for 10 hours after the dripping is finished, and after phosphotungstic acid is separated and removed, solvent toluene, unreacted alpha-pinene and isomerism products thereof are distilled off under normal pressure. 10mL of the obtained dimerization product was taken and added to a stainless steel autoclave together with 1g of 10wt% Pd/C, and after the autoclave was sealed, the reaction mixture was treated with N 2 4 times with H 2 3 times replacement, recharging with 3MPaH 2 The reaction was stirred at 120℃for 4h. After the reaction, the exhaust gas was cooled, and the fuel properties of the dimerization-hydrogenation product obtained after the separation and removal of the solid catalyst were shown in table 1.
TABLE 1 composition and fuel properties of alpha-pinene and phenol alkylation-hydrodeoxygenation products
Claims (7)
1. An alpha-pinene-based biomass high-energy density fuel is characterized in that alpha-pinene and phenol are adopted to carry out alkylation reaction under the catalysis of acid, and then catalytic hydrodeoxygenation and purification are carried out, so that a polycyclic saturated hydrocarbon product with a heat value of more than 39MJ/L, a density of more than 0.9g/mL and a viscosity of less than 300mm at minus 15 ℃ is prepared -2 And/s, the freezing point is lower than-60 ℃.
2. The alpha-pinene based biomass high energy density fuel according to claim 1, characterized in that the heat value of the product is 39-42 MJ/L, the density is 0.9-0.95 g/mL, and the viscosity at 15 ℃ is 150-300 mm -2 And/s, freezing point is-60 to-70 ℃.
3. The alpha-pinene based biomass high energy density fuel of claim 2, wherein the product has a calorific value of 40.1MJ/L, a density of 0.93g/mL, and a viscosity of 200mm at-15 ℃ -2 S, freezing point-65. DEG C
4. A method of preparing the α -pinene based biomass high energy density fuel of claim 1, comprising the steps of:
(1) The method comprises the steps of taking alpha-pinene and phenol as raw materials, sequentially carrying out acid catalytic alkylation reaction and catalytic hydrodeoxygenation reaction, and separating a catalyst and a solvent after the reaction is finished to obtain a hydrodeoxygenation product;
(2) And (3) distilling the hydrodeoxygenation product obtained in the step (1) under reduced pressure to obtain the alpha-pinene-based biomass high-energy density fuel.
5. A method of preparing the α -pinene based biomass high energy density fuel of claim 2, characterized by comprising the following process:
(1) Alpha-pinene and phenol are used as raw materials, phosphotungstic acid is used as an acid catalyst, pd/C and HZSM-5 zeolite are used as hydrodeoxygenation catalysts, and alkylation reaction and hydrodeoxygenation reaction are carried out successively; wherein the alkylation reaction conditions are: the reaction temperature is 160 ℃, the reaction time is 4 hours, and the feeding mode of the alpha-pinene is dropwise adding; separating out the catalyst after the alkylation reaction is finished, and further hydrodeoxygenation is carried out on the obtained liquid product in a stainless steel high-pressure reaction kettle, wherein the reaction conditions are as follows: the initial hydrogen pressure is 4MPa, the reaction temperature is 200 ℃, the reaction time is 48 hours, and after the reaction is finished, the catalyst and water are separated to obtain a hydrodeoxygenation product;
(2) Distilling the hydrodeoxygenation product obtained in the step (1) under reduced pressure at a vacuum degree of-0.1 MPa, and collecting the hydrodeoxygenation product at 140+/-10 DEG C
And (3) obtaining the alpha-pinene-based biomass high-energy density fuel.
6. A method of preparing the α -pinene based biomass high energy density fuel of claim 3, characterized by comprising the following process:
(1) Alpha-pinene and phenol are used as raw materials, phosphotungstic acid roasted for 3 hours at 250 ℃ is used as an acid catalyst, pd/C and HZSM-5 zeolite are used as hydrodeoxygenation catalysts, and alkylation reaction and hydrodeoxygenation reaction are carried out successively; wherein the alkylation reaction conditions are: the amount of the phenol is twice that of the alpha-pinene, the dosage of the phosphotungstic acid catalyst is 10 percent of the mass of the phenol, the reaction temperature is 160 ℃, the reaction time is 4 hours, and the feeding mode of the alpha-pinene is dripping; separating out the catalyst after the alkylation reaction is finished, and further hydrodeoxygenation is carried out on the obtained liquid product in a stainless steel high-pressure reaction kettle, wherein the reaction conditions are as follows: 10wt% Pd/C5% based on the mass of phenol, HZSM-5 having a silica-alumina ratio of 27
The zeolite amount is 10% of the phenol mass, the solvent water amount is 10 mL/g phenol, the initial hydrogen pressure is 4MPa,
the reaction temperature is 200 ℃, the reaction time is 48 hours, and after the reaction is finished, the catalyst and water are separated to obtain a hydrodeoxygenation product;
(2) And (3) carrying out reduced pressure distillation on the hydrodeoxygenation product obtained in the step (1) under the vacuum degree of-0.1 MPa, and collecting fractions at the temperature of 140+/-2 ℃ to obtain the alpha-pinene-based biomass high-energy density fuel.
7. Use of the α -pinene based biomass high energy density fuel of any one of claims 1-3 in the aerospace field.
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