CN101314724A - Combined catalytic conversion method for biological oil and fat and mineral oil - Google Patents
Combined catalytic conversion method for biological oil and fat and mineral oil Download PDFInfo
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Abstract
A method for catalytically transforming bio-oil and mineral oil combination comprises the following steps: contacting bio-oil and mineral oil with catalyst containing modified beta-zeolite in a compound reactor to carry out catalytic cracking reaction, separating the reaction resultant with the spent catalyst, processing the spent catalyst by stripping and burning and adding into the reactor for recycling, introducing the separated resultant from the reactor, and distilling to obtain target product low-carbon alkenes, gasoline, diesel and heavy oil. By adopting the catalyst containing modified beta-zeolite and zeolite with MFT structure as the necessary active component, the method can achieve higher yield of low-carbon alkenes, particularly propylene, wherein the total yield of C2 to C4 alkenes based on carbon balance is larger than 40wt percent, and the yield of propylene is above 21wt percent.
Description
Technical field
The present invention more particularly, makes up highly selective to produce the method for low-carbon alkene about a kind of by catalyzed conversion bio-oil and mineral oil about a kind of bio-oil and mineral oil combined catalytic conversion method.
Background technology
The main component of Vegetable oil lipoprotein, animal grease is a triglyceride fat acid fat, mainly contain carbon, hydrogen, oxygen element, sulphur, nitrogen content are a kind of environmental protection, renewable resources seldom, and along with the application of transgenic technology, the output of Vegetable oil lipoprotein, animal grease increases fast.Early stage research is mainly carried out thermo-cracking with Vegetable oil lipoprotein, animal grease, produce fuel, but the purpose product selectivity is low.And Vegetable oil lipoprotein, animal grease being converted into fuel by catalyst cracking method, the selectivity of purpose product will increase.
US2006/0151357 A1 discloses a kind of method of handling organic waste, and this method is converted into fuel by the multistage art breading with organic waste.At first, its moisture is reduced to below 15% the organic waste drying, again under certain temperature and pressure, with the exsiccant organic waste in organic solvent by the multistep pyrolytic reaction, pyrolysis product separates and obtains the light Fuel product.
US2006/0186020 A1 discloses the method for a vegetable oil and mineral oil hydrocracking.By the mixing of vegetables oil and mineral oil, utilize this method can obtain high-quality diesel oil.
US2007/0015947 A1 discloses a kind of method of utilizing renewable raw materials to produce alkene.This method is at first carried out pre-treatment with raw material such as vegetables oil, by contacting with acidic ion exchange resin, removes impurity such as basic metal wherein.Refining raw material is at 566～630 ℃, and gauge pressure is at 138～240kPa, and agent-oil ratio is under 5～20 the condition, and products such as the alkene that generates C2～C5, gasoline take place to transform in catalytic cracking riser reactor.
Prior art mainly is converted into hydrocarbon fuel with Vegetable oil lipoprotein, animal grease, does not have fully, effectively utilizes the straight-chain alkyl in Vegetable oil lipoprotein, the animal grease.
Summary of the invention
The purpose of this invention is to provide a kind of bio-oil and mineral oil combined catalytic conversion method, to obtain a large amount of low-carbon alkenes.
Method provided by the invention comprises: bio-oil contacts to carry out catalytic cracking reaction with the catalyzer of the β zeolite that contains modification in compound reactor with mineral oil, then reaction product is separated with reclaimable catalyst, the Returning reactor internal recycle uses behind isolated reclaimable catalyst process stripping, the coke burning regeneration, isolated reaction product is drawn from described reactor, obtains purpose product low-carbon alkene and gasoline, diesel oil, heavy oil through fractionation.
In the context of the invention, unless special explanation is arranged, term " low-carbon alkene " all refers to C2～C4 alkene.
Bio-oil raw material of the present invention is or comprises one or more mixture in tri-glyceride, the free lipid acid, is selected from but is not limited to one or more mixture in Vegetable oil lipoprotein, animal grease, microbial oil, depleted edible oil, the nigre of vegetable oil; Wherein the carbon number of the chain substituted alkyl that links to each other with carbonyl carbon in tri-glyceride and the free fatty acid molecule is 5～25.
