CN109852441A - A kind of polycyclic high-density biology matter liquid fuel and the preparation method and application thereof - Google Patents

A kind of polycyclic high-density biology matter liquid fuel and the preparation method and application thereof Download PDF

Info

Publication number
CN109852441A
CN109852441A CN201910017003.9A CN201910017003A CN109852441A CN 109852441 A CN109852441 A CN 109852441A CN 201910017003 A CN201910017003 A CN 201910017003A CN 109852441 A CN109852441 A CN 109852441A
Authority
CN
China
Prior art keywords
liquid fuel
acid
reaction
biology matter
matter liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910017003.9A
Other languages
Chinese (zh)
Other versions
CN109852441B (en
Inventor
王伟
张田雷
邵先钊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Technology
Original Assignee
Shaanxi University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Technology filed Critical Shaanxi University of Technology
Priority to CN201910017003.9A priority Critical patent/CN109852441B/en
Publication of CN109852441A publication Critical patent/CN109852441A/en
Application granted granted Critical
Publication of CN109852441B publication Critical patent/CN109852441B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of polycyclic high-density biology matter liquid fuels and the preparation method and application thereof.The present invention passes through aldol reaction under acid catalyst effect using cyclic ketones object, vanillic aldehyde as reaction raw materials, by the reaction raw materials and the first solvent, obtains Primary product；Wherein, cyclic ketones object is at least one of cyclopentanone and cyclohexanone；Hydrogenation deoxidation reaction is directly carried out in the second solvent to Primary product by load type metal catalyst, obtaining by carbochain is C19And/or C20Polycyoalkane constitute polycyclic high-density biology matter liquid fuel.The polycyclic high-density biology matter liquid fuel of the present invention can be used as aviation fuel or aviation fuel additive uses.Polycyclic high-density biology matter liquid fuel yield prepared by the present invention is up to 90% or more, and the polycyclic biomass liquid fuel can be used directly as the additive of high-quality aviation fuel or aviation fuel.

Description

A kind of polycyclic high-density biology matter liquid fuel and the preparation method and application thereof
Technical field
The invention belongs to biomass energy technology field more particularly to a kind of polycyclic high-density biology matter liquid fuel and its Preparation method and application.
Background technique
Space flight and aviation science and technology is the important embodiment of national science and technology level, research strength, and aerospace vehicle includes aircraft, leads Bullet, rocket, airship, satellite etc..The performances such as voyage, the speed of a ship or plane and the load of aircraft depend greatly on fuel combustion institute The heat of release.High Density Hydrocarbon Fuels also have bigger mass density and body in addition to having the advantages that general liquid fuel Accumulated heat value.In the case where aircraft fuel case given volume, the boat of aircraft can be greatly improved using high Density Hydrocarbon Fuels Journey, the speed of a ship or plane and payload.In the case where keeping flying quality constant, fuel tank is significantly reduced using high Density Hydrocarbon Fuels Volume leaves space for other purposes, realizes the miniaturization of aircraft.Therefore, both met using high Density Hydrocarbon Fuels novel Aircraft, which promotes, to be required, and the propulsive performance of existing aircraft is also improved.To meet requirement, high Density Hydrocarbon Fuels are also answered There is the features such as lower freezing point, suitable flash-point, low viscosity, stable storing and low toxicity.
Biomass higher density fluid fluid fuel is a kind of renewable New-type fuel.Application number is respectively 201310231662.5, 201410736866.9, in 201710130759.5 Chinese patent, use lignocellulosic based platform compound for raw material warp Aldol condensation obtains the oxygenatedchemicals with polycyclic diesel range, and obtains these compound direct hydrogenation deoxidations with height Spend the hydro carbons of diesel range.It is reacted using cyclopentanone condensation or cyclopentanol through Guerbet and generates two ring (C10) and tricyclic (C15) contain Oxygen compound, the selection of cyclopentanone dimer plus hydrogen are condensed and (C are made20) oxygenatedchemicals, then hydrogenation deoxidation be made two rings (C10), tricyclic (C15) and Fourth Ring (C20) high density cyclic hydrocarbon fuel.
Summary of the invention
The primary purpose of the present invention is that providing a kind of polycyclic high-density biology matter liquid fuel.
Another object of the present invention is to provide the preparation methods of above-mentioned polycyclic high-density biology matter liquid fuel.
A further object of the present invention is to provide the applications of above-mentioned polycyclic high-density biology matter liquid fuel.
The invention is realized in this way a kind of preparation method of polycyclic high-density biology matter liquid fuel, this method include Following steps:
(1) using cyclic ketones object, vanillic aldehyde as reaction raw materials, the reaction raw materials and the first solvent are passed through into hydroxyl under acid catalyst effect Aldehyde condensation reaction, obtains Primary product；Wherein, the cyclic ketones object is at least one of cyclopentanone and cyclohexanone；
(2) as load type metal catalyst Primary product made from step (1) is directly carried out in the second solvent plus hydrogen Deoxygenation, obtaining by carbochain is C19And/or C20Polycyoalkane constitute polycyclic high-density biology matter liquid fuel.
