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 PDFInfo
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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
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.
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