Described Vegetable oil lipoprotein is selected from but is not limited to one or more mixture in plam oil, Oleum Cocois, soybean oil, rapeseed oil, Cortex jatrophae seed kernel oil, Viscotrol C, Oleum Gossypii semen, Semen Maydis oil, sweet oil, sunflower seed oil, oleum lini, tung oil, sesame oil, the peanut oil.Described animal grease is selected from but is not limited to one or more mixture in fish oil, lard, tallow, the suet.
Described mineral oil is selected from one or more in C4 hydro carbons, gasoline, diesel oil, hydrogenation tail oil, vacuum gas oil, residual oil, the crude oil.Described C4 hydro carbons, gasoline, diesel oil can be the products of device itself.
In bio-oil provided by the invention and mineral oil combined catalytic conversion method, the weight ratio of described bio-oil and described mineral oil is 0.1～10: 1, preferred 0.2～8: 1.
Described compound reactor is the compound reactor that is made of more than one riser reactor and fluidized-bed reactor, or the compound reactor that constitutes by riser reactor and downstriker transfer limes reactor, or the compound reactor that constitutes by two or more riser reactors, or the compound reactor that constitutes by two or more fluidized-bed reactors, or the compound reactor that constitutes by two or more downstriker transfer limes reactors, or the compound reactor that constitutes by two or more moving-burden bed reactors.In addition, above-mentioned every kind of reactor can be divided into two or more reaction zones as required.Preferred reactor is the compound reactor that is made of more than one riser reactor and fluidized-bed reactor, and preferred reactor is the compound reactor that is made of two riser reactors and fluidized-bed reactor.
Wherein, described riser tube be selected from the equal diameter riser reactor, etc. linear speed riser reactor and become in the diameter riser reactor one or more.Described fluidized-bed reactor is selected from one or more in fixed fluidized-bed reactor, particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor, fast bed reactor, transport bed reactor and the dense fluidized bed bioreactor.
The wherein said catalyzer that contains the β zeolite of modification is a benchmark with the gross weight of catalyzer, and it contains 1%～60% zeolite mixture, 5%～99% heat-resistant inorganic oxide and 0～70% clay.Gross weight with described zeolite mixture is a benchmark, contains 1%～75% the β zeolite by phosphorus and transition metal M modification, 25%～99% the zeolite with MFI structure and 0～74% large pore zeolite in the described zeolite mixture.
Described β zeolite by phosphorus and transition metal M modification can adopt the whole bag of tricks to be prepared, such as in the process of synthetic β zeolite, introducing phosphorus and described transition metal M, perhaps behind synthetic β zeolite, adopt steps such as ammonium exchange, phosphorus modification, described transition metal M modification and calcination process to introduce phosphorus and described transition metal M.Described transition metal M is selected from one or more among Fe, Co, Ni and the Cu, more preferably Fe and/or Cu.
The zeolite of the described MFI of having structure is the supersiliceous zeolite with pentasil structure, be selected from ZSM-5 and the ZRP series zeolite one or more, particularly be selected from the ZRP zeolite (CN1052290A that contains rare earth, CN1058382A, US5232675), phosphorated ZRP zeolite (CN1194181A, US5951963), the ZRP zeolite (CN1147420A) of phosphorous and rare earth, ZRP zeolite (the CN1211469A of phosphorous and alkaline-earth metal, CN1211470A, US6080698) and phosphorous and ZRP zeolite (CN1465527A transition metal, CN1611299A) one or more in.
Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, such as being selected from y-type zeolite, L zeolite, β zeolite, omega zeolite, mordenite and the ZSM-18 zeolite one or more, particularly be selected from the overstable gamma zeolite of y-type zeolite, overstable gamma zeolite and phosphorous and/or rare earth of y-type zeolite, phosphorous and/or rare earth one or more.
In addition, the zeolite of the described MFI of having structure and described large pore zeolite can adopt commercially available product, also can adopt the whole bag of tricks well known in the art to be prepared, and do not give unnecessary details at this.
Described heat-resistant inorganic oxide is selected from SiO
2And/or Al
2O
3Clay is selected from kaolin and/or halloysite.
In a preferred embodiment of bio-oil of the present invention and mineral oil combined catalytic conversion method, gross weight with described bio-oil and mineral oil conversion catalyst is a benchmark, and described bio-oil and mineral oil conversion catalyst contain 10%～50% described zeolite mixture, 10%～70% described heat-resistant inorganic oxide and 0～60% described clay.