Preferably, in step (1), mass concentration of the reaction raw materials in the first solvent is 5 ~ 90%；The cyclic ketones Object, vanillic aldehyde molar ratio be 1:(1 ~ 4)；The mass ratio of the acid catalyst and cyclic ketones object is (1 ~ 20): 100；The aldol Condensation reaction time be 0.5 ~ for 24 hours, reaction temperature be 40 ~ 100 DEG C；
In step (2), mass concentration of the Primary product in the second solvent is 1 ~ 60%；The load type metal catalysis The mass ratio of agent and Primary product is (1 ~ 20): 100；The hydrogenation deoxidation reaction carries out in intermittent tank reactor, In, the reaction condition in tank reactor are as follows: 150 ~ 400 DEG C of reaction temperature, the reaction time is 6 ~ 48 h, Hydrogen Vapor Pressure 0.5 To 10.0 MPa.
Preferably, in step (1), mass concentration of the reaction raw materials in the first solvent is 30 ~ 60%；The ring The molar ratio of pentanone and vanillic aldehyde is 1:2；The mass ratio of the acid catalyst and cyclic ketones object is (5 ~ 10): 100；The aldol contracting The conjunction reaction time is 4 ~ 12h, and reaction temperature is 60 ~ 90 DEG C；
In step (2), mass concentration of the Primary product in the second solvent is 3 ~ 20%；The load type metal catalysis The mass ratio of agent and Primary product is (5 ~ 10): 100；Reaction condition in the tank reactor are as follows: reaction temperature be 240 ~ 350 DEG C, the reaction time is 12 ~ 24 h, and Hydrogen Vapor Pressure is 2.0 ~ 6.0MPa.
Preferably, in step (1), the acid catalyst is solid acid or liquid acid；First solvent is ethyl alcohol, first At least one of alcohol, tetrahydrofuran (THF)；
In step (2), the carrier of the load type metal catalyst includes active carbon, SiO2、SiO2/Al2O3、H-ZSM-5、 H- beta-molecular sieve, H-Y molecular sieve and montmorillonite K10, at least one in the supported on carriers precious metals pt, Pd, Ru and Ir Kind；Second solvent is at least one of hexamethylene, n-hexane, normal octane, tridecane and decahydronaphthalene.
Preferably, the solid acid is Nafion resin, in Amberlyst15, Amberlyst36, Amberlyst70 It is at least one；The liquid acid is at least one of sulfuric acid, nitric acid, fluoroform acetic acid, phosphoric acid and p-methyl benzenesulfonic acid.
Preferably, the preparation of the load type metal catalyst is the following steps are included: the active carbon that nitric acid treatment is crossed adds Enter the precious metal solution to mass concentration 1 ~ 10%；By carrier after 500 DEG C of temperature lower calcination 4h incipient impregnation in your above-mentioned gold Belong in solution, dries 6 ~ 24 h at 80 ~ 120 DEG C after standing 24 h, then use 1 ~ 10 h of hydrogen reducing at 200 ~ 600 DEG C, to After temperature is reduced to room temperature, it is passed through nitrogen inerting 4 h or more that oxygenous volumetric concentration is 1%.
The present invention further discloses the polycyclic high-density biology matter liquid fuels that the above method is prepared.
The present invention further discloses above-mentioned polycyclic high-density biology matter liquid fuels in terms of as aviation fuel Application.
The present invention further discloses above-mentioned polycyclic high-density biology matter liquid fuels to add as aviation fuel Application in terms of agent.
The present invention overcomes the deficiencies of the prior art and provide a kind of polycyclic high-density biology matter liquid fuel and preparation method thereof With application, the present invention is by the way that using cyclic ketones object, vanillic aldehyde as reaction raw materials, the reaction raw materials and the first solvent are made in acid catalyst Pass through aldol reaction with lower, obtains Primary product；Wherein, the cyclic ketones object is at least one in cyclopentanone and cyclohexanone Kind；By load type metal catalyst hydrogenation deoxidation reaction is directly carried out to Primary product in the second solvent, obtained by carbochain For C19And/or C20Polycyoalkane constitute high-density biology matter liquid fuel.Wherein, when cyclic ketones object is cyclopentanone, gained The Primary product arrived is bis- (the 4- hydroxy-3-methoxy benzal) cyclopentanone of 2,6-, and finally obtaining by carbochain is C19It is polycyclic The high-density biology matter liquid fuel (density 0.9261g/mL, freezing point temperature are -31.8 DEG C) that alkane is constituted, the reaction process Specifically:
；
When cyclic ketones object is cyclohexanone, obtained Primary product is bis- (the 4- hydroxy-3-methoxy benzal) cyclohexanone of 2,6-, And finally obtaining by carbochain is C20Polycyoalkane constitute high-density biology matter liquid fuel (density 0.9312g/mL, ice Point temperature is -32.1 DEG C), the reaction process specifically:
。
When cyclic ketones object is the mixture of cyclopentanone and cyclohexanone, obtained Primary product is the bis- (4- hydroxyl -3- of 2,6- Benzylidene) cyclopentanone, bis- (the 4- hydroxy-3-methoxy benzal) cyclohexanone of 2,6- mixture, and finally obtain by Carbochain is C19、C20Polycyoalkane constitute high-density biology matter liquid fuel.
