CN105132003B - Preparation method for biological aircraft fuel - Google Patents
Preparation method for biological aircraft fuel Download PDFInfo
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- CN105132003B CN105132003B CN201510535922.7A CN201510535922A CN105132003B CN 105132003 B CN105132003 B CN 105132003B CN 201510535922 A CN201510535922 A CN 201510535922A CN 105132003 B CN105132003 B CN 105132003B
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Abstract
The invention relates to a method for preparing aircraft fuel from a biomass resource through hydrogenolysis, condensation and deoxygenation. The method comprises: carrying out hydrogenation and hydrogenolysis on the biomass resource rich in hydroxyl and derivatives thereof to obtain a dihydric alcohol product and a mono-alcohol product; then condensing the mono-alcohol product under an efficient condensation catalyst to obtain high carbon chain branch chain alcohol; and then carrying out hydrogenation and deoxidization to obtain a hydrocarbon mixture rich in branched hydrocarbon, and obtaining a highly-branched product with the boiling range in an aircraft fuel range by reasonably regulating the condensation process.
Description
Technical field
The present invention relates to a kind of method for preparing aviation fuel, belongs to green chemical technology and bioenergy technical field,
More particularly to a kind of method for preparing aviation fuel through hydrogenolysis, condensation, deoxygenation from biomass resource.
Background technology
Generally, aviation fuel is that mineral oil product goes out product of the boiling point in the range of aviation fuel by separated.With
The continuous exhausted and continuous growth to demand for fuel of fossil resources, the shortage of liquid fuel will be puzzlement human kind sustainable development
Prominent sex chromosome mosaicism, actively find the succedaneum of Fossil fuel has become countries in the world focus of attention.Biomass resource, is ground
The Renewable resource of liquid fuel can be uniquely converted on ball.The resource of more than one thousand years as a kind of human use, in recent years
To cause the extensive concern of people.With Semen Maydiss and agriculture and forestry organic waste material as raw material production bio-ethanol, and use in recent years
The biodiesel of the productions such as Jatropha curcas oil, Petiolus Trachycarpi oil and biological aerial kerosene, have begun to try out on the different vehicles,
Bio-fuel has become an important ring in world fuel market, and development prospect is wide.
At present, preparing fuel as raw material with biomass mainly has two big class routes, and a class is to utilize oil resource, Jing Guojia
The processes such as hydrogen deoxidation, isomery obtain meeting the alkane of fuel standard；Another kind of is through F- T synthesis system using synthesis gas route
The alkane of standby particular range.
Oil resource enriches very much, the carbon skeleton with composite fluid fuel.Vegetable oil, such as Semen Maydiss, Semen Brassicae campestriss, Brassica campestris L
Seed, Semen sojae atricolor, algae oil；Animal fat, such as Adeps Bovis seu Bubali, fish oil and waste oil.These glyceride and fatty acid resource become preparation can be again
One big classification of raw fuel.Praxair Technology, Inc discloses a kind of fatty acid, fatty acid ester through adding in CN 101952392A
Hydrogen, decarboxylation, decarbonylation base, hydroisomerization and selective cracking prepare aviation fuel.The mobil oil in US 4300009
Company discloses a kind of crystalline aluminosilicate zeolitic in the purposes that vegetable oil, algae oil are converted into hydrocarbon such as gasoline.In CN
Praxair Technology, Inc discloses and a kind of has boiling point in aviation fuel as raw material production with plant and animal oil in 102027097A
In the range of hydrocarbon product stream method, the method include by comprising have hydrogenation, deoxidation, isomerization and selective hydrogenation split
In changing the multifunction catalyst of function or the single reactor of one group of catalyst, add raw material hydrogenation, deoxidation, isomerization and selectivity
Hydrogen cracking processes renewable raw materials, alkane of the production with 9-16 carbon atom and Gao Yi/positive rate.
Disclose by hydroprocessing vegetable oils to prepare the side of hydrocarbon products in diesel boiling range in US 4992605
Method.Tianjin Nankai Univ. castor Engineering Science Co., Ltd discloses a kind of Semen Ricini base biology aviation in the A of CN 103320153
The preparation method of fuel, the method obtains n-alkane with Oleum Ricini as raw material by hydrogenation deoxidation reaction, then different by being hydrogenated with
Structure reaction generates isoparaffin, and fractional distillation fraction obtains final products.