In bio-oil provided by the invention and mineral oil combined catalytic conversion method, operational condition when carrying out described catalytic cracking reaction in described compound reactor is: the preheating temperature of bio-oil and mineral oil is at 150～420 ℃, preferred 200～400 ℃, temperature of reaction is 460～700 ℃, preferably at 520～650 ℃, the pressure of reaction zone (absolute pressure) is 0.15～0.3MPa, preferred 0.2～0.3MPa, and the weight hourly space velocity of described bio-oil and mineral oil feed is 0.2～40h
-1, preferred 3～30h
-1, the ratio (hereinafter to be referred as agent-oil ratio) 4～30: 1 of the weight of catalyzer and the gross weight of bio-oil, mineral oil feed.
In bio-oil provided by the invention and mineral oil combined catalytic conversion method, for reducing oil gas dividing potential drop in the reactor, in the process of carrying out described catalytic cracking reaction, can in described reactor, inject the thinner that is selected from water vapour, nitrogen and C1～C4 alkane, carbonic acid gas, carbon monoxide etc., wherein, the preferably water steam, and the weight ratio of water vapour and hydrocarbon raw material is preferably 0.01～2: 1.
In bio-oil provided by the invention and mineral oil combined catalytic conversion method in possibility, for improving the particularly productive rate of propylene of low-carbon alkene, separate the C4 hydro carbons, the petroleum naphtha that obtain being rich in alkene, can return compound reactor and further transform.
In a possibility of bio-oil of the present invention and mineral oil combined catalytic conversion method, described reaction product is drawn from described reactor with reclaimable catalyst (used described an acidic catalyst), after the stripping separation, this catalyzer that reclaims is returned described compound reactor internal recycle behind coke burning regeneration use, isolated this reaction product is then carried out described fractionation, to obtain described low-carbon alkene, gasoline, diesel oil, heavy oil and other low molecule saturated hydrocarbons.
In bio-oil of the present invention and mineral oil combined catalytic conversion method, after described reaction product and described reclaimable catalyst are drawn from described reactor together, separate through separator (such as cyclonic separator).Isolated catalyzer again through a stripping stage, is gone out the hydrocarbon product that adsorbs on the catalyzer with water vapour or other gas stripping.To utilize fluidization technique to be transported in the revivifier through steam stripped this catalyzer, contact under with oxygen-containing gas such as 650～720 ℃ temperature, this coke deposited on catalyst charcoal and tar oxidation are burnt and make this catalyzer obtain regeneration, then this regenerated catalyzer is turned back in the described reactor for recycling.After isolated described reaction product (optional be included in the described hydrocarbon product that stripping stage obtains) carried out fractionation, obtain gas (comprising carbonic acid gas, carbon monoxide, dry gas and liquefied gas), gasoline, diesel oil and heavy oil.Just can from described gas, isolate described low-carbon alkene by isolation technique, comprise ethene, propylene, butylene and other component etc.
The advantage of bio-oil provided by the invention and mineral oil combined catalytic conversion method is: by using with particular modification β zeolite and having bio-oil and the mineral oil conversion catalyst of the zeolite of MFI structure as essential active, show higher bio-oil conversion capability, higher productivity of low carbon olefin hydrocarbon, particularly higher productivity of propylene.Transform by bio-oil and mineral oil combination, can better keep thermal equilibrium in the conversion process, improve the handiness that utilizes bio-oil.Yield based on the C2～C4 alkene of carbon balance surpasses 40 heavy %, and the yield of propylene is up to more than the 21 heavy %.
Description of drawings
Fig. 1 is when adopting the compound reactor of single riser tube and fluidized-bed formation, the schematic flow sheet of bio-oil and mineral oil combined catalytic conversion method.
Fig. 2 is when adopting the compound reactor of double lifting leg and fluidized-bed formation, the schematic flow sheet of bio-oil and mineral oil combined catalytic conversion method.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Fig. 1 is when adopting the compound reactor of single riser tube and fluidized-bed formation, the schematic flow sheet of bio-oil and mineral oil combined catalytic conversion method.
Wherein 1 is riser reactor, and 3 is fluidized-bed reactor, and 4 is stripping stage, and 5 is revivifier.This synoptic diagram is the simplification flow process, but this does not influence those of ordinary skills' the understanding of the present invention.