Compared with the prior art the shortcomings that and deficiency, the invention has the following advantages: the present invention provide it is a kind of new The route of polycyclic high-density biology matter liquid fuel is prepared, yield is up to 90% or more, and the polycyclic biomass liquid fuel can be straight It connects and is used as the additive of high-quality aviation fuel or aviation fuel.
Detailed description of the invention
Fig. 1 is the H-NMR figure of bis- (the 4- hydroxy-3-methoxy benzal) cyclopentanone of 2,6- in the present invention；
Fig. 2 is the H-NMR figure of bis- (the 4- hydroxy-3-methoxy benzal) cyclohexanone of 2,6- in the present invention；
Fig. 3 is the gas chromatogram of bis- (4- hydroxy-3-methoxy benzal) the cyclopentanone hydrogenation deoxidation products of 2,6-；
Fig. 4 is the gas chromatogram of bis- (4- hydroxy-3-methoxy benzal) the cyclohexanone hydrogenation deoxidation products of 2,6-；
Fig. 5 is the mass spectrogram of bis- (cyclohexyl methyl) pentamethylene of 1,3-；
Fig. 6 is the mass spectrogram of bis- (cyclohexyl methyl) hexamethylenes of 1,3-.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
One, the preparation of catalyst
(1) preparation of acid catalyst
Acid catalyst sulfuric acid, nitric acid, phosphoric acid, p-methyl benzenesulfonic acid, trifluoroacetic acid, Nafion resin, Amberlyst15, Amberlyst36, Amberlyst70 etc. are purchased from commercial reagents.
(2) preparation of load type metal catalyst
Palladium chloride, ruthenic chloride, chloroplatinic acid, the chloro-iridic acid for preparing mass ratio 10%, by one such or two or more metal salt Solution is crossed than addition nitric acid treatment according to metering and (nitric acid solution of 250mL33% is added in 50g active carbon, in 80 DEG C of water-bath Middle processing 12 hours, filtering are washed with deionized water to neutrality, then 120 DEG C 12 hours active carbons of oven drying (AC), SiO2、SiO2/Al2O3, H-ZSM-5, H- beta-molecular sieve or the medium volume impregnation of montmorillonite K10,24 h are then allowed to stand, at 80 DEG C Under be dried overnight, at 500 DEG C use 2 h of hydrogen reducing, 1% O is passed through after temperature is reduced to room temperature2Nitrogen inerting 2 h, can make Standby monometallic or bimetallic load type metal catalyst.
1 load type metal catalyst of table
Embodiment Carrier Metal and its loading Embodiment Carrier Metal and its loading
1 AC 0.5% Pd 16 SiO2 5% Pt
2 AC 1% Pd 17 SiO2/Al2O3 5% Pt
3 AC 2% Pd 18 H-ZSM-5 5% Pt
4 AC 5% Pd 19 H- beta-molecular sieve 5% Pt
5 AC 10% Pd 20 Montmorillonite K10 5% Pt
6 AC 5% Ru 21 HY 5% Pt
7 AC 5% Pt 22 Fly ash base carrier 5% Pt
8 AC 5% Ir 23 HY 5% Ir
9 SiO2 5% Pd 24 SiO2 5% Ru
10 SiO2/Al2O3 5% Pd 25 SiO2/Al2O3 5% Ru
11 H-ZSM-5 5% Pd 26 H-ZSM-5 5% Ru
12 H- beta-molecular sieve 5% Pd 27 H- beta-molecular sieve 5% Ru
13 Montmorillonite K10 5% Pd 28 Montmorillonite K10 5% Ru
14 HY 5% Pd 29 HY 5% Ru
15 Fly ash base carrier 5% Pd 30 Fly ash base carrier 5% Ru
Two, the preparation of biomass liquid fuel
(1) be added in the round-bottomed flask or stainless steel cauldron of 100 mL a certain amount of cyclopentanone, vanillic aldehyde, the first solvent and Acid catalyst reacts certain time under stirring in the water bath with thermostatic control or oil bath of set temperature, and end of reaction is down to room temperature, rotation Steam the first solvent.If making catalyst with liquid acid, addition appropriate amount of deionized water, appropriate dehydrated alcohol successively wash away sour and not anti- The product for the raw material answered.If making catalyst with solid acid, it is added appropriate tetrahydrofuran dissolved product, filter filtration catalizer, Organic phase rotates out the first solvent, appropriate amount of deionized water is added, appropriate dehydrated alcohol successively washes away sour and unreacted raw material Product.
