CN104711012A - Applications of hydrodeoxygenation catalyst in synthesis of renewable diesel fuel or aviation kerosene - Google Patents
Applications of hydrodeoxygenation catalyst in synthesis of renewable diesel fuel or aviation kerosene Download PDFInfo
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Abstract
The present invention relates to a new method for preparing diesel fuel or aviation kerosene range hydrocarbons by using isophorone, 3,3,5-trimethyl cyclopentanol, 3,3,5-trimethyl cyclopentanone, 2-ethyl-2-hexenal, 2-ethyl-2-hexanol, 2-ethyl-2-hexanal, fatty acids, fatty acid methyl (or ethyl) esters, a biomass fatty acid triglyceride and other oxygen-containing organic compounds obtained from biomasses as raw materials through a hydrodeoxygenation reaction. According to the present invention, the direct low-temperature hydrodeoxygenation of the biomass oxygen-containing organic compound under the solvent-free condition is achieved, and a series of the high-yield chain alkanes or cycloalkanes having the diesel fuel or aviation kerosene chain length range are obtained; and the catalyst of the present invention has characteristics of no requirement of solvent, simple operation process, mild reaction conditions, good aviation kerosene (or diesel fuel) selectivity, and the like, and is the ideal catalyst for preparation of the diesel fuel or aviation kerosene range hydrocarbon fuels through the hydrodeoxygenation of the biomass oxygen-containing organic compound.
Description
Technical field
The present invention relates to a kind of oxygen-containing organic compound obtained by biomass is raw material, is prepared the novel method of aviation kerosene scope hydro carbons by hydrogenation deoxidation.Adopt load type metal-silicon oxide catalyst to achieve the direct hydrogenation deoxidation of biomass aviation kerosene precursor under solvent-free mild conditions, high yield obtains the hydrocarbon compound of a series of aviation kerosene (or diesel oil) chain length range.Compared with existing hydrodeoxygenation process, the method has the advantages such as solvent-free, operating procedure is simple, less energy-consumption, low cost.
Background technology
Aviation kerosene is the liquid fuel be in great demand in the world at present, is national strategic goods and materials.Its kind is a lot, is generally made up of chain alkane, aromatic hydrocarbons and the naphthenic hydrocarbon of carbon number between 8-16.For current common JP-8, its classics are composed as follows: C
8to C
16straight-chain paraffin account for 35%, C
8to C
16branched paraffin account for 35%, C
7to C
10aromatic hydrocarbon account for 18%, C
6to C
10naphthenic hydrocarbon account for 7%.Diesel oil is one of main transport fuel, mainly by C
9to C
21chain hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbon composition, its boiling point is between 170-390 DEG C.At present, aviation kerosene and diesel oil mainly with fossil resource (coal and oil) for waste, coal and oil are all the non-renewable energy, by their synthesis aviation kerosene and diesel oil manufacture and use procedure can produce a large amount of carbonic acid gas, cause Greenhouse effect.And in recent years along with the minimizing day by day of petroleum resources, crude oil price constantly rises, the price of aviation kerosene and diesel oil is also climbed up and up.China is as energy expenditure big country and petroleum import big country, and petroleum import amount in recent years constantly increases, and the petroleum import interdependency of 2009 is 53.6%, has broken through the national security barrier line of 50%.2012, the dependence on foreign countries for oil of China reached the historic high of 58% especially.Thus, the variation route developing alternative conventional fossil fuel is very urgent.Different with fossil energy, biomass belong to renewable energy source, the carbonic acid gas that the carbonic acid gas that biomass fuel produces in combustion can be consumed by photosynthesis by its process of growth offset, therefore biomass fuel is carbonic acid gas neutrality in whole use procedure.Therefore from the viewpoint of national energy security, protection of the environment and potential economic worth three, need to greatly develop biomass aviation kerosene technology.
