CN104711012B - 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, aviation is prepared by hydrogenation deoxidation
The new method of kerosene range hydro carbons.Biomass aerial kerosene precursor is realized in nothing using load type metal-silicon oxide catalyst
Direct hydrogenation deoxidation under the temperate condition of solvent, high yield obtains a series of aerial kerosene（Or diesel oil）The hydrocarbon of chain length range
Class compound.Compared with existing hydrodeoxygenation process, the method has simple solvent-free, operating procedure, low energy consumption, low cost
Etc. advantage.
Background technology
Aerial kerosene is the liquid fuel being in great demand in the world at present, is the strategic goods and materials of a country.It
Species is a lot, and the chain alkane, aromatic hydrocarbons and cycloalkane usually by carbon number between 8-16 is constituted.By taking current common JP-8 as an example,
Its classics composition is as follows：C8To C16Linear paraffin account for 35%, C8To C16Branched paraffin account for 35%, C7To C10Aromatic hydrocarbon account for
18%, C6To C10Cycloalkane account for 7%.Diesel oil is one of main transport fuel, mainly by C9To C21Chain hydrocarbon, cyclic hydrocarbon, virtue
Fragrant hydrocarbon composition, its boiling point is between 170-390 DEG C.At present, aerial kerosene and diesel oil are mainly with fossil resource（Coal and oil）For
Waste, coal and oil are all the non-renewable energy, synthesize aerial kerosene and diesel oil by them and are manufacturing and using process
Substantial amounts of carbon dioxide can be produced, greenhouse effect is caused.And recently as the increasingly reduction of petroleum resources, crude oil price is continuous
It is soaring so that the price of aerial kerosene and diesel oil also climbs up and up.China as energy-consuming big country and petroleum import big country, closely
The petroleum import amount of several years is continuously increased, and the petroleum import interdependency of 2009 is 53.6%, has broken through 50% national security
Warning line.2012, the dependence on foreign countries for oil of China was even more the historic high for reaching 58%.Thus, develop alternative tradition
The variation route of Fossil fuel is very urgent.Different with fossil energy, biomass belong to regenerative resource, and biomass fuel exists
The carbon dioxide produced in combustion process can be offset by its growth course by the carbon dioxide of photosynthesis consumption, therefore
Biomass fuel is that carbon dioxide is neutral during whole use.Therefore from national energy security, environmental protection and dive
Economic worth three from the aspect of, need to greatly develop biomass aerial kerosene technology.
At present, biomass liquid fuel can be divided into first generation biomass liquid fuel and second filial generation biomass liquid fuel.
First generation biomass liquid fuel is with edible corn and soybean and Helianthi etc. as raw material, by fermentation and transesterification etc.
Bio-ethanol and biodiesel are produced in reaction.First generation biomass liquid fuel is in the area such as Europe, America as transport fuel
Existing practical application.But, its combustibility is bad, and primary motivation must be improved, and can use.Second filial generation biomass
Liquid fuel is that, with unedible lignocellulose as raw material, mainly have three kinds of approach to generate fuel：1）Heat chemistry gasification life
Then material produces alkane to synthesis gas by F- T synthesis, the process comparative maturity, however it is necessary that the bar of High Temperature High Pressure
Part；2）High temperature pyrolysis biomass produce bio-oil, and the process is complicated, and obtained bio-oil inferior quality, it is impossible to directly
As engine fuel, further refine need to be carried out；3) the biomass platform chemicals point obtained as raw material with lignocellulose
Son, by the C-C coupling reaction such as aldol condensation, alkylation be anti-, then hydrogenation deoxidation produces liquid alkane, the process condition phase
Gentle to comparing, synthetic route is relatively more flexible.