2 cyclopentanone of table and vanillic aldehyde response parameter and its result
Embodiment Cyclopentanone/g Vanillic aldehyde/g Acid catalyst/g First solvent/mL Temperature/DEG C Time/h Yield/%
31 0.84 3.04 0.05g sulfuric acid 6ml ethyl alcohol 80 8 92.4
32 0.84 3.04 0.05g nitric acid 6ml ethyl alcohol 80 8 50.8
33 0.84 3.04 0.05g phosphoric acid 12ml ethyl alcohol 80 8 64.7
34 0.84 3.04 0.05g p-methyl benzenesulfonic acid 12ml ethyl alcohol 80 8 85.8
35 0.84 3.04 0.05g trifluoroacetic acid 6ml ethyl alcohol 80 8 72.8
36 0.84 3.04 0.05gNafion 6ml ethyl alcohol 80 10 58.8
37 0.84 3.04 0.05g Amberlyst15 6ml ethyl alcohol 80 10 45.5
38 0.84 3.04 0.05gAmberlyst36 6ml ethyl alcohol 80 10 48.8
39 0.84 3.04 0.05gAmberlyst70 6ml ethyl alcohol 80 10 42.7
40 0.84 3.04 0.05g sulfuric acid 6ml ethyl alcohol 60 6 82.7
41 0.84 3.04 0.05g sulfuric acid 6ml methanol 60 4 62.5
42 0.84 3.04 0.05g nitric acid 6ml methanol 60 6 32.6
43 0.84 3.04 0.05g phosphoric acid 6ml methanol 60 10 48.8
44 0.84 3.04 0.05g p-methyl benzenesulfonic acid 6ml methanol 60 10 78.9
45 0.84 3.04 0.05g trifluoroacetic acid 6ml methanol 60 8 65.7
46 0.84 3.04 0.05gNafion 20ml methanol 60 12 58.7
47 0.84 3.04 0.05g Amberlyst15 20ml methanol 60 6 43.8
48 0.84 3.04 0.05gAmberlyst36 20ml methanol 60 10 38.9
49 0.84 3.04 0.05gAmberlyst70 12ml methanol 60 10 39.4
50 0.84 3.04 0.05g sulfuric acid 6ml methanol 40 10 64.2
51 0.84 3.04 0.05g sulfuric acid 6ml THF 40 4 88.5
52 0.84 3.04 0.05g nitric acid 6ml THF 40 6 40.6
53 0.84 3.04 0.05g phosphoric acid 6ml THF 40 10 78.8
54 0.84 3.04 0.05g p-methyl benzenesulfonic acid 6ml THF 100 10 89.9
55 0.84 3.04 0.05g trifluoroacetic acid 4ml THF 100 12 87.7
56 0.84 3.04 0.05gNafion 6ml THF 100 8 88.9
57 0.84 3.04 0.05g Amberlyst15 6ml THF 100 12 75.8
58 0.84 3.04 0.05gAmberlyst36 6ml THF 100 12 77.8
59 0.84 3.04 0.05gAmberlyst70 6ml THF 100 12 79.4
60 0.84 1.52 0.05g sulfuric acid 4ml THF 80 8 42.8
3 cyclohexanone of table and vanillic aldehyde response parameter and its result
Embodiment Cyclopentanone/g Vanillic aldehyde/g Acid catalyst/g First solvent/mL Temperature/DEG C Time/h Yield/%
61 0.98 3.04 0.05g sulfuric acid 6ml ethyl alcohol 80 8 92.5
62 0.98 3.04 0.05g sulfuric acid 6ml THF 80 10 91.2
63 0.98 3.04 0.05g phosphoric acid 6ml ethyl alcohol 80 12 92.5
64 0.98 3.04 0.05g p-methyl benzenesulfonic acid 6ml ethyl alcohol 80 12 91.6
65 0.98 3.04 0.05g trifluoroacetic acid 6ml ethyl alcohol 80 10 88.4
66 0.98 3.04 0.05gNafion 6ml ethyl alcohol 80 10 70.5
67 0.98 3.04 0.05g Amberlyst15 6ml ethyl alcohol 80 8 60.8
68 0.98 3.04 0.05gAmberlyst36 6ml ethyl alcohol 80 12 50.8
69 0.98 3.04 0.05gAmberlyst70 6ml ethyl alcohol 80 12 96.7
70 0.98 3.04 0.05g sulfuric acid 6ml THF 80 8 95.8
The separation of bis- (the 4- hydroxy-3-methoxy benzal) cyclopentanone of the target product 2,6- provided by embodiment 31 ~ 60 in table 2 Yield, there it can be seen that cyclopentanone and vanillic aldehyde aldol reaction, in different acid catalysts: Nafion resin, In Amberlyst15, Amberlyst36, Amberlyst70, sulfuric acid, nitric acid, trifluoroacetic acid and p-methyl benzenesulfonic acid extremely Few one kind has the product of certain yield to generate.Fig. 1 is that the H-NMR of Aldol Condensation Products schemes, it was demonstrated that synthesizing target product is Bis- (the 4- hydroxy-3-methoxy benzal) cyclopentanone of 2,6-.