At present, biomass liquid fuel can be divided into first-generation biomass liquid fuel and s-generation biomass liquid fuel.First-generation biomass liquid fuel is with edible corn, soybean and Sunflower Receptacle etc. for raw material, produces bio-ethanol and biofuel by fermentation and the reaction such as transesterification.First-generation biomass liquid fuel is in Europe, and the area such as America has practical application as transport fuel.But its combustionproperty is bad, must improves former engine, can use.S-generation biomass liquid fuel is for raw material with unedible lignocellulose, mainly contain three kinds of approach and generate fuel: 1) thermochemistry gasified bio-matter is to synthetic gas, then produce alkane by F-T synthesis, this process comparative maturity, but need the condition of High Temperature High Pressure; 2) high temperature pyrolysis biomass produce bio-oil, and this process is complicated, and obtained bio-oil inferior quality, directly cannot be used as motor spirit, need further refining be carried out; 3) take lignocellulose as the biomass platform chemicals molecule that raw material obtains, by C-C coupling reactions such as aldol condensation, alkylation are anti-, then hydrogenation deoxidation produces liquid alkane, and this process condition is relatively gentle, and synthetic route is relatively more flexible.
2005, the people such as Dumesic, Huber are at [Science, 2005,308,1446-1450] and patent [US7,671,246] report hydroxymethylfurfural or furfural and acetone (or tetrahydrofurfural is intermolecular) and produced the oxygen-containing organic compound with aviation kerosene chain length range by the aldol reaction of base catalysis, then produce C by the step such as hydrogenation and hydrogenation deoxidation
8to C
15the liquid alkane of scope.Use Pt/SiO
2-Al
2o
3as hydrogenation deoxidation catalyst, adopt fixed bed four phase reactor, need to add n-Hexadecane and prevent catalyst deactivation in reaction process, technics comparing is complicated.In [ChemSusChem, 2008, Isosorbide-5-Nitrae 17-424] and patent [US7,880,049], they improve the preparation technology of hydroxymethylfurfural and furfural, and adopt the niobium oxide of phosphorylation to make carrier.Do not need after finding to adopt novel vector to use n-Hexadecane can obtain good effect yet, thus simplify technique.But the alkane synthesized due to this process is straight-chain paraffin, the zero pour of these hydro carbons is very high (Pentadecane: 8.5-10 DEG C, n-tridecane :-5.5 DEG C, n-dodecane :-12 DEG C), does not meet the requirement (fusing point is lower than-40 DEG C) of aviation kerosene.Recently, the people such as Corma [Angew.Chem.Int.Ed.2011,50,1-5] report methyl furan and butyraldehyde, 5 methyl furfural, 5 hydroxymethyl furfural and himself trimerization reaction, prepare the oxygen-containing organic compound with aviation kerosene or diesel oil chain length range, obtain a series of low-freezing side chain hydro carbons with aviation kerosene chain length range by gradient bed bioreactor hydrogenation deoxidation thereafter.Subsequently, the people such as Corma [ChemSusChem, 2011,4,1574-1577] again the method for hydrogenation deoxidation is improved, and adopt Pt/C, Pt/C-TiO2 as catalyzer, by obtaining higher liquid phase alkane yield to alkylate direct hydrogenation deoxidation (350 DEG C).[Chinese patent: application number: 201110346501.1 in the work in this seminar early stage; 201210169817.2; 20121043947.9; 201310150270.6], furyl oxygen-containing organic compound is adopted to obtain a series of oxygen-containing organic compound with aviation kerosene chain length range by alkylated reaction or aldol reaction, by obtaining the low-freezing branched-chain hydrocarbon with aviation kerosene chain length range to these organic compound direct hydrogenation deoxidations.Further developed tungsten carbide catalyst and the metal-solids acid dual-function catalyst of nickel promotion simultaneously, alternative precious metal can be realized and carry out hydrogenation deoxidation reaction.But the temperature of reaction that these methods need at hydrodeoxygenation step still higher (350 DEG C) or need acid carrier.In this patent, we find low temperature (100-260 DEG C) the complete hydrogenation deoxidation that can realize biomass aviation kerosene precursor on load type metal-silicon oxide catalyst, thus highly selective obtains the biomass liquid fuel with aviation kerosene chain length range.
Summary of the invention
The present invention is that load type metal silicon oxide catalyst prepares the application in liquid alkane reaction at the oxygen-containing organic compound hydrogenation deoxidation that biomass obtain.Such catalyzer can make hydrogenation deoxidation reaction carry out efficiently at lower temperatures, thus reduces energy consumption of reaction.Such catalyzer divides for and is made up of two portions: active component A is one or more in W metal, Pt, Pd, Ru, Rh, Ir, Fe, Co, Cu etc.; Carrier X is silica support as one or both mixture in: commercial silica and ordered meso-porous silicon oxide SBA-15.Such catalyzer can carry out hydrogenation deoxidation reaction to biomass aviation kerosene precursor in a mild condition.In the present invention, catalyzer has the features such as solvent-free, operating procedure is simple, less energy-consumption, low cost, provides a kind of desirable hydrogenation deoxidation new way being prepared aviation kerosene chain hydrocarbon by biomass aviation kerosene precursor hydrogenation deoxidation.