2005, Dumesic, Huber et al. [Science, 2005,308,1446-1450] and patent [US7,671,
246] Hydroxymethylfurfural or furfural and acetone are reported（Or tetrahydrofurfural is intermolecular）By the aldol reaction system of base catalysiss
The oxygen-containing organic compound with aerial kerosene chain length range is taken, then C is produced by steps such as hydrogenation and hydrogenation deoxidations8To C15
The liquid alkane of scope.Use Pt/SiO2-Al2O3As hydrogenation deoxidation catalyst, using the phase reaction device of fixed bed four, course of reaction
In need to add hexadecane to prevent catalyst from inactivating, technics comparing is complicated.At [ChemSusChem, 2008,1,417-424] and
They are improved the preparation technology to Hydroxymethylfurfural and furfural patent [US7,880,049], and using the niobium of phosphorylation
Oxide makees carrier.It was found that using after new support good effect also need not can be obtained using hexadecane, so as to simplify work
Skill.But because the alkane of the process synthesis is linear paraffin, the freezing point of these hydro carbons is very high（Pentadecane：8.5-10
DEG C, n-tridecane：- 5.5 DEG C, n-dodecane:-12℃）, do not meet the requirement of aerial kerosene（Fusing point is less than -40 DEG C）.Recently,
Corma et al. [Angew.Chem.Int.Ed.2011,50,1-5] reports methylfuran and butyraldehyde, 5 methyl furfural, 5- hydroxyls
Methyl furfural and its own trimerization reaction, are prepared for the oxygen-containing organic compound with aerial kerosene or diesel oil chain length range,
A series of low-freezing branched-chain hydrocarbons with aerial kerosene chain length range are obtained thereafter by gradient bed reactor hydrogenation deoxidation
Class.Subsequently, Corma et al. [ChemSusChem, 2011,4,1574-1577] and the method to hydrogenation deoxidation is improved,
And adopt Pt/C, Pt/C-TiO2 as catalyst, by alkylate direct hydrogenation deoxidation（350℃）Obtain higher
Liquid phase alkane yield.[the Chinese patent in the work of this seminar early stage：Application number：201110346501.1；
201210169817.2；20121043947.9；201310150270.6], alkyl is passed through using furyl oxygen-containing organic compound
Change reaction or aldol reaction obtains a series of oxygen-containing organic compounds with aerial kerosene chain length range, by this
The deoxidation of a little organic compound direct hydrogenations obtains the low-freezing branched-chain hydrocarbons with aerial kerosene chain length range.Also develop simultaneously
Tungsten carbide catalyst and metal-solids acid bifunctional catalyst that nickel promotes, it is possible to achieve substitute noble metal and be hydrogenated with
Deoxygenation.But these methods are still higher in the reaction temperature that hydrodeoxygenation step needs（350℃）Or need acidity
Carrier.In this patent, it has been found that biomass aerial kerosene precursor can be realized on load type metal-silicon oxide catalyst
Low temperature（100-260℃）Complete hydrogenation deoxidation, so as to obtain the biomass with aerial kerosene chain length range with high selectivity
Liquid fuel.
The content of the invention
The oxygen-containing organic compound hydrogenation deoxidation system that the present invention is obtained for load type metal silicon oxide catalyst in biomass
Application in standby liquid alkane reaction.Such catalyst can cause hydrogenation deoxidation reaction efficiently to enter at lower temperatures
OK, so as to reducing energy consumption of reaction.Such catalyst is divided into and being made up of two parts：Active component A be W metal, Pt, Pd, Ru,
One or more in Rh, Ir, Fe, Co, Cu etc.；Carrier X be silica support such as：Commercial silica and order mesoporous oxygen
One or two mixture in SiClx SBA-15.Such catalyst can in a mild condition to biomass aerial kerosene precursor
Carry out hydrogenation deoxidation reaction.The features such as catalyst has simple solvent-free, operating procedure, low energy consumption, low cost in the present invention, carries
A kind of preferable hydrogenation deoxidation new way that aerial kerosene chain hydrocarbon is prepared by biomass aerial kerosene precursor hydrogenation deoxidation is supplied.
The present invention is achieved by the following technical solutions：
The present invention realizes body hypothermia direct hydrogenation before biomass aerial kerosene using load type metal-silicon oxide catalyst
Deoxidation prepares the alkane of aerial kerosene or diesel range.
Biomass aerial kerosene precursor main component includes one of the following kind or more than two kinds of mixture：Isophorone,
3,3,5- trimethyl cyclopentanol, 3,3,5- trimethyl Ketocyclopentane, 2- ethyls, 2- hexenoic aldehydes, 2- ethyls, 2- hexanols, 2- ethyls, 2-
Hexanal, C8-C20Fatty acid, C8-C20Fatty acid methyl ester, C8-C20Fatty-acid ethyl ester, fatty acid carbon chain between 8-20
One kind or two kinds of mixture in fatty acid triglyceride.