Bis- (the 4- hydroxy-3-methoxy benzal) cyclohexanone of the target product 2,6- provided by embodiment 61 ~ 70 in table 3 Yield is separated, there it can be seen that cyclohexanone and vanillic aldehyde aldol reaction, in different acid catalysts: Nafion resin, In Amberlyst15, Amberlyst36, Amberlyst70, sulfuric acid, nitric acid, trifluoroacetic acid and p-methyl benzenesulfonic acid extremely Few one kind has the product of certain yield to generate.Figure Fig. 2 is that the H-NMR of Aldol Condensation Products schemes, it was demonstrated that synthesizes target product For bis- (the 4- hydroxy-3-methoxy benzal) cyclohexanone of 2,6-.
(2) 100mL's plus in hydrogen tank reactor, by a certain amount of aldol reaction product, catalyst and second Solvent is fitted into reaction kettle, is filled in hydrogen displacement kettle into reactor after air, is filled with certain pressure.Setting temperature and It is reacted under time conditions.In this step, different catalysts, different solvents, the differential responses time, differential responses pressure, The parameters such as differential responses temperature are as shown in table 4 below to hydrogenation deoxidation reaction result:
Bis- (the 4- hydroxy-3-methoxy benzal) cyclopentanone (X of 4 2,6- of table2Cp) hydrogenation deoxidation reacts under different experimental conditions Result
Embodiment X2Cp/g Catalyst/g Second solvent/g Temperature/DEG C Pressure/MPa Time/h C19Cycloalkanes Auditory steady-state responses/%
71 1.00 Pd/C Hexamethylene 350 2.0 12 92.5
72 1.00 Pd/C Hexamethylene 350 4.0 12 91.8
73 1.00 Pd/C Hexamethylene 350 6.0 12 90.4
74 1.00 Pt/C Hexamethylene 350 2.0 8 78.3
75 1.00 Pt/C Hexamethylene 350 2.0 10 85.2
76 1.00 Pt/C Hexamethylene 350 2.0 18 90.9
77 1.00 Ru/C Hexamethylene 350 2.0 10 82.7
78 1.00 Ru/C Hexamethylene 350 4.0 10 85.6
79 1.00 Ru/C N-hexane 350 4.0 24 75.5
80 1.00 Ir /C N-hexane 350 2.0 5 90.5
81 1.00 Ir /C N-hexane 350 4.0 10 90.6
82 1.00 Ir /C N-hexane 350 2.0 30 90.5
83 1.00 Pd /SiO2 Normal octane 310 1.0 12 91.3
84 1.00 Pd /SiO2 Normal octane 310 2.0 12 91.2
85 1.00 Pd /SiO2 Normal octane 310 1.0 24 92.5
86 1.00 Pd /SiO2/Al2O3 Normal octane 300 2.0 12 94.3
87 1.00 Pd /SiO2/Al2O3 Tridecane 300 2.0 10 92.7
88 1.00 Pd /SiO2/Al2O3 Tridecane 300 6.0 8 89.8
89 1.00 Pd /H-ZSM-5 Tridecane 280 4.0 12 89.8
90 1.00 Pd /H-ZSM-5 Tridecane 280 4.0 24 88.9
91 1.00 Pd /H-ZSM-5 Decahydronaphthalene 300 2.0 15 87.5
92 1.00 Pd /H-β Decahydronaphthalene 300 2.0 5 88.8
93 1.00 Pd /H-β Decahydronaphthalene 300 3.0 10 89.5
94 1.00 Pd /H-β Decahydronaphthalene 300 4.0 24 89.9
95 1.00 Pd/montmorillonite K10 Decahydronaphthalene 280 3.0 12 91.6
96 1.00 Pd/montmorillonite K10 Decahydronaphthalene 280 4.0 10 91.2
97 1.00 Pd/montmorillonite K10 Decahydronaphthalene 280 2.0 24 92.0
98 1.00 Pd /H-β Hexamethylene 260 2.0 12 90.1
99 1.00 Pd /H-β Hexamethylene 250 2.0 10 88.2
100 1.00 Pd /H-β Hexamethylene 240 7.0 24 84.1
Bis- (the 4- hydroxy-3-methoxy benzal) cyclohexanone (X of 5 2,6- of table2He) hydrogenation deoxidation reacts under different experimental conditions Result
Embodiment X2He/g Catalyst/g Second solvent/g Temperature/DEG C Pressure/MPa Time/h C20Cycloalkanes Auditory steady-state responses/%
101 1.00 Pd/C Hexamethylene 350 2.0 12 91.5
102 1.00 Pt/C Hexamethylene 350 2.0 18 90.5
103 1.00 Ru/C Hexamethylene 350 2.0 10 83.9
104 1.00 Ir /C N-hexane 350 4.0 10 89.7
105 1.00 Pd /SiO2 Normal octane 310 1.0 24 90.1
106 1.00 Pd /SiO2/Al2O3 Normal octane 300 2.0 12 91.3
107 1.00 Pd /SiO2/Al2O3 Tridecane 300 2.0 10 91.6
108 1.00 Pd /H-ZSM-5 Tridecane 280 4.0 24 89.8
109 1.00 Pd /H-ZSM-5 Decahydronaphthalene 300 2.0 15 88.6