The present invention is achieved by the following technical solutions:
Before the present invention adopts load type metal-silicon oxide catalyst to achieve biomass aviation kerosene, the alkane of aviation kerosene or diesel range is prepared in the deoxidation of body hypothermia direct hydrogenation.
Biomass aviation kerosene precursor main component comprises the mixture of one of the following kind or more than two kinds: isophorone, 3,3,5-trimethylammonium cyclopentanol, 3,3,5-trimethylammonium cyclopentanone, 2-ethyl, 2-hexenoic aldehyde, 2-ethyl, 2-hexanol, 2-ethyl, 2-hexanal, C
8-C
20lipid acid, C
8-C
20fatty acid methyl ester, C
8-C
20fatty-acid ethyl ester, a kind of in the lipid acid triglyceride of fatty acid carbon chain between 8-20 or two kinds mixture.
Load type metal silicon oxide A/X type catalyzer: active component A is one or more in W metal, Cu, Co, Fe, Pt, Pd, Ru, Rh, Ir etc.; Carrier X is: one or more mixture of commercial silica and ordered meso-porous silicon oxide SBA-15.The content of active component A is: 0.1-80%, and preferable range is 2-50%.
Load type metal-silicon oxide catalyst adopts pickling process or deposition-precipitation method preparation.
Pickling processes is as follows: first by the soluble salt solutions of A by metering than being added to the medium volume impregnation of carrier X shaping in advance, room temperature leaves standstill more than 2 hours, then dry and in 300-600 DEG C of roasting 2-5 hour, obtain baked catalyzer.
Deposition-precipitation method process is as follows: first by the soluble salt solutions of A by metering than being added in the suspension liquid of carrier X shaping in advance, under continuous stirring, add corresponding precipitation agent.And aging more than 2 hours, filter, dry.And in 300-600 DEG C of roasting 2-5 hour, obtained baked catalyzer.
Baked catalyzer needs to carry out reduction treatment before use: can reduce at fixed-bed reactor situ: reductive condition is hydrogen pressure is 0.1-10MPa, hydrogen/catalyst volume air speed 800-5000h
-1, reduction temperature 200-600 DEG C, the recovery time is 1-10 hour.
Also can carry out in tube furnace: hydrogen is normal pressure, hydrogen/catalyst volume air speed 800-5000h
-1, reduction temperature 200-600 DEG C, the recovery time is 1-10 hour.Be down to after room temperature until temperature, need volume ratio 1%O be passed into
2/ N
2passivation more than 2 hours.
This reaction can be carried out or carry out in fixed-bed reactor in batch reactor.
Time in batch reactor, temperature of reaction 25-350 DEG C, preferable reaction temperature is 100-260 DEG C, hydrogen pressure 0.1-20MPa, reaction times 0.5-24 hour.
Time in fixed-bed reactor, temperature of reaction 25-350 DEG C, preferable reaction temperature is 100-260 DEG C, hydrogen pressure 0.1-20MPa; Moving phase reactor lignocellulose base aviation kerosene presoma liquid material/catalyst quality air speed is 0.1-10h
-1, preferred air speed is 0.5-2h
-1, hydrogen/catalyst volume air speed is 600-15000h
-1.
By above step, load type metal silicon oxide catalyst can be implemented in 100-260 DEG C under low temperature, prepared by the hydrogenation deoxidation of the oxygen-containing organic compound highly selective high yield that biomass obtain to the hydrocarbon fuel of diesel oil or aviation kerosene chain length range.
Tool of the present invention has the following advantages:
The features such as the catalyzer related in the present invention has without the need to solvent, operating procedure is simple, reaction conditions is gentle, aviation kerosene (or diesel oil) selectivity is good are a kind of desirable catalyzer being prepared diesel oil or aviation kerosene range hydrocarbons class A fuel A by biomass oxygen-containing organic compound hydrogenation deoxidation.Especially, namely such catalyzer starts have hydrogenation deoxidation active at 100 DEG C; At about 150 DEG C, under condition of no solvent, alkane yield can reach 30%.This is the best result reported so far.