80% bio-oil and 20% mineral oil are through after being preheated to 200～400 ℃, spray into riser reactor 1 with water vapour by pipeline 11,460～700 ℃ preferred 520～650 ℃ of temperature, preferred 0.2～the 0.3MPa of pressure 0.15～0.3MPa (absolute pressure), the weight ratio of catalyzer and bio-oil and mineral oil is 4～30, weight hourly space velocity 0.2～40h
-1Preferred 3～30h
-1Condition under, with contact, react by hot regenerated catalyst from pipeline 53, reaction product is at fluidized-bed layer reactor 3,460～680 ℃ preferred 540～650 ℃ of temperature, the weight ratio of catalyzer and bio-oil and mineral oil is 4～30, weight hourly space velocity 0.2～40h
-1Preferred 2～20h
-1Condition under, further reaction is converted into low-carbon alkene with bio-oil and mineral oil highly selective.
In alternatives of the present invention, 40% bio-oil and 20% mineral oil are through after being preheated to 200～400 ℃, spray into riser reactor 1 with water vapour by pipeline 11,40 heavy % bio-oils are through after being preheated to 200～400 ℃, with water vapour by pipeline 11 ' spray into riser reactor 1.
In another alternatives of the present invention, in order to improve the particularly productive rate of propylene of low-carbon alkene, separate the C4 hydro carbons that is rich in alkene, the petroleum naphtha component that obtain and spray into fluidized-bed reactor 3 by pipeline 12,460～700 ℃ preferred 520～650 ℃ of temperature, preferred 0.2～the 0.3MPa of pressure 0.15～0.3MPa (absolute pressure), catalyzer and C4 hydro carbons, petroleum naphtha components by weight are 4～50, weight hourly space velocity 0.2～40h
-1Preferred 3～30h
-1Condition under, contact, react with hot regenerated catalyst, generating propylene is main low-carbon alkene.
Final reacting product is with after reclaimable catalyst separates, isolated reaction product is left reactive system by pipeline 14, further separate, obtain products such as low-carbon alkene, separate the reclaimable catalyst stripping in stripping stage 4 that obtains and go out the hydrocarbon product of absorption, deliver to revivifier 5 by pipeline 13 and regenerate.Warm air enters revivifier by pipeline 51, and flue gas leaves revivifier by pipeline 52.Regenerated catalyst is delivered to compound reactor by pipeline 53 and reuses.
Fig. 2 is when adopting the compound reactor of double lifting leg and fluidized-bed formation, the schematic flow sheet of bio-oil and mineral oil combined catalytic conversion method.
1,2 is riser reactor among Fig. 2, and 3 is fluidized-bed reactor, and 4 is stripping stage, and 5 is revivifier.
80% bio-oil and 20% mineral oil are through after being preheated to 200～400 ℃, spray into riser reactor 1 with water vapour by pipeline 11,460～700 ℃ preferred 520～650 ℃ of temperature, preferred 0.2～the 0.3MPa of pressure 0.15～0.3MPa (absolute pressure), the weight ratio of catalyzer and bio-oil is 4～30, weight hourly space velocity 0.2～40h
-1Preferred 3～30h
-1Condition under, and contact, react by hot regenerated catalyst from pipeline 54, reaction product is at bed reactor 3,460～680 ℃ preferred 540～650 ℃ of temperature, the weight ratio of catalyzer and bio-oil and mineral oil is 4～30, weight hourly space velocity 0.2～40h
-1Preferred 2～20h
-1Condition under, further reaction is converted into low-carbon alkene with the bio-oil highly selective.For effective controlling flow fluidized bed reactor bed temperature, part is supplemented to fluidized-bed reactor 3 from the hot regenerated catalyst of pipeline 55 by riser tube 2.
In alternatives of the present invention, part biological grease and mineral oil are through after being preheated to 200～400 ℃, spray into riser reactor 1 with water vapour by pipeline 11, the bio-oil of part preheating sprays into riser reactor 2 with water vapour by pipeline 21,460～680 ℃ preferred 540～650 ℃ of temperature, the weight ratio of catalyzer and bio-oil is 4～30, weight hourly space velocity 0.2～40h
-1Preferred 3～30h
-1Condition under, react, reaction product enters fluidized-bed reactor with catalyzer and continues reaction.Described bio-oil and mineral oil weight ratio are 0.1～10: 1, preferred 0.2～8: 1.The described bio-oil that sprays into riser reactor 2 and the bio-oil weight ratio that sprays into riser reactor 1 are 0.1～5: 1, preferred 0.2～4: 1.
In another alternatives of the present invention, in order to improve the particularly productive rate of propylene of low-carbon alkene, separate the C4 hydro carbons that is rich in alkene, the petroleum naphtha component that obtain and can spray into riser reactor 2 by pipeline 21, perhaps spray into fluidized-bed reactor 3 by pipeline 12,460～700 ℃ preferred 520～650 ℃ of temperature, preferred 0.2～the 0.3MPa of pressure 0.15～0.3MPa (absolute pressure), catalyzer and C4 hydro carbons, petroleum naphtha components by weight are 4～50, weight hourly space velocity 0.2～40h
-1Preferred 3～30h
-1Condition under, contact, react with hot regenerated catalyst, generating propylene is main low-carbon alkene.
Final reacting product is with after reclaimable catalyst separates, isolated reaction product is left reactive system by pipeline 14, further separate, obtain products such as low-carbon alkene, separate the reclaimable catalyst stripping in stripping stage 4 that obtains and go out the hydrocarbon product of absorption, deliver to revivifier 5 by pipeline 13 and regenerate.Warm air enters revivifier by pipeline 51, and flue gas leaves revivifier by pipeline 52.Regenerated catalyst is delivered to compound reactor by pipeline 53 and reuses.By regulating the regenerated catalyst flow of pipeline 54,55, the agent-oil ratio in the control riser reactor 1,2.
The following examples will give further instruction to present method, but therefore not limit present method.Test is to carry out on medium-sized tester.
Bio-oil in embodiment and the Comparative Examples, mineral oil are respectively plam oil, long residuum, and the character of plam oil, long residuum sees Table 1 respectively, table 2.
Effect when bio-oil provided by the invention and mineral oil combined catalytic conversion method are adopted in embodiment 1～4 explanation.
Catalyzer (is contained 7 heavy %USY zeolites, 8 heavy % β zeolites, 20 heavy %ZSM-5 zeolites, surplus is a carrier, all is benchmark with the total catalyst weight) at 800 ℃, wore out 10 hours with 100% water vapour, use medium-sized tester, the loading amount of catalyzer is 60 kilograms in the compound reactor.
80% plam oil and 20% long residuum only advance riser reactor 1 among the embodiment 1;
40% plam oil and 20% long residuum enter riser reactor 1 bottom among the embodiment 2, and 40% plam oil enters riser reactor 1 middle and lower part;
80% plam oil and 20% long residuum advance riser reactor 1 among the embodiment 3, and riser tube 2 is given the agent of fluidized-bed reactor compensation regeneration.
50% plam oil and 20% long residuum advance riser reactor 1,30% plam oil and advance riser reactor 2 among the embodiment 4.
Agent-oil ratio is meant the weight ratio of catalyzer and fresh feed (plam oil+long residuum) among the embodiment.
Evaluation result sees Table 3.A refers to riser reactor 1 in the table 3, and B refers to riser reactor 2, and C refers to fluidized-bed reactor 3.
Comparative Examples 1
Effect when Comparative Examples 1 explanation adopts riser reactor to carry out bio-oil and mineral oil combined catalytic conversion method, raw material is 80% plam oil and 20% long residuum.The results are shown in Table 3.
As can be seen from Table 3, based on carbon balance, adopt ethene, the propylene of the Comparative Examples 1 of single riser reactor, the yield of ethene+propylene+butylene to be lower than 5,20,40 heavy % respectively, and the yield of ethene, propylene, ethene+propylene+butylene that adopts the embodiment 1～4 of compound reactor is respectively up to more than 6,21, the 40 heavy %.
Table 1
| Project | Plam oil |
| Density (20 ℃), g/cm 3 | 0.9107 |
| Refractive power (70 ℃) | 1.4464 |
| Kinematic viscosity, mm 2/s | |
| 80℃ | 12.95 |
| 100℃ | 8.561 |
| Condensation point, ℃ | 26 |
| Aniline point, ℃ | ＜25 |
| Carbon residue, heavy % | 0.26 |
| Elementary composition | |
| C, heavy % | 76.48 |
| H, heavy % | 11.92 |
| O, heavy % | 10.56 |
| S，mg/L | 3.5 |
| N，mg/L | / |
Table 2
| The stock oil title | Long residuum |
| Density (20 ℃), gram per centimeter 3 | 0.8906 |
| Viscosity, millimeter 2/ second | 24.84 |
| Bituminous matter, % | 0.8 |
| Conradson carbon residue, % | 4.3 |
| Boiling range, ℃ | |
| IBP | 282 |
| 10% (volume) | 370 |
| 30% (volume) | 482 |
| 50% (volume) | 553 |
| 70% (volume) | - |
| 90% (volume) | - |
Table 3
Claims (15)
1, a kind of bio-oil and mineral oil combined catalytic conversion method, it is characterized in that this method comprises: bio-oil contacts to carry out catalytic cracking reaction with the catalyzer of the β zeolite that contains modification in compound reactor with mineral oil, then reaction product is separated with reclaimable catalyst, the Returning reactor internal recycle uses behind isolated reclaimable catalyst process stripping, the coke burning regeneration, isolated reaction product is drawn from described reactor, obtains purpose product low-carbon alkene and gasoline, diesel oil, heavy oil through fractionation.
2, in accordance with the method for claim 1, it is characterized in that described bio-oil raw material is or comprises one or more mixture in tri-glyceride, the free lipid acid, be selected from one or more the mixture in Vegetable oil lipoprotein, animal grease, microbial oil, depleted edible oil, the nigre of vegetable oil.
3, in accordance with the method for claim 2, it is characterized in that described Vegetable oil lipoprotein is selected from one or more the mixture in plam oil, Oleum Cocois, soybean oil, rapeseed oil, Cortex jatrophae seed kernel oil, Viscotrol C, Oleum Gossypii semen, Semen Maydis oil, sweet oil, sunflower seed oil, oleum lini, tung oil, sesame oil, the peanut oil; Described animal grease is selected from one or more the mixture in fish oil, lard, tallow, the suet.
4, in accordance with the method for claim 1, it is characterized in that described mineral oil is selected from one or more in C4 hydro carbons, gasoline, diesel oil, hydrogenation tail oil, vacuum gas oil, residual oil, the crude oil.
5, in accordance with the method for claim 1, the weight ratio that it is characterized in that described bio-oil and described mineral oil is 0.1～10: 1.
6, in accordance with the method for claim 1, the weight ratio that it is characterized in that described bio-oil and described mineral oil is 0.2～8: 1.
7, in accordance with the method for claim 1, it is characterized in that described compound reactor is the compound reactor that is made of more than one riser reactor and fluidized-bed reactor, or the compound reactor that constitutes by riser reactor and downstriker transfer limes reactor, or the compound reactor that constitutes by two or more riser reactors, or the compound reactor that constitutes by two or more fluidized-bed reactors, or the compound reactor that constitutes by two or more downstriker transfer limes reactors, or the compound reactor that constitutes by two or more moving-burden bed reactors.
8, in accordance with the method for claim 1, it is characterized in that described compound reactor is the compound reactor that is made of more than one riser reactor and fluidized-bed reactor.
9, in accordance with the method for claim 1, it is characterized in that described compound reactor is the compound reactor that is made of two riser reactors and fluidized-bed reactor.
10, in accordance with the method for claim 1, it is characterized in that the described catalyzer that contains the β zeolite of modification, is benchmark with the gross weight of catalyzer, and it contains 1%～60% zeolite mixture, 5%～99% heat-resistant inorganic oxide and 0～70% clay.Gross weight with described zeolite mixture is a benchmark, contains 1%～75% the β zeolite by phosphorus and transition metal M modification, 25%～99% the zeolite with MFI structure and 0～74% large pore zeolite in the described zeolite mixture.
11, in accordance with the method for claim 10, it is characterized in that described transition metal M is selected from one or more among Fe, Co, Ni and the Cu.
12, in accordance with the method for claim 10, it is characterized in that described transition metal M is Fe and/or Cu.
13, in accordance with the method for claim 1, it is characterized in that temperature of reaction is 460～700 ℃,, pressure is 0.15～0.3MPa, the weight hourly space velocity of described bio-oil and mineral oil feed is 0.2～40h
-1, the ratio 4～30: 1 of the weight of catalyzer and the gross weight of bio-oil, mineral oil feed.
14, in accordance with the method for claim 1, it is characterized in that temperature of reaction is 520～650 ℃, pressure is 0.2～0.3MPa, and the weight hourly space velocity of described bio-oil and mineral oil feed is 3～30h
-1
15, in accordance with the method for claim 1, it is characterized in that separating the C4 hydro carbons that is rich in alkene, the petroleum naphtha component that obtain returns compound reactor and further transforms.
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