110 1.00 Pd /H-β Decahydronaphthalene 300 2.0 5 90.8
111 1.00 Pd/montmorillonite K10 Decahydronaphthalene 280 3.0 12 90.6
112 1.00 Pd /H-β Hexamethylene 260 2.0 12 92.5
113 1.00 Pd /H-β Hexamethylene 250 4.0 10 90.2
114 1.00 Pd /H-β Hexamethylene 240 7.0 24 85.2
As can be seen from Table 4, when 240 ~ 350 DEG C of temperature, bis- (the 4- hydroxy-3-methoxy benzal of 2,6- in embodiment 71 ~ 100 Base) cyclopentanone hydrogenation deoxidation product C19Polycyclic hydrocarbon yield up to 92.7%.The density and freezing point of product is respectively 0.926g/mL and -31.8 DEG C.The gas-chromatography of bis- (4- hydroxy-3-methoxy benzal) the cyclopentanone hydrogenation deoxidation products of 2,6- The mass spectrogram of figure and bis- (cyclohexyl methyl) pentamethylene of principal product 1,3- difference is as shown in Figure 3 and Figure 5；It can be used as aerospace Fuel directly uses, or as the additive for improving Cetane number, is added to existing aviation fuel with certain proportion Middle use.
As can be seen from Table 5, when 240 ~ 350 DEG C of temperature, bis- (the 4- hydroxy-3-methoxies of 2,6- in embodiment 101 ~ 114 Benzal) cyclohexanone hydrogenation deoxidation product C20Polycyclic hydrocarbon yield up to 92.5%.The density and freezing point of product is respectively 0.931g/mL and -32.1 DEG C.The gas-chromatography of bis- (4- hydroxy-3-methoxy benzal) the cyclohexanone hydrogenation deoxidation products of 2,6- The mass spectrogram of figure and bis- (cyclohexyl methyl) hexamethylenes of principal product 1,3- difference is as shown in Figure 4 and Figure 6.It can be used as aviation kerosine It is directly used with high-quality diesel oil, or as the additive for improving Cetane number, existing aviation is added to certain proportion It is used in kerosene and diesel oil.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in spirit of that invention With any modifications, equivalent replacements, and improvements made within principle etc., should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of preparation method of polycyclic high-density biology matter liquid fuel, which is characterized in that method includes the following steps:
(1) using cyclic ketones object, vanillic aldehyde as reaction raw materials, the reaction raw materials and the first solvent are passed through into hydroxyl under acid catalyst effect Aldehyde condensation reaction, obtains Primary product；Wherein, the cyclic ketones object is at least one of cyclopentanone and cyclohexanone；
(2) as load type metal catalyst Primary product made from step (1) is directly carried out in the second solvent plus hydrogen Deoxygenation, obtaining by carbochain is C19And/or C20Polycyoalkane constitute polycyclic high-density biology matter liquid fuel.
2. the preparation method of polycyclic high-density biology matter liquid fuel as described in claim 1, which is characterized in that in step (1) in, mass concentration of the reaction raw materials in the first solvent is 5 ~ 90%；The cyclic ketones object, vanillic aldehyde molar ratio be 1: (1 ~ 4)；The mass ratio of the acid catalyst and cyclic ketones object is (1 ~ 20): 100；The aldol reaction time be 0.5 ~ for 24 hours, Reaction temperature is 40 ~ 100 DEG C；
In step (2), mass concentration of the Primary product in the second solvent is 1 ~ 60%；The load type metal catalysis The mass ratio of agent and Primary product is (1 ~ 20): 100；The hydrogenation deoxidation reaction carries out in intermittent tank reactor, In, the reaction condition in tank reactor are as follows: 150 ~ 400 DEG C of reaction temperature, the reaction time is 6 ~ 48 h, Hydrogen Vapor Pressure 0.5 To 10.0 MPa.