Accompanying drawing explanation
Fig. 1 is the products distribution GC spectrogram of embodiment 32.
Fig. 2-(a-e) is GC-MS spectrogram; Fig. 2-(a) embodiment 32GC-MS total ion current figure; Fig. 2-(b) embodiment 32GC-MS principal product 1 coupling figure; Fig. 2-(c) embodiment 32GC-MS principal product 2 coupling figure; Fig. 2-(d) embodiment 32GC-MS by product 1 coupling figure; Fig. 2-(e) embodiment 32GC-MS by product 2 coupling figure.
Can find out that the reaction primary product of embodiment 32 is 1,1,3-trimethyl-cyclohexane and isomer thereof from the GC-MS spectrogram of Fig. 2-(a-e), by product is 3,3,5-cyclonol.The alkane products generated in other embodiment is similar with it.
Embodiment
To be illustrated the present invention with specific embodiment below, but protection scope of the present invention is not limited to these examples.
Embodiment
1. the preparation of catalyzer:
(1) pickling process: the nickel nitrate solution of preparation mass concentration 10%, dilute accordingly according to the saturated water adsorptive value of carrier, to add in commercial silica and ordered meso-porous silicon oxide SBA-15 among one, then 2 hours are left standstill, dried overnight at 120 DEG C, 500 DEG C of air roastings 2 hours, with hydrogen reducing 2 hours at 500 DEG C, be reduced to after room temperature until temperature and pass into volume ratio 1%O
2/ N
2passivation, can prepare the nickel catalyzator (see table 1, embodiment 1,2) of different carriers load.
Palladous chloride, ruthenium chloride, Platinic chloride, chloro-iridic acid, rhodium chloride, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cupric nitrate, the iron nitrate solution of preparation mass ratio 10%, by one wherein according to necessarily measuring than adding in commercial silica, then 2 hours are left standstill, dried overnight at 120 DEG C, 500 DEG C of air roastings 2 hours, use hydrogen reducing 2 hours at 500 DEG C, be reduced to after room temperature until temperature and pass into volume ratio 1%O
2/ N
2passivation, can prepare loading type single-metal reforming catalyst (see table 1, embodiment 2-10).
Rhodium chloride, Palladous chloride, ruthenium chloride, chloro-iridic acid, Platinic chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cupric nitrate, the iron nitrate solution of preparation mass ratio 10%, it is added in commercial silica according to different meterings than together with nickel nitrate solution, then 2 hours are left standstill, dried overnight at 120 DEG C, 500 DEG C of air roastings 2 hours, use hydrogen reducing 2 hours at 500 DEG C, be reduced to after room temperature until temperature and pass into volume ratio 1%O
2/ N
2passivation, can prepare the nickel alloy catalyst (see table 1, embodiment 11-18) of loading type different metal ratio.
The nickel nitrate solution of preparation mass ratio 10%, dilutes it according to different content, adds in commercial silica, then 2 hours are left standstill, dried overnight at 120 DEG C, 500 DEG C of air roastings 2 hours, use hydrogen reducing 2 hours at 500 DEG C, be reduced to after room temperature until temperature and pass into volume ratio 1%O
2/ N
2passivation, can prepare nickel catalyst carried (see the table 1, embodiment 19-23) of different Ni contents.
(2) deposition-precipitation method: the nickel nitrate solution of preparation mass ratio 10%, add commercial silica and ordered meso-porous silicon oxide SBA-15, in 80 DEG C of water-baths, add a certain amount of urea, stir 10 hours after being warming up to 90 DEG C, cooling, filter, washing, dried overnight at 120 DEG C, 500 DEG C of air roastings 2 hours, use hydrogen reducing 2 hours at 500 DEG C, be reduced to after room temperature until temperature and pass into volume ratio 1%O
2/ N
2passivation, can prepare nickel catalyst carried (see table 1, embodiment 24,25).
The nickel nitrate solution of preparation mass ratio 10%, add commercial silica, in 80 DEG C of water-baths, add a certain amount of urea, stir 10 hours after being warming up to 90 DEG C, cooling, filter, washing, dried overnight at 120 DEG C, 500 DEG C of air roastings 2 hours, use hydrogen reducing 2 hours at 500 DEG C, be reduced to after room temperature until temperature and pass into volume ratio 1%O
2/ N
2passivation, can prepare nickel catalyst carried (see the table 1, embodiment 26-32) of different Ni contents.
Table 1 load type metal catalyst
| Embodiment | Carrier | Metal and loading (weight percent) thereof |
| Embodiment 1 | Ordered meso-porous silicon oxide SBA-15 | 5%Ni |
| Embodiment 2 | Commercial silica | 5%Ni |
| Embodiment 3 | Commercial silica | 5%Pt |
| Embodiment 4 | Commercial silica | 5%Pd |
| Embodiment 5 | Commercial silica | 5%Ru |
| Embodiment 6 | Commercial silica | 5%Ir |
| Embodiment 7 | Commercial silica | 5%Fe |
| Embodiment 8 | Commercial silica | 5%Co |
| Embodiment 9 | Commercial silica | 5%Cu |
| Embodiment 10 | Commercial silica | 5%Rh |
| Embodiment 11 | Commercial silica | 4%Ni1%Ir |
| Embodiment 12 | Commercial silica | 4%Ni1%Pd |
| Embodiment 13 | Commercial silica | 4%Ni1%Ru |
| Embodiment 14 | Commercial silica | 4%Ni1%Rh |
| Embodiment 15 | Commercial silica | 4%Ni1%Pt |
| Embodiment 16 | Commercial silica | 4%Ni1%Fe |
| Embodiment | Carrier | Metal and loading (weight percent) thereof |
| Embodiment 17 | Commercial silica | 4%Ni1%Co |
| Embodiment 18 | Commercial silica | 4%Ni1%Cu |
| Embodiment 19 | Commercial silica | 4%Ni0.1%Pt |
| Embodiment 20 | Commercial silica | 4%Ni0.3%Pt |
| Embodiment 21 | Commercial silica | 4%Ni4%Pt |
| Embodiment 22 | Commercial silica | 0.5%Ni |
| Embodiment 23 | Commercial silica | 2%Ni |
| Embodiment 24 | Commercial silica | 10%Ni |
| Embodiment 25 | Commercial silica | 40%Ni |
| Embodiment 26 | Commercial silica | 80%Ni |
| Embodiment 27 | Ordered meso-porous silicon oxide SBA-15 | 5%Ni |
| Embodiment 28 | Commercial silica | 5%Ni |
| Embodiment 29 | Commercial silica | 0.1%Ni |
| Embodiment 30 | Commercial silica | 0.5%Ni |
| Embodiment 31 | Commercial silica | 2%Ni |
| Embodiment 32 | Commercial silica | 10%Ni |
| Embodiment 33 | Commercial silica | 20%Ni |
| Embodiment 34 | Commercial silica | 40%Ni |
| Embodiment 35 | Commercial silica | 80%Ni |
2. hydrogenation deoxidation reaction:
1) in the Parr reactor of 100mL, add biomass aviation kerosene precursor (isophorone, 2-ethyl, 2-hexenoic aldehyde, methyl stearate, soft-methyl ester, Witconol 2301, micro-algae oil, soya-bean oil etc.) 40mL, 2.0 grams of catalyzer, at 230 DEG C, using metal-oxide Si catalyst (embodiment 1-35) as hydrogenation deoxidation catalyst, hydrogen pressure 6.0MPa, reacts 10 hours.By gas chromatographic analysis, detailed reaction the results are shown in Table 2.
The impact of table 2 catalyzer, raw material composition on hydrogenation reaction
As can be seen from Table 2, under condition of no solvent, catalyzer selected in table all can obtain the liquid phase alkane of certain productive rate, wherein with the Ni-based monometallic of noble metal catalyst, load and alloy catalyst activity higher.And with different biomass aviation kerosene precursors for raw material all can obtain higher liquid alkane yield.
2) in the Parr reactor of 100mL, add isophorone 40mL, 2.0g catalyzer, investigate temperature using 5% nickel-commercial oxidation Si catalyst as hydrogenation deoxidation catalyst, impact that pressure, reaction times react hydrogenation deoxidation.Detailed reaction the results are shown in Table 3.