Load type metal silicon oxide A/X type catalyst：Active component A is W metal, Cu, Co, Fe, Pt, Pd, Ru, Rh, Ir
One or more in；Carrier X is：Commercial silica and ordered meso-porous silicon oxide SBA-15 one or more
Mixture.The content of active component A is：0.1-80%, preferred scope is 2-50%.
Load type metal-silicon oxide catalyst is prepared using infusion process or deposition-precipitation method.
Pickling processes are as follows：It is first that the soluble salt solutions of A are medium to the carrier X of advance comprising than adding by metering
Volume impregnation, is stored at room temperature more than 2 hours, is then dried and in 300-600 DEG C of roasting 2-5 hour, and baked catalysis is obtained
Agent.
Deposition-precipitation method process is as follows：First by the soluble salt solutions of A by metering than adding to the carrier X of advance comprising
Suspension in, lower add corresponding precipitant being stirred continuously.And aging more than 2 hours, filter, it is dried.And in 300-600
DEG C roasting 2-5 hours, are obtained baked catalyst.
Baked catalyst need to carry out reduction treatment using before：Can reduce in fixed bed reactors situ：Also
Old terms is that Hydrogen Vapor Pressure is 0.1-10MPa, hydrogen/catalyst volume air speed 800-5000h-1, 200-600 DEG C of reduction temperature,
Recovery time is 1-10 hours.
Can also carry out in tube furnace：Hydrogen is normal pressure, hydrogen/catalyst volume air speed 800-5000h-1, reduction temperature
200-600 DEG C of degree, the recovery time is 1-10 hours.After temperature is down to room temperature, volume ratio 1%O need to be passed through2/N2Passivation 2 hours with
On.
The reaction can be carried out in batch reactor or carried out in fixed bed reactors.
When in batch reactor, reaction temperature 25-350 DEG C, preferable reaction temperature is 100-260 DEG C, Hydrogen Vapor Pressure
0.1-20MPa, response time 0.5-24 hour.
When in fixed bed reactors, reaction temperature 25-350 DEG C, preferable reaction temperature is 100-260 DEG C, Hydrogen Vapor Pressure
0.1-20MPa；Mobile phase reactor lignocellulose base aerial 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 realize 100-260 DEG C at low temperature, to biomass
The hydrogenation deoxidation of the oxygen-containing organic compound high selectivity high yield of acquisition prepares the hydro carbons of diesel oil or aerial kerosene chain length range
Fuel.
The invention has the advantages that：
The catalyst being related in the present invention has without the need for solvent, operating procedure is simple, reaction condition is gentle, aerial kerosene
（Or diesel oil）The features such as selectivity is good, is that one kind prepares diesel oil or aerial kerosene by biomass oxygen-containing organic compound hydrogenation deoxidation
The preferable catalyst of scope HC fuel.Especially, such catalyst begins with hydrogenation deoxidation activity at 100 DEG C；150
DEG C or so, under condition of no solvent, alkane yield is up to 30%.This is the best result reported so far.
Description of the drawings
Fig. 1 is the products distribution GC spectrogram of embodiment 32.
Fig. 2-(a-e) is GC-MS spectrograms；Fig. 2-(a) embodiment 32GC-MS total ion current figures；Fig. 2-(b) embodiments
The matching figure of 32GC-MS principal products 1；The matching figure of Fig. 2-(c) embodiments 32GC-MS principal product 2；Fig. 2-(d) embodiment 32GC-MS pairs
The matching figure of product 1；The matching figure of Fig. 2-(e) embodiments 32GC-MS by-product 2.
It can be seen that the reaction primary product of embodiment 32 is 1,1,3- trimethyls from the GC-MS spectrograms of Fig. 2-(a-e)
Hexamethylene and its isomer, by-product is 3,3,5- cyclonols.The alkane products generated in other embodiments are therewith
It is similar.
Specific embodiment
The present invention will be illustrated with specific embodiment below, but protection scope of the present invention is not limited to these
Example.
Embodiment
1. the preparation of catalyst：
（1）Infusion process：The nickel nitrate solution of mass concentration 10% is prepared, is carried out accordingly according to the saturated water adsorptive value of carrier
Dilution, adds in commercial silica and ordered meso-porous silicon oxide SBA-15 among one kind, then stands 2 hours, does at 120 DEG C
It is dry overnight, in 500 DEG C of air roastings 2 hours, with hydrogen reducing 2 hours at 500 DEG C, after temperature is reduced to room temperature volume is passed through
Compare 1%O2/N2Passivation, can prepare the Raney nickel of different carriers load（1 is shown in Table, embodiment 1,2）.
Prepare Palladous chloride., ruthenic chloride, chloroplatinic acid, chloro-iridic acid, radium chloride, nickel nitrate, cobalt nitrate, the nitric acid of mass ratio 10%
Copper, iron nitrate solution, will be therein a kind of according to necessarily measuring in ratio addition commercial silica, then 2 hours is stood, 120
It is dried overnight at DEG C, in 500 DEG C of air roastings 2 hours, with hydrogen reducing 2 hours at 500 DEG C, leads to after temperature is reduced to room temperature
Enter volume ratio 1%O2/N2Passivation, can prepare support type single-metal reforming catalyst（1 is shown in Table, embodiment 2-10）.
Prepare radium chloride, Palladous chloride., ruthenic chloride, chloro-iridic acid, chloroplatinic acid, cobalt nitrate, copper nitrate, the nitric acid of mass ratio 10%
Ferrous solution, it is compared according to different meterings and is added together with nickel nitrate solution in commercial silica, then stands 2 hours,
It is dried overnight at 120 DEG C, in 500 DEG C of air roastings 2 hours, with hydrogen reducing 2 hours at 500 DEG C, treats that temperature is reduced to room temperature
After be passed through volume ratio 1%O2/N2Passivation, can prepare the nickel alloy catalyst of support type different metal ratio（1 is shown in Table, embodiment 11-
18）.
The nickel nitrate solution of mass ratio 10% is prepared, it is diluted according to different content, in adding commercial silica,
Then 2 hours are stood, is dried overnight at 120 DEG C, in 500 DEG C of air roastings 2 hours, with hydrogen reducing 2 hours at 500 DEG C,
Volume ratio 1%O is passed through after temperature is reduced to room temperature2/N2Passivation, can prepare the nickel catalyst carried of different Ni contents（It is shown in Table
1, embodiment 19-23）.
（2）Deposition-precipitation method：The nickel nitrate solution of mass ratio 10% is prepared, commercial silica and order mesoporous oxidation is added
Silicon SBA-15, adds a certain amount of carbamide in 80 DEG C of water-baths, stirs 10 hours after being warming up to 90 DEG C, and cooling is filtered, washing,
It is dried overnight at 120 DEG C, in 500 DEG C of air roastings 2 hours, with hydrogen reducing 2 hours at 500 DEG C, treats that temperature is reduced to room
Volume ratio 1%O is passed through after temperature2/N2Passivation, can prepare nickel catalyst carried（1 is shown in Table, embodiment 24,25）.
The nickel nitrate solution of mass ratio 10% is prepared, commercial silica is added, a certain amount of urine is added in 80 DEG C of water-baths
Element, stirs 10 hours after being warming up to 90 DEG C, and cooling is filtered, and washing is dried overnight at 120 DEG C, little in 500 DEG C of air roastings 2
When, use hydrogen reducing 2 hours at 500 DEG C, it is passed through volume ratio 1%O after temperature is reduced to room temperature2/N2Passivation, can prepare different nickel
Content it is nickel catalyst carried（1 is shown in Table, embodiment 26-32）.
The load type metal catalyst of table 1
| Embodiment | Carrier | Metal and its loading（Percentage by weight） |
| 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 its loading（Percentage by weight） |
| 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 reactors of 100mL, biomass aerial kerosene precursor is added（Isophorone, 2- ethyls, 2- hexenes
Aldehyde, methyl stearate, soft-methyl ester, methyl oleate, microalgae oil, Oleum Glycines etc.）40mL, 2.0 grams of catalyst, at 230 DEG C, with
Metal-oxide Si catalyst（Embodiment 1-35）As hydrogenation deoxidation catalyst, Hydrogen Vapor Pressure 6.0MPa, react 10 hours.It is logical
Gas chromatographic analysiss are crossed, detailed reaction the results are shown in Table 2.
The impact of the catalyst of table 2, raw material composition to hydrogenation reaction
As can be seen from Table 2, under condition of no solvent, selected catalyst can obtain the liquid phase of certain yield in table
Alkane, wherein higher with noble metal catalyst, the Ni-based monometallic of load and alloy catalyst activity.And with different biologies
Matter aerial kerosene precursor can obtain higher liquid alkane yield for raw material.
2）In the Parr reactors of 100mL, isophorone 40mL, 2.0g catalyst, with 5% nickel-commercial silica are added
The impact that catalyst is reacted hydrogenation deoxidation as hydrogenation deoxidation catalyst investigation temperature, pressure, response time.Detailed reaction is tied
Fruit is shown in Table 3.
The temperature of table 3, the impact of pressure, response time to hydrogenation reaction
| Embodiment | Temperature/DEG C | Pressure/MPa | Response time/hour | C9Alkane yield |
| 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 more than 230 DEG C, pressure is more than 2MPa, when the response time is more than 3 hours, different Buddhist
The hydrogenation deoxidation effect of your ketone just significantly, is further improved reaction temperature or time, it is possible to obtain the receipts of more preferable liquid phase alkane
Rate.
3）In fixed bed reactors, the mass space velocity and hydrogen of temperature, reaction raw materials and catalyst and reaction raw materials
Ratio impact.2.0 grams of catalyst are packed into, hydrogen flows through from bottom to top beds by mass flowmenter control, instead
Raw material is answered to be isophorone, Jing efficient liquid-phase chromatographic pumps pump into from bottom to top beds.Using 5% nickel-commercial silica as
Hydrogenation catalyst, detailed results are shown in Table 4.
The mass space velocity and hydrogen of the temperature of table 4, pressure, reaction raw materials and catalyst and the ratio pair of reaction raw materials add
The impact of hydrogen reaction
As can be seen from Table 4, when temperature is more than 230 DEG C, pressure is more than 2MPa, and mass space velocity is less than 1h-1, hydrogen flowing quantity
It is just notable to the hydrogenation deoxidation effect of isophorone during more than 120mL/min, hydrogen flow rate is further improved, reaction is affected
Less；Improving temperature, pressure or reduce mass space velocity can obtain higher conversion ratio and yield.
By above example, a series of detailed process (embodiment 1-35) of catalyst preparations is detailed, and to them
It is fully discussed in the hydrogenation deoxidation reactivity of furyl oxygen-containing organic compound.Under conditions of given above
（Embodiment 36-102）, obtain very high C8-C18The yield of liquid alkane.They can be used as aerial kerosene and high-quality bavin
Oil is directly used, or as the additive of Cetane number is improved, is added in existing aerial kerosene and diesel oil with certain proportion
Use.
Claims (6)
1. application of the hydrogenation deoxidation catalyst in synthesis renewable diesel or aerial kerosene, it is characterised in that：
Using load type metal silicon oxide catalyst, prepared by the oxygen-containing organic compound hydrogenation deoxidation that catalysis biomass is obtained can be again
The liquid alkane of raw diesel oil or aerial kerosene, wherein：
The oxygen-containing organic compound that biomass are obtained is isophorone, 3,3,5- trimethyl cyclopentanol, 3,3,5- front threes basic ring penta
Ketone, 2- ethyls, 2- hexenoic aldehydes, 2- ethyls, 2- hexanols, 2- ethyls, 2- hexanals, C8-C20Fatty acid, C8-C20Fatty acid methyl
Ester, C8-C20Fatty acid triglyceride between 8-20 of fatty-acid ethyl ester, fatty acid carbon chain in one kind or two kinds of mixing
Thing；
Load type metal silicon oxide A/X type catalyst：Active component A is in W metal, Cu, Co, Fe, Pt, Pd, Ru, Rh, Ir
One or more；Carrier X is silicon oxide, and the mass content of active component A is in catalyst：0.1-80%.
2. according to the application described in claim 1, it is characterised in that：
Silicon oxide is commercial silica；
The mass content of active component A is in catalyst：2-50%.
3. according to the application described in claim 1, it is characterised in that：
Load type metal silicon oxide A/X types catalyst is prepared using incipient impregnation or deposition sedimentation method：
Pickling processes are as follows：First by the soluble salt solutions of A by metering volume more medium than the carrier X of addition to advance comprising
Dipping, is stored at room temperature more than 2 hours, is then dried and in 300-600 DEG C of roasting 2-5 hour, and baked catalyst is obtained；
Deposition-precipitation method process is as follows：First by the soluble salt solutions of A by metering than adding hanging to the carrier X of advance comprising
In turbid liquid, the corresponding precipitant of lower addition is being stirred continuously；And aging more than 2 hours, filter, it is dried；In 300-600 DEG C of roasting
2-5 hours, are obtained baked catalyst；
Wherein precipitant is one or more mixture in carbamide, ammonia, ammonium carbonate, sodium hydroxide.
4. according to the application described in claim 3, it is characterised in that：
Catalyst need to carry out reduction treatment using before：In the reduction of fixed bed reactors situ：Reducing condition is Hydrogen Vapor Pressure
0.1-10MPa, hydrogen/catalyst volume air speed 800-5000h-1, 200-600 DEG C of reduction temperature, recovery time 1-10 hour；
Or, carrying out in tube furnace：Hydrogen Vapor Pressure is normal pressure, hydrogen/catalyst volume air speed 800-5000h-1, reduction temperature
200-600 DEG C, the recovery time is 1-10 hours；After temperature is down to room temperature, volume ratio 1%O need to be passed through2/N2Passivation 2 hours with
On.
5. according to the application described in claim 1, it is characterised in that：
The hydrogenation deoxidation reaction of the oxygen-containing organic compound that the catalyst is used to be obtained by biomass, under being capable of achieving temperate condition
Solvent-free direct hydrogenation deoxidation；
The reaction can be carried out in batch reactor or carried out in fixed bed reactors；
When in batch reactor, reaction temperature 25-350 DEG C, Hydrogen Vapor Pressure 0.1-20MPa, response time 0.5-24 hour；
When in fixed bed reactors, reaction temperature 25-350 DEG C, Hydrogen Vapor Pressure 0.1-20MPa；Mobile phase reactor organisms matter
The liquid material of the oxygen-containing organic compound of acquisition/catalyst quality air speed is 0.1-10h-1, hydrogen/catalyst volume air speed is 600-
15000h-1。
6. according to the application described in claim 5, it is characterised in that：
When in batch reactor, reaction temperature is 100-260 DEG C；
When in fixed bed reactors, reaction temperature is 100-260 DEG C, and biomass acquisition is oxygen-containing organic in fixed bed reactors
The liquid material of compound/catalyst quality air speed is 0.5-2h-1。
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| CN109433211A (en) * | 2018-11-22 | 2019-03-08 | 东南大学 | A kind of preparation method of octanoic acid hydrogenation deoxidation catalyst |
| 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 |
| CN111111679B (en) * | 2020-01-06 | 2023-05-02 | 湘潭大学 | Sulfur-free nickel-molybdenum bimetallic hydrodeoxygenation catalyst |
| CN111302891B (en) * | 2020-04-01 | 2022-12-30 | 华东师范大学 | Method for preparing gasoline and antifreeze from PET plastic |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1142980A2 (en) * | 2000-04-04 | 2001-10-10 | Toyota Jidosha Kabushiki Kaisha | Process for synthesis of lower isoparaffins from synthesis gas |
| CN102676201A (en) * | 2011-03-18 | 2012-09-19 | 赵晨 | Method for preparing high-quality gasoline from cracking biological oil |
| CN103087748A (en) * | 2011-11-04 | 2013-05-08 | 中国科学院大连化学物理研究所 | Preparation method of aviation kerosene or diesel |
-
2013
- 2013-12-11 CN CN201310689593.2A patent/CN104711012B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1142980A2 (en) * | 2000-04-04 | 2001-10-10 | Toyota Jidosha Kabushiki Kaisha | Process for synthesis of lower isoparaffins from synthesis gas |
| CN102676201A (en) * | 2011-03-18 | 2012-09-19 | 赵晨 | Method for preparing high-quality gasoline from cracking biological oil |
| CN103087748A (en) * | 2011-11-04 | 2013-05-08 | 中国科学院大连化学物理研究所 | Preparation method of aviation kerosene or diesel |
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