3. the preparation method of polycyclic high-density biology matter liquid fuel as claimed in claim 2, which is characterized in that in step (1) in, mass concentration of the reaction raw materials in the first solvent is 30 ~ 60%；The molar ratio of the cyclopentanone and vanillic aldehyde is 1:2；The mass ratio of the acid catalyst and cyclic ketones object is (5 ~ 10): 100；The aldol reaction time is 4 ~ 12h, reaction Temperature is 60 ~ 90 DEG C；
In step (2), mass concentration of the Primary product in the second solvent is 3 ~ 20%；The load type metal catalysis The mass ratio of agent and Primary product is (5 ~ 10): 100；Reaction condition in the tank reactor are as follows: reaction temperature be 240 ~ 350 DEG C, the reaction time is 12 ~ 24 h, and Hydrogen Vapor Pressure is 2.0 ~ 6.0MPa.
4. the preparation method of polycyclic high-density biology matter liquid fuel as described in claim 1, which is characterized in that in step (1) in, the acid catalyst is solid acid or liquid acid；First solvent is ethyl alcohol, methanol, at least one in tetrahydrofuran Kind；
In step (2), the carrier of the load type metal catalyst includes active carbon, SiO2、SiO2/Al2O3、H-ZSM-5、H- Beta-molecular sieve, H-Y molecular sieve and montmorillonite K10, at least one of supported on carriers precious metals pt, Pd, Ru and the Ir； Second solvent is at least one of hexamethylene, n-hexane, normal octane, tridecane and decahydronaphthalene.
5. the preparation method of polycyclic high-density biology matter liquid fuel as claimed in claim 4, which is characterized in that the solid Acid is at least one of Nafion resin, Amberlyst15, Amberlyst36, Amberlyst70；The liquid acid is sulphur At least one of acid, nitric acid, fluoroform acetic acid, phosphoric acid and p-methyl benzenesulfonic acid.
6. the preparation method of polycyclic high-density biology matter liquid fuel as claimed in claim 4, which is characterized in that the load The preparation of type metallic catalyst is the following steps are included: the active carbon that nitric acid treatment is crossed is added to your gold of mass concentration 1 ~ 10% Belong to solution；By carrier, incipient impregnation is in above-mentioned precious metal solution after 500 DEG C of temperature lower calcination 4h, 80 after 24 h of standing Dry 6 ~ 24 h at ~ 120 DEG C, then be passed through and contained after temperature is reduced to room temperature with 1 ~ 10 h of hydrogen reducing at 200 ~ 600 DEG C Nitrogen inerting 4 h or more that oxygen volumetric concentration is 1%.
7. the polycyclic high-density biology matter liquid fuel that the described in any item methods of claim 1 ~ 6 are prepared.
8. application of the polycyclic high-density biology matter liquid fuel as claimed in claim 7 in terms of as aviation fuel.
9. polycyclic high-density biology matter liquid fuel answering in terms of as aviation fuel additive as claimed in claim 7 With.
CN201910017003.9A 2019-01-08 2019-01-08 Polycyclic high-density biomass liquid fuel and preparation method and application thereof Active CN109852441B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910017003.9A CN109852441B (en) 2019-01-08 2019-01-08 Polycyclic high-density biomass liquid fuel and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910017003.9A CN109852441B (en) 2019-01-08 2019-01-08 Polycyclic high-density biomass liquid fuel and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109852441A true CN109852441A (en) 2019-06-07
CN109852441B CN109852441B (en) 2021-03-23

Family

ID=66894234

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910017003.9A Active CN109852441B (en) 2019-01-08 2019-01-08 Polycyclic high-density biomass liquid fuel and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109852441B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552949A (en) * 2020-12-02 2021-03-26 中国科学院广州能源研究所 Method for synthesizing high-density low-freezing-point hydrocarbon component by biomass platform compound
CN113019435A (en) * 2021-03-26 2021-06-25 福州大学 Monoatomic palladium/molecular sieve catalyst, preparation thereof and application thereof in preparation of ketone by selective hydrogenation of biomass molecules
CN114213560A (en) * 2021-12-27 2022-03-22 中国科学院兰州化学物理研究所 Method for synthesizing renewable polycycloolefin material
CN115093879A (en) * 2022-07-18 2022-09-23 陕西理工大学 Method for synthesizing high-density aviation fuel by taking vanillin as raw material
CN116621719A (en) * 2022-04-02 2023-08-22 南京工业大学 Synthesis method of full-biology-based aryl diamine chain extender applied to preparation of polyurethane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232140A (en) * 2013-06-09 2014-12-24 中国科学院大连化学物理研究所 Method for synthesizing high-density aviation fuel by using cyclopentanone as raw material
CN104711007A (en) * 2013-12-11 2015-06-17 中国科学院大连化学物理研究所 Preparation method of aviation kerosene or diesel oil scope liquid alkane