Table 3 temperature, pressure, reaction times are on the impact of hydrogenation reaction
| Embodiment | Temperature/DEG C | Pressure/MPa | Reaction times/hour | C 9Alkane productive rate |
| Embodiment 77 | 30 | 6 | 10 | 1 |
| Embodiment 78 | 100 | 6 | 10 | 12 |
| Embodiment 79 | 150 | 6 | 10 | 30 |
| Embodiment 80 | 230 | 6 | 10 | 90 |
| Embodiment 81 | 350 | 6 | 10 | 78 |
| Embodiment 82 | 180 | 6 | 10 | 80 |
| Embodiment 83 | 180 | 0.1 | 10 | 35 |
| Embodiment 84 | 180 | 2 | 10 | 72 |
| Embodiment 85 | 180 | 20 | 10 | 85 |
| Embodiment 86 | 180 | 6 | 0.5 | 50 |
| Embodiment 87 | 180 | 6 | 3 | 74 |
| Embodiment 88 | 180 | 6 | 24 | 84 |
As can be seen from Table 3, when temperature is greater than 230 DEG C, pressure is greater than 2MPa, and the reaction times is greater than 3 constantly little, and the hydrogenation deoxidation effect of isophorone is just remarkable, improves temperature of reaction or time further, can obtain the yield of better liquid phase alkane.
3) in fixed-bed reactor, the impact of the ratio of the mass space velocity of temperature, reaction raw materials and catalyzer and hydrogen and reaction raw materials.Be packed into 2.0 grams of catalyzer, hydrogen is controlled to flow through beds from bottom to top by mass flowmeter, and reaction raw materials is isophorone, pumps into beds from bottom to top through efficient liquid-phase chromatographic pump.Using 5% nickel-commercial silica as hydrogenation catalyst, detailed results is in table 4.
The ratio of the mass space velocity of table 4 temperature, pressure, reaction raw materials and catalyzer and hydrogen and reaction raw materials is on the impact of hydrogenation reaction
As can be seen from Table 4, when temperature is greater than 230 DEG C, pressure is greater than 2MPa, and mass space velocity is less than 1h
-1, when hydrogen flowing quantity is greater than 120mL/min, just remarkable to the hydrogenation deoxidation effect of isophorone, improve hydrogen flow rate further, little on reaction impact; Improve temperature, pressure or reduce mass space velocity and can obtain higher transformation efficiency and yield.
By above embodiment, detail the detailed process (embodiment 1-35) of a series of catalyst preparing, and in the hydrogenation deoxidation reactive behavior of furyl oxygen-containing organic compound, comprehensive discussion has been carried out to them.Under above given condition (embodiment 36-102), obtain very high C
8-C
18the yield of liquid alkane.They directly can use as aviation kerosene and high-quality diesel oil, or as improving the additive of cetane value, adding in existing aviation kerosene and diesel oil use with certain proportion.
Claims (5)
1. the application of hydrogenation deoxidation catalyst in synthesis renewable diesel or aviation kerosene, is characterized in that:
Adopt load type metal silicon oxide catalyst, the oxygen-containing organic compound hydrogenation deoxidation that catalysis biomass obtains prepares the liquid alkane of renewable diesel or aviation kerosene, wherein:
The oxygen-containing organic compound that biomass obtain is isophorone, 3,3,5-trimethylammonium cyclopentanol, 3,3,5-trimethylammonium cyclopentanone, 2-ethyl, 2-hexenoic aldehyde, 2-ethyl, 2-hexanol, 2-ethyl, 2-hexanal, C
8-C
20lipid acid, C
8-C
20fatty acid methyl ester, C
8-C
20fatty-acid ethyl ester, a kind of in the lipid acid triglyceride of fatty acid carbon chain between 8-20 or two kinds mixture;
Load type metal silicon oxide A/X type catalyzer: active component A is one or more in W metal, Cu, Co, Fe, Pt, Pd, Ru, Rh, Ir; Carrier X is silicon oxide, and in catalyzer, the mass content of active component A is: 0.1-80%, and preferable range is 2-50%.
2., according to application according to claim 1, it is characterized in that:
Silicon oxide is one or both mixture in commercial silica and ordered meso-porous silicon oxide SBA-15.
3., according to application according to claim 1, it is characterized in that:
Load type metal silicon oxide A/X type catalyzer adopts incipient impregnation or the preparation of deposition sedimentation method:
Pickling processes is as follows: first by the soluble salt solutions of A by metering than being added to the medium volume impregnation of carrier X shaping in advance, room temperature leaves standstill more than 2 hours, then dry and in 300-600 DEG C of roasting 2-5 hour, obtain baked catalyzer;
Deposition-precipitation method process is as follows: first by the soluble salt solutions of A by metering than being added in the suspension liquid of carrier X shaping in advance, under continuous stirring, add corresponding precipitation agent; And aging more than 2 hours, filter, dry; In 300-600 DEG C of roasting 2-5 hour, obtained baked catalyzer;
Wherein precipitation agent is one or more mixtures in urea, ammoniacal liquor, volatile salt, sodium hydroxide.
4., according to the application described in claim 1 or 3, it is characterized in that:
Described baked catalyzer needs to carry out reduction treatment before use: reduce at fixed-bed reactor situ: reductive condition is hydrogen pressure 0.1-10MPa, hydrogen/catalyst volume air speed 800-5000h
-1, reduction temperature 200-600 DEG C, recovery time 1-10 hour;
Or, carry out in tube furnace: hydrogen pressure is normal pressure, hydrogen/catalyst volume air speed 800-5000h
-1, reduction temperature 200-600 DEG C, the recovery time is 1-10 hour; Be down to after room temperature until temperature, need volume ratio 1%O be passed into
2/ N
2passivation more than 2 hours.
5., according to application according to claim 1, it is characterized in that:
This catalyzer is used for the hydrogenation deoxidation reaction of the oxygen-containing organic compound obtained by biomass, the solvent-free direct hydrogenation deoxidation under mild conditions can be realized;
This reaction can be carried out or carry out in fixed-bed reactor in batch reactor;
Time in batch reactor, temperature of reaction 25-350 DEG C, preferable reaction temperature is 100-260 DEG C, hydrogen pressure 0.1-20MPa, reaction times 0.5-24 hour;
Time in fixed-bed reactor, temperature of reaction 25-350 DEG C, preferable reaction temperature is 100-260 DEG C, hydrogen pressure 0.1-20MPa; Liquid material/catalyst quality the air speed of moving phase reactor furyl oxygen-containing organic compound is 0.1-10h
-1, preferred air speed is 0.5-2h
-1, hydrogen/catalyst volume air speed is 600-15000h
-1.
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| CN109705985A (en) * | 2017-10-25 | 2019-05-03 | 中国科学院大连化学物理研究所 | A kind of method that PET, PTT, PBT manufacture object are converted into aviation kerosine range cyclic hydrocarbon |
| CN109433211A (en) * | 2018-11-22 | 2019-03-08 | 东南大学 | A kind of preparation method of octanoic acid hydrogenation deoxidation catalyst |
| CN111217657A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for synthesizing methyl cyclopentadiene from 3-methyl-2-cyclopentene-1-ketone |
| CN111217657B (en) * | 2018-11-25 | 2021-04-30 | 中国科学院大连化学物理研究所 | Method for synthesizing methyl cyclopentadiene from 3-methyl-2-cyclopentene-1-ketone |
| CN111111679A (en) * | 2020-01-06 | 2020-05-08 | 湘潭大学 | Sulfur-free nickel-molybdenum bimetallic hydrodeoxygenation catalyst |
| CN111111679B (en) * | 2020-01-06 | 2023-05-02 | 湘潭大学 | Sulfur-free nickel-molybdenum bimetallic hydrodeoxygenation catalyst |
| CN111302891A (en) * | 2020-04-01 | 2020-06-19 | 华东师范大学 | Method for preparing gasoline and antifreeze from PET plastic |
| CN113004953A (en) * | 2021-03-16 | 2021-06-22 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
| CN113004953B (en) * | 2021-03-16 | 2022-05-20 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
| CN116459824A (en) * | 2023-04-13 | 2023-07-21 | 西安华大骄阳绿色科技有限公司 | Multi-metal supported transition metal oxide catalyst, preparation method thereof and application thereof in production of renewable fuel oil |
| CN116590044A (en) * | 2023-05-12 | 2023-08-15 | 中国科学技术大学 | Method for preparing biological aviation fuel by using bagasse waste |
| CN116590044B (en) * | 2023-05-12 | 2024-09-10 | 中国科学技术大学 | Method for preparing biological aviation fuel by using bagasse waste |
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