It with synthesis gas (mixed gas of carbon monoxide and hydrogen) is raw material in catalyst and felicity condition that F- T synthesis are
Lower synthesis is with the hydrocarbon of liquid or the technical process of Hydrocarbon.Synthesis gas can be from biomass or fossil resource through splitting
The processes such as change, pyrolysis, reformation are obtained.Sasol Tech Pty Ltd. discloses a kind of fischer tropsch process and prepares boat in CN102124085A
The method of air-fuel material, to use itself as fuel or as a kind of component of aviation fuel mixture, it fires the fuel
The isoparaffin of material is more than 3 with the mass ratio of normal paraffin hydrocarbons.
However, either from oil resource or by F- T synthesis, the raw material of its synthesis is all linear paraffin, all
Need that through further isomerization or through mediation the demand of aviation fuel could be met.
The content of the invention
For the problem that above-mentioned prior art is present, the invention provides a kind of preparation method of bio-based aviation fuel,
In the method, dihydroxylic alcohols product can be obtained by hydrogenation, hydrogenolysis by will be enriched in the biomass resource and its derivant of hydroxyl
Product and single methanol product, then single methanol product high carbon chain branched-chain alcoho can be condensed to yield under efficient condensation catalyst, then enter one
Step hydrogenation deoxidation can obtain the hydrocarbon mixture rich in branched paraffin, by rational regulation and control condensation course, can obtain height
Product of the boiling range of degree side chain in the range of aviation fuel.
Specifically, the preparation method of the invention is a kind of alkane for preparing from renewable raw materials and can be used as aviation fuel
Method, comprise the following steps：
1) in 0.5-12MPa, under preferred 4-6MPa hydrogen atmospheres, by biomass material or biomass derived raw material, many work(
Energy catalyst a and reaction dissolvent are added in hydrogenolysis device, make raw material be hydrocracked generation single methanol, the binary that carbon side chain is 2 to 6
Alcohol and other polyol product mixture, reaction temperature 160-260 DEG C, preferred 180-220 DEG C, the response time is 1-5 hours, excellent
2-3 hours are selected, and is isolated single methanol and glycol products from product mixtures respectively by rectification under vacuum finishing reactor
Come, other polyol products are returned in the hydrogenolysis device of this step and further carry out hydrogenolysis；
2) by step 1) in the glycol products isolated, multifunction catalyst b and reaction dissolvent add another hydrogenolysis anti-
Further hydrogenolysis in device is answered, so that glycol products are reacted to single methanol, wherein Hydrogen Vapor Pressure in another hydrogenolysis device
For 0.5-12MPa, preferred 4-8MPa, reaction temperature 80-215 DEG C, preferred 120-180 DEG C, the response time is 1-5 hours, preferably
2-3 hours；
3) by step 1) and 2) in the single methanol that obtains merge, together with multifunction catalyst c, promoter and reaction dissolvent
It is 9 to 20 carbon atoms condensation to be carried out in addition condensation reaction kettle and prepares carbon number, and side chain number is that 2 to the 6 high unit's single methanol of side chain is produced
Thing, wherein reaction temperature 80-220 DEG C, preferred 160-200 DEG C, response time 2-48 hour, preferred 10-30 hours；With
4) in 0.5-12MPa, under preferred 5-8MPa hydrogen atmospheres, by step 3 in hydrogenation deoxidation reactor) in obtain
High unit's alcohol is contacted in reaction dissolvent with multi-functional hydrogenation catalyst d and carries out hydrogenation deoxidation, reaction temperature 150-350 DEG C, preferably
200-300 DEG C, reaction contact time 1-20 hours, preferred 2-8 hours, the carbon side chain for preparing 9 to 20 carbon atoms is 2 to 6
Branched paraffin, alkane products of the material stream for obtaining through the isolated boiling range of rectifying column in the range of aviation fuel.
Preferably, preparation method according to the present invention is further comprising the steps：
1a) carrying out step 1) before the step of carry out pretreatment to biomass material or biomass derived raw material, in institute
In stating pre-treatment step, such as washing is carried out to biomass material or biomass derived raw material, decolourized, removed by ion exchange
To techniques such as the poisonous and hazardous materials of catalyst used in subsequent step.
Preferably, step 1) used in reaction dissolvent can be selected from water, methanol, ethanol, propanol, butanol, acetaldehyde, third
One or more in aldehyde and acetone, the mixture of preferred water, methanol and ethanol as reaction dissolvent, water, methanol and ethanol
Part by weight is 1:0.5-0.8:0.2-0.5, preferably 1:0.5:0.5.
In preparation method according to the present invention, step 1) described in biomass material or biomass derived raw material include
Selected from straw, wood flour, syrup, paper pulp, cellulose, hemicellulose, glucose, Fructose, xylose, arabinose, Sorbitol, manna
One or more component in alcohol, xylitol, 1,2,3,4,5-pentanepentol and glycerol.
In step 1) described in multifunction catalyst a comprising be selected from VIII elemental metals, IBRace's elemental metals, VIBRace's list
Matter metal, VIIBThe sulfide of race's elemental metals and the above each race's metal be carried on zeolite, silicon dioxide, aluminium oxide, two
Silica-alumina, activated carbon and the oxide selected from group VIII metal, IBThe oxide of race's metal, VIBThe oxygen of race's metal
Compound, VIIBThe catalyst of the oxide component composition of race's metal.
Preferably, step 1) described in multifunction catalyst a be selected from by the one kind in Ru, Ni, Cu, Co, Mo, Re, W or
Two kinds are carried on ZnO, ZrO2, aluminium oxide, the catalyst that is prepared from zeolite and/or activated carbon, preferably Ni-ZnO loads
Type catalyst, Ni-Cu/ZrO2Loaded catalyst, Ni-Cu/ZnO loaded catalysts or Ni-W/Al2O3Loaded catalyst.
Preferably, step 2) described in multifunction catalyst b be to be carried on ZrO selected from Pt, Rh, Ru, Ir, W, Re, Mo2、
The catalyst that aluminium oxide, zeolite, aluminium oxide, activated carbon are prepared from, preferably Rh-Mo/ZrO2Loaded catalyst, Rh-Re/
Al2O3Loaded catalyst or Ru-W/Al2O3Loaded catalyst.
Preferably, step 2) used in reaction dissolvent can be molten selected from water, dioxane, methanol, ethanol, propanol
One or more in agent, preferably water, methanol and ethanol.
Preferably, step 3) described in multifunction catalyst c be selected from Pd, Pt, Rh, Ru, Ir one or two kinds of load
In catalyst prepared by activated carbon, preferably Pd, Ir is carried on the catalyst prepared on activated carbon.
Preferably, step 3) used in reaction dissolvent can be in methanol, ethanol, hexamethylene, normal hexane one
Plant or various.
Preferably, step 3) described in promoter be selected from Phen, sodium hydroxide, potassium hydroxide potassium phosphate, hydrogen
One or two in oxidation triethylammonium tetrakis, preferably Phen and sodium hydroxide.
Preferably, step 4) described in multifunction catalyst d be one or two in Pt, Ru, Ni, Mo, Re, W
Be carried on the catalyst that aluminium oxide, silica-alumina, zeolite are prepared from, preferably Pt-Mo be carried on silicon dioxide-
On aluminium oxide.
Preferably for step 4) in carbon atom is less than 9 or carbon side chain is less than 2 in the branched paraffin products that are condensed to yield of Jing
Alkane, then be isolated and reenter step 4) condensation reactor in react.
Preferably, step 4) used in reaction dissolvent can be the one kind or many in methanol, hexamethylene, normal hexane
Kind.
Preferably, in step 4) described in branched paraffin preferably comprising having 9 to 15 carbon atoms, carbochain is 2 to 3
Branched paraffin.
It is further preferred that in step 4) described in the branched paraffin branched paraffin that is preferably selected from following compound：
Beneficial effect
1) formation of side chain carbon skeleton is realized using the method for condensation in the present invention, process is easy to regulation and control, is added than traditional
Hydrogen isomerate process has obvious advantage.
2) branched paraffin that preparation in accordance with the present invention is obtained has on molecular structure and petroleum base jet fuel
Similar, sulfur content is low, and flash-point is high, the low feature of post combustion emission amount, and need not more reengine and fuel system, is aviation
Industry reduces carbon emission, realizes the important channel of Green Sustainable target.
3) apply the present invention prepares the technique of aviation fuel compared to other technologies, and raw material does not rely on oil
Work, and it is inexhaustible；Only product need to be obtained through the catalytic reaction of several series connection.Technique is compared to other
Technology, reaction condition is gentle, green.
4) preparation method of the invention has broad application prospects, and technological process used is simple, small investment, energy consumption
Low, yield is high, pollution is little, and technology controlling and process is easily, is adapted to industrialized production.
Specific embodiment
1 the step of preparation method according to the present invention) hydrogenolysis device in, Hydrogen Vapor Pressure is in 0.5-12MPa
In the range of, preferred 4-6MPa.If less than 0.5MPa, then reaction is difficult to；If greater than 12MPa, then response speed is too fast,
Simultaneous reactions thing excessive fragmentation, causes the by-product that there is excessive lower alkyl hydro carbons in product.
1 the step of preparation method according to the present invention) hydrogenolysis device in, reaction temperature should be controlled in 160-
260 DEG C, preferred 180-220 DEG C, the response time be 1-5 hours, preferred 2-3 hours, if reaction temperature is too low or too high, or
Response time is long or too short, is all unfavorable for the selection of alcohols product, particularly for single methanol and glycol.
In addition, the step of preparation method according to the present invention 1) used in reaction dissolvent can be selected from water, first
One or more in alcohol, ethanol, propanol, butanol, acetaldehyde, propionic aldehyde and acetone, the mixture conduct of preferred water, methanol and ethanol
Reaction dissolvent, the part by weight of water, methanol and ethanol is 1:0.5-0.8:0.2-0.5, preferably 1:0.5:0.5.When water, methanol
During with the mixture of ethanol as reaction dissolvent, can effectively suppress the excessive fragmentation of C-C keys in reactant, so as to prevent shape
Into the gaseous product such as undesirable lower paraffin hydrocarbon (for example, methane, ethane etc.) or carbon dioxide.When water, methanol and ethanol
In mixed solvent the ratio of three kinds of solvents within the above range when, it can be ensured that hydrogenolysis milder, hydrogenolysis are played
Certain " buffering " effect, the selectivity for making single methanol and glycol in product is maximized.
Similarly, 2 the step of preparation method according to the present invention) hydrogenolysis device in need suitable control hydrogen
Atmospheric pressure is 0.5-12MPa, preferred 4-8MPa, reaction temperature 80-215 DEG C, preferred 120-180 DEG C, and the response time is that 1-5 is little
When, preferred 2-3 hours, when reaction condition within this range when, it can be ensured that the selectivity highest of single methanol in product, react by-product
Thing is minimum, it is possible to achieve the optimization of reaction efficiency.
3 the step of preparation method according to the present invention) in, except the choosing of multifunction catalyst c and reaction dissolvent
Select outer, the use of promoter is extremely important, the promoter selected from Phen, sodium hydroxide, potassium hydroxide potassium phosphate,
One or two in tetraethylamine hydroxide, preferably Phen and sodium hydroxide.Only with multifunction catalyst c, and
In the case of not adopting promoter, the step 3) reaction yield it is very low, additionally as product the high unit's single methanol of side chain
Chain number is difficult to control to, and easily generates a large amount of straight chain single methanols, and is not used to aviation fuel.
1 the step of preparation method according to the present invention) to the composition and system of catalyst a, b, c, d used in 4)
Preparation Method can refer to existing known technology in prior art, for example, can adopt infusion process, coprecipitation and deposition sedimentation
Prepared by method, the then reduction activation or in formaldehyde, formic acid, sodium formate, methanol, ethanol, propanol, butanol, water in hydrogen atmosphere
Closing in hydrazine, sodium borohydride, the liquid medium with reducing property such as vitamin C carries out reduction activation, for example can be according to《Catalysis
Agent preparation process technology》, Zhang Jiguang, Sinopec publishing house, 2004 and Ertl, G.；H.；Weitkamp,
J., the universal method disclosed in Handbook of heterogeneous catalysis.1997 is carried out.Catalyst activity group
The product that the selection and content for dividing can be obtained as requested is selected.
Below in conjunction with specific embodiment, the invention will be further described.Embodiment party of the embodiment only as the present invention
The example of case is enumerated, and does not constitute any restriction to the present invention, it will be appreciated by those skilled in the art that without departing from the present invention's
Modification in the range of essence and design each falls within protection scope of the present invention.
Embodiment 1
Step 1a)：Straw is crushed, enzymolysis is carried out after washing through pretreated straw and is obtained raw sugar liquid, slightly
The composition of sugar liquid mainly contains the soluble oligosaccharides such as glucose, xylose, arabinose and xylan, cellobiose, trisaccharide
And the degradation product of sugar, such as furfural, 5 hydroxymethyl furfural, make sugared concentration in solution reach 10-50wt%, all dissolvable sugared Jing
Activated carbon decolorizing is crossed, ion exchange is removed to the poisonous and hazardous material of catalyst used in subsequent step.
Step 1)：By step 1a) in the sugar content concentration that obtains pump into hydrogen in 20wt% biomass material saccharified liquid 500ml
Solution reactor, while the methanol and ethanol that prevent sugar liquid raw material excessive fragmentation are added in hydrogenolysis device as solvent, solvent
Methanol, amount of alcohol added are 0.5 times of water consumption in sugar liquid, are subsequently adding with the preparation of co-precipitation-gel method and in 500 DEG C of hydrogen
The Ni-Cu-ZnO catalyst 5g (such as can according to disclosed in CN102286548 method prepare) of middle reduction activation, 180 DEG C,
2h is reacted under the reaction condition of 6MPa hydrogen atmospheres, that is, obtains hydrogenolysis liquid, hydrogenolysis liquid respectively is isolated by through rectification under vacuum
Lower boiling dihydroxylic alcohols and single methanol product, high boiling alcohol therein, such as erythritol, glycerol, Mannitol, Sorbitol are returned
Hydrogenolysis device.
Step 2)：By step 1) in the dihydroxylic alcohols that obtain be adjusted to 50% aqueous solution and pump into another hydrogenolysis device, and
Add the Rh/SiO prepared with infusion process2Catalyst 10g (for example can be according to Wang, X.C.；Wu,F.；Yao,S.X.；
Jiang,Y.J.；Guan,J.；Mui,X.D.,Ni-Cu/ZnO-catalyzed Hydrogenolysis of Cellulose
for the Production of 1,2-Alkanediols in Hot Compressed Water.Chemistry
It is prepared by Letters 2012,41, (5), the method disclosed in 476-478), under 120 DEG C, the reaction condition of 8MPa hydrogen atmospheres
Reaction 12h, Jing rectifications under vacuum can be prepared by single methanol, and unreacted raw material returns hydrogenolysis device to be continued to convert；The single methanol of acquisition
Product according to weight than respectively containing 5% methanol, 30% ethanol, 42% propanol, 10% butanol, 2% amylalcohol, 3% hexanol, 8%
Isopropanol.
Step 3)：By step 2) in the single methanol product that obtains add in condensation reactor, in the Ir/C prepared with infusion process
In the presence of catalyst 5g and promoter Phen 0.3g and sodium hydroxide 0.8g, react under 180 DEG C of reaction condition
16h, is obtained high unit's branched-chain alcoho.Material stream is separated through rectification under vacuum, and low condensed products of the carbon number less than 9 are returned into condensation
Reactor is further reacted.
Step 4)：By step 3) in the carbon number that obtains be that more than 9 height unit branched-chain alcoho product adds deoxidation hydrogenation anti-
Device is answered, the Pt/Al prepared with infusion process is filled in reactor2O3Catalyst 10ml, at 280 DEG C, the reaction bar of 6MPa hydrogen atmospheres
React under part, control sample introduction air speed is in 0.5L/h.Product compares right by gas chromatography mass spectrometry (GC-MS) and reference material GC retention times
Product carries out qualitative analyses, and after rectification under vacuum is separated, according to percentage by weight, C9 product assays are for 10%, C10 product assays
It is that 20%, C15 product assays are 20% that 25%, C11 product assay is 18%, C12 product assays, and balance of carbon number exists
The product of more than C15.
Embodiment 2
Specific implementation process with embodiment 1, except that step 1) in added catalyst be Ni-ZrO2, it is final to produce
After rectification under vacuum separation, according to percentage by weight, it is 30%, C11 products that C9 product assays are 5%, C10 product assays to product
It is 28% for 16%, C15 product assays that content is 21%, C12 product assays, product of the balance of carbon number in more than C15.
Embodiment 3
Specific implementation process with embodiment 1, except that step 2) in add catalyst be Ru/Al2O3Catalyst,
After rectification under vacuum separation, according to percentage by weight, C9 product assays are consisted of final products for 7%, C10 product assays
28%, C11 product assay be 15%, C12 product assays be 12%, C15 product assays be 29%, balance of carbon number C15 with
On product.
Embodiment 4
Specific implementation process is with embodiment 1, except that only Sorbitol is raw material, in the hydrogenolysis device of step 2
The catalyst of addition select Ni-Mo/MgO catalyst, final products through rectification under vacuum separation after, according to percentage by weight, C9
Product assay is that 8%, C10 product assays contain for 22%, C12 product assays for 26%, C11 product assays for 17%, C15 products
Measure as 22%, product of the balance of carbon number in more than C15.
Preparation in accordance with the present invention, realizes polysaccharide to dihydroxylic alcohols, dihydroxylic alcohols to single methanol, and single methanol further contracts
The height unit alcohol molecule depolymerization cracking of conjunction rebuilds the process of long-chain molecule to small molecule and small molecule.In cracking process,
Using the catalyst of matching, aid in controlling the generation of excessive fragmentation with appropriate catalystic converter system, realize biomass material
Efficiently to the conversion of end product branched paraffin.
Claims (16)
1. a kind of preparation method of bio-based aviation fuel, comprises the following steps：
1) under 0.5-12MPa hydrogen atmospheres, by biomass material or biomass derived raw material, multifunction catalyst a and reaction
Solvent is added in hydrogenolysis device, makes raw material be hydrocracked generation single methanol, the dihydroxylic alcohols that carbon side chain is 2 to 6 and other polyhydric alcohol
Product mixture, reaction temperature 160-260 DEG C, the response time is 1-5 hours, and by rectification under vacuum finishing reactor by single methanol
Separate from product mixtures respectively with glycol products, other polyol products are returned in the hydrogenolysis device of this step
Hydrogenolysis are further carried out, the reaction dissolvent is selected from the mixture of water, methanol and ethanol, the weight of water, methanol and ethanol
Ratio is 1:0.5-0.8:0.2-0.5；
2) by step 1) in the glycol products isolated, multifunction catalyst b and reaction dissolvent add another hydrogenolysis device
In further hydrogenolysis, so that glycol products are reacted to single methanol, wherein Hydrogen Vapor Pressure is in another hydrogenolysis device
0.5-12MPa, reaction temperature 80-215 DEG C, the response time is 1-5 hours；
3) by step 1) and 2) in the single methanol that obtains merge, with multifunction catalyst c, helping selected from Phen and sodium hydroxide
Catalyst and reaction dissolvent add carry out in condensation reaction kettle condensation to prepare carbon number for 9 to 20 carbon atoms together, and side chain number is 2
To the 6 high unit's single methanol product of side chain, wherein reaction temperature 80-220 DEG C, response time 2-48 hour；With
4) under 0.5-12MPa hydrogen atmospheres, by step 3 in hydrogenation deoxidation reactor) in obtain height unit alcohol with it is multi-functional
Hydrogenation catalyst d is contacted in reaction dissolvent carries out hydrogenation deoxidation, and reaction temperature 150-350 DEG C, reaction contact time 1-20 is little
When, the carbon side chain for preparing 9 to 20 carbon atoms is 2 to 6 branched paraffin, and the material stream for obtaining is through the isolated boiling of rectifying column
Alkane products of the journey in the range of aviation fuel.
2. the preparation method of bio-based aviation fuel according to claim 1, wherein the step 1) described in hydrogen gas
Atmosphere is 4-6MPa, and reaction temperature is 180-220 DEG C, and the response time is 2-3 hours；The step 2) described in Hydrogen Vapor Pressure be 4-
8MPa, reaction temperature is 120-180 DEG C, and the response time is 2-3 hours；The step 3) described in reaction temperature be 160-200
DEG C, the response time is 10-30 hours；The step 4) described in hydrogen atmosphere be 5-8MPa, reaction temperature be 200-300 DEG C,
Reaction contact time 2-8 hours.
3. the preparation method of bio-based aviation fuel according to claim 1, wherein the preparation method is further included
Following steps：
1a) carrying out step 1) before the step of carry out pretreatment to biomass material or biomass derived raw material, described pre-
In process step, biomass material or biomass derived raw material are washed, decolourized, being removed to follow-up by ion exchange
The poisonous and hazardous material technique of catalyst used in step.
4. the preparation method of bio-based aviation fuel according to claim 1, wherein the weight of the water, methanol and ethanol
Ratio is 1:0.5:0.5.
5. the preparation method of bio-based aviation fuel according to claim 1, wherein the step 1) described in biomass
Raw material or biomass derived raw material include selected from straw, wood flour, syrup, paper pulp, cellulose, hemicellulose, glucose, Fructose,
One or more component in xylose, arabinose, Sorbitol, Mannitol, xylitol, 1,2,3,4,5-pentanepentol and glycerol.
6. the preparation method of bio-based aviation fuel according to claim 1, wherein the step 1) described in it is multi-functional
Catalyst a is comprising selected from VIII elemental metals, IBRace's elemental metals, VIBRace's elemental metals, VIIBRace's elemental metals and more than
The sulfide of each race's metal is carried on zeolite, silicon dioxide, aluminium oxide, silica-alumina, activated carbon and is selected from
The oxide of group VIII metal, IBThe oxide of race's metal, VIBThe oxide of race's metal, VIIBThe oxide component group of race's metal
Into catalyst.
7. the preparation method of bio-based aviation fuel according to claim 6, wherein the step 1) described in it is multi-functional
Catalyst a is to be carried on ZnO, ZrO selected from by one or two in Ru, Ni, Cu, Co, Mo, Re, W2, aluminium oxide, zeolite and/
Or the catalyst being prepared from activated carbon.
8. the preparation method of bio-based aviation fuel according to claim 6, wherein the step 1) described in it is multi-functional
Catalyst a is Ni-ZnO loaded catalysts, Ni-Cu/ZrO2Loaded catalyst, Ni-Cu/ZnO loaded catalysts or Ni-
W/Al2O3Loaded catalyst.
9. the preparation method of bio-based aviation fuel according to claim 1, wherein the step 2) described in it is multi-functional
Catalyst b is to be carried on ZrO selected from Pt, Rh, Ru, Ir, W, Re, Mo2, aluminium oxide, zeolite, aluminium oxide, activated carbon be prepared from
Catalyst, the step 2) used in reaction dissolvent be selected from water, dioxane, methanol, ethanol, propanol solvent.
10. the preparation method of bio-based aviation fuel according to claim 9, wherein the step 2) described in it is multi-functional
Catalyst b is Rh-Mo/ZrO2Loaded catalyst, Rh-Re/Al2O3Loaded catalyst or Ru-W/Al2O3Supported catalyst
Agent, the step 2) used in reaction dissolvent be water, methanol and ethanol in one or more.
The preparation method of 11. bio-based aviation fuel according to claim 1, wherein the step 3) described in it is multi-functional
Catalyst c is the catalyst that activated carbon preparation is carried on selected from Pd, Pt, Rh, Ru, Ir one or two kinds of；The step 3) in
The reaction dissolvent for using is one or more in methanol, ethanol, hexamethylene, normal hexane.
The preparation method of 12. bio-based aviation fuel according to claim 11, wherein the step 3) described in many work(
Energy catalyst c is that Pd, Ir are carried on the catalyst prepared on activated carbon.
The preparation method of 13. bio-based aviation fuel according to claim 1, wherein the step 4) described in it is multi-functional
Catalyst d is that one or two in Pt, Ru, Ni, Mo, Re, W are carried on aluminium oxide, silica-alumina, zeolite
The catalyst being prepared from；The step 4) used in reaction dissolvent can be in methanol, hexamethylene, normal hexane one
Plant or various；The step 4) described in branched paraffin be that carbochain is 2 to 3 branched alkane comprising with 9 to 15 carbon atoms
Hydrocarbon.
The preparation method of 14. bio-based aviation fuel according to claim 13, wherein the step 4) described in many work(
Energy catalyst d is carried on the catalyst on silica-alumina for Pt-Mo.
The preparation method of 15. bio-based aviation fuel according to claim 13, wherein the step 4) described in side chain
Alkane is the branched paraffin in following compound：
The preparation method of 16. bio-based aviation fuel according to claim 1, wherein methods described includes：
Step 1)：Sugar content concentration is pumped into into hydrogenolysis device in 20wt% biomass material saccharified liquid 500ml, while in hydrogenolysis
Add the methanol and ethanol that prevent sugar liquid raw material excessive fragmentation as solvent in reactor, solvent methanol, amount of alcohol added are sugar
0.5 times of water consumption in liquid, be subsequently adding with co-precipitation-gel method preparation and in 500 DEG C of hydrogen reduction activation Ni-Cu-
ZnO catalyst 5g, under 180 DEG C, the reaction condition of 6MPa hydrogen atmospheres 2h is reacted, that is, obtain hydrogenolysis liquid, hydrogenolysis liquid Jing
Cross rectification under vacuum and respectively be isolated by lower boiling dihydroxylic alcohols and single methanol product, high boiling alcohol therein returns hydrogenolysis device；
Step 2)：By step 1) in the dihydroxylic alcohols that obtain be adjusted to 50% aqueous solution and pump into another hydrogenolysis device, and add
With Rh/SiO prepared by infusion process2Catalyst 10g, reacts 12h, Jing decompressions under 120 DEG C, the reaction condition of 8MPa hydrogen atmospheres
Rectification can be prepared by single methanol, and unreacted raw material returns hydrogenolysis device to be continued to convert；The single methanol product of acquisition is according to weight ratio
Contain 5% methanol, 30% ethanol, 42% propanol, 10% butanol, 2% amylalcohol, 3% hexanol, 8% isopropanol respectively；
Step 3)：By step 2) in the single methanol product that obtains add in condensation reactor, in the Ir/C catalysis prepared with infusion process
In the presence of agent 5g and promoter Phen 0.3g and sodium hydroxide 0.8g, 16h is reacted under 180 DEG C of reaction condition,
High unit's branched-chain alcoho is obtained, material stream is separated through rectification under vacuum, and low condensed products of the carbon number less than 9 are returned into condensation reaction
Device is further reacted；
Step 4)：By step 3) in the carbon number that obtains be that more than 9 height unit branched-chain alcoho product adds deoxidation hydrogenation reactor,
The Pt/Al prepared with infusion process is filled in reactor2O3Catalyst 10ml, at 280 DEG C, under the reaction condition of 6MPa hydrogen atmospheres
Reaction, control sample introduction air speed is separated in 0.5L/h, product through rectification under vacuum, and according to percentage by weight, C9 product assays are
It is that 20%, C15 product assays are 20% for 18%, C12 product assays that 10%, C10 product assay is 25%, C11 product assays,
Product of the balance of carbon number in more than C15.
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| CN110079355B (en) * | 2019-04-26 | 2020-08-04 | 中国科学院山西煤炭化学研究所 | Aviation fuel oil synthesized by methyl isobutyl ketone aldol condensation and synthesis method |
| CN110964548B (en) | 2019-12-24 | 2020-10-16 | 东南大学 | Biomass-based long-chain alcohol ether oxygen-containing additive and preparation method and application thereof |
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