WO2017097434A1 (en) * 2015-12-06 2017-06-15 Symrise Ag A fragrance composition
CN106867565A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of preparation method of high density liquid hydrocarbon fuel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232140A (en) * 2013-06-09 2014-12-24 中国科学院大连化学物理研究所 Method for synthesizing high-density aviation fuel by using cyclopentanone as raw material
CN104711007A (en) * 2013-12-11 2015-06-17 中国科学院大连化学物理研究所 Preparation method of aviation kerosene or diesel oil scope liquid alkane
WO2017097434A1 (en) * 2015-12-06 2017-06-15 Symrise Ag A fragrance composition
CN106867565A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of preparation method of high density liquid hydrocarbon fuel

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552949A (en) * 2020-12-02 2021-03-26 中国科学院广州能源研究所 Method for synthesizing high-density low-freezing-point hydrocarbon component by biomass platform compound
CN113019435A (en) * 2021-03-26 2021-06-25 福州大学 Monoatomic palladium/molecular sieve catalyst, preparation thereof and application thereof in preparation of ketone by selective hydrogenation of biomass molecules
CN114213560A (en) * 2021-12-27 2022-03-22 中国科学院兰州化学物理研究所 Method for synthesizing renewable polycycloolefin material
CN116621719A (en) * 2022-04-02 2023-08-22 南京工业大学 Synthesis method of full-biology-based aryl diamine chain extender applied to preparation of polyurethane
CN116621719B (en) * 2022-04-02 2024-01-30 南京工业大学 Synthesis method of full-biology-based aryl diamine chain extender applied to preparation of polyurethane
CN115093879A (en) * 2022-07-18 2022-09-23 陕西理工大学 Method for synthesizing high-density aviation fuel by taking vanillin as raw material

Also Published As

Publication number Publication date
CN109852441B (en) 2021-03-23

Similar Documents

Publication Publication Date Title
CN109852441A (en) A kind of polycyclic high-density biology matter liquid fuel and the preparation method and application thereof
CN104711021B (en) Method for preparing cycloparaffin as aviation kerosene or diesel oil by biomass route
CN104232140B (en) A kind of method of synthesizing high density aviation fuel taking cyclopentanone as raw material
CN111054390B (en) Catalyst for preparing methyl propionate by hydrogenating methyl acrylate and preparation and application thereof
CN107304367B (en) Preparation method of branched alkane in range of gasoline, aviation kerosene or diesel oil
CN105273739B (en) Preparation method for aviation kerosene
Thibault et al. Cyclopentadienyl and pentamethylcyclopentadienyl ruthenium complexes as catalysts for the total deoxygenation of 1, 2-hexanediol and glycerol
CA2783875C (en) Production of liquid fuels (sylvan-liquid-fuels) from 2-methylfuran
CN106867565A (en) A kind of preparation method of high density liquid hydrocarbon fuel
CN103450940A (en) Method for preparation of aviation kerosene and diesel oil from biomass derivative
CN103265400A (en) Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives
CN107398276A (en) A kind of catalyst and preparation method for being catalyzed 5 hydroxymethylfurfural selective hydrogenation deoxidations and preparing 2,5 dimethyl furans
CN111233615B (en) Norbornene-based four-membered ring space fuel, heterogeneous photocatalytic cyclization preparation method and application thereof
CN113171792A (en) Aluminum modified molecular sieve loaded bimetallic catalyst, preparation thereof and application thereof in lignin depolymerization by hydrogenation
CN113528176B (en) Preparation method of biomass liquid fuel
CN107814676B (en) Preparation method of decahydronaphthalene and tetrahydronaphthalene
US10960386B2 (en) Method and catalyst for producing methylbenzyl alcohol from ethanol by catalytic conversion
CN107488457A (en) A kind of biomass liquid fuel and preparation method and application
CN108722495A (en) A kind of bifunctional catalyst of catalysis one step of fructose 2,5- dimethyl furans directly processed
CN112295571B (en) PtNi cage catalyst and application thereof in furfuryl alcohol preparation by catalyzing selective hydrogenation of furfural
CN108569943A (en) A method of using cyclopentanone as Material synthesis high density aviation fuel
CN100553764C (en) A kind of Catalysts and its preparation method that is used to prepare o-phenyl phenol
CN114522716A (en) Bimetal supported catalyst, preparation method thereof and application of bimetal supported catalyst in preparation of biological aviation kerosene through palm oil hydro-conversion
CN107446611A (en) A kind of preparation method of aviation kerosine cycloalkane and aromatic hydrocarbons
CN112552949B (en) Method for synthesizing high-density low-freezing-point hydrocarbon component by biomass platform compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant