CN101314724B - Combined catalytic conversion method for biological oil and fat and mineral oil - Google Patents

Abstract

A combined catalytic conversion method of bio-grease and mineral oil, in which the bio-grease and mineral oil are contacted with a catalyst containing modified β zeolite in a composite reactor to carry out a catalytic cracking reaction, and then the reaction product is separated from the unborn catalyst, and the The spent catalyst is stripped, burnt and regenerated, and then returned to the reactor for recycling. The separated reaction product is drawn from the reactor and subjected to fractional distillation to obtain the target products of low-carbon olefins, gasoline, diesel, and heavy oil. The method uses modified β zeolite and zeolite with MFI structure as the catalyst of the necessary active components to obtain higher yields of low-carbon olefins, especially propylene, and the total yield of C2-C4 olefins based on carbon balance exceeds 40 wt. %, the yield of propylene is as high as 21% by weight or more.

Description

A kind of combined catalytic conversion method of biological oil and mineral oil

technical field

The present invention relates to a method for combined catalytic conversion of bio-grease and mineral oil, more specifically, a method for producing low-carbon olefins with high selectivity through catalytic conversion of bio-grease and mineral oil.

Background technique

The main components of vegetable oils and animal oils are triglyceride fatty acid lipids, which mainly contain carbon, hydrogen, and oxygen elements, and the content of sulfur and nitrogen is very small. It is a green and renewable resource. With the application of transgenic technology, vegetable oil , The output of animal fat increased rapidly. Early studies mainly used vegetable oil and animal oil to pyrolyze to produce fuel, but the selectivity of the target product was low. However, by converting vegetable oil and animal oil into fuel through catalytic cracking, the selectivity of the target product will be improved.

US2006/0151357A1 discloses a method for treating organic waste, which converts organic waste into fuel through multi-stage processing. Firstly, the organic waste is dried to reduce its moisture to below 15%, and then the dried organic waste is subjected to multi-step pyrolysis reaction in an organic solvent under a certain temperature and pressure, and the pyrolysis product is separated to obtain a light fuel product.

US2006/0186020A1 discloses a method for mixed hydroconversion of vegetable oil and mineral oil. By mixing vegetable oil and mineral oil, high-quality diesel oil can be obtained by using this method.

US2007/0015947A1 discloses a method for producing olefins from renewable raw materials. In this method, raw materials such as vegetable oil are firstly pretreated, and impurities such as alkali metals are removed by contacting with acidic ion exchange resins. The refined raw material is converted into C2-C5 olefins, gasoline and other products in the catalytic cracking riser reactor under the conditions of 566-630°C, gauge pressure of 138-240kPa, and catalyst-to-oil ratio of 5-20.

The prior art mainly converts vegetable oils and animal oils into hydrocarbon fuels, but does not fully and effectively utilize the straight-chain hydrocarbon groups in vegetable oils and animal oils.

Contents of the invention

The purpose of the present invention is to provide a combined catalytic conversion method of bio-grease and mineral oil to obtain a large amount of low-carbon olefins.

The method provided by the invention comprises: biogrease and mineral oil are contacted with the catalyst containing the modified β zeolite in the compound reactor to carry out the catalytic cracking reaction, then the reaction product is separated from the raw catalyst, and the separated raw catalyst is passed through After stripping and coke regeneration, it is returned to the reactor for recycling, and the separated reaction product is drawn out from the reactor, and subjected to fractional distillation to obtain the target products of low-carbon olefins, gasoline, diesel oil, and heavy oil.

In the context of the present invention, unless otherwise specified, the term "low-carbon olefins" refers to C2-C4 olefins.

The bio-oil raw material described in the present invention is or contains one or more mixtures of triglycerides and free fatty acids, selected from but not limited to vegetable oils, animal oils, microbial oils, waste edible oils, A mixture of one or more kinds of vegetable oil soapstock; wherein the carbon number of the chain-like substituted alkyl group connected to the carbonyl carbon in the triglyceride and free fatty acid molecules is 5-25.

The vegetable oil is selected from but not limited to palm oil, coconut oil, soybean oil, rapeseed oil, jatropha seed oil, castor oil, cottonseed oil, corn oil, olive oil, sunflower oil, linseed oil, tung oil, One or a mixture of sesame oil and peanut oil. The animal fat is selected from, but not limited to, one or a mixture of fish oil, lard, tallow, suet.

The mineral oil is selected from one or more of C4 hydrocarbons, gasoline, diesel oil, hydrogenated tail oil, vacuum gas oil, residual oil, and crude oil. The C4 hydrocarbons, gasoline and diesel may be the products of the device itself.

In the combined catalytic conversion method of bio-oil and mineral oil provided by the present invention, the weight ratio of the bio-oil to the mineral oil is 0.1-10:1, preferably 0.2-8:1.

The composite reactor is a composite reactor composed of more than one riser reactor and a fluidized bed reactor, or a composite reactor composed of a riser reactor and a descending conveyor line reactor, or a composite reactor composed of two A composite reactor composed of one or more riser reactors, or a composite reactor composed of two or more fluidized bed reactors, or a composite reactor composed of two or more A composite reactor composed of line reactors, or a composite reactor composed of two or more moving bed reactors. In addition, each of the above-mentioned reactors can be divided into two or more reaction zones as required. A preferred reactor is a composite reactor composed of more than one riser reactor and a fluidized bed reactor, and a more preferred reactor is a composite reactor composed of two riser reactors and a fluidized bed reactor.

Wherein, the riser is selected from one or more of riser reactors with equal diameters, riser reactors with constant linear velocity and riser reactors with variable diameters. The fluidized bed reactor is selected from a fixed fluidized bed reactor, a dispersed fluidized bed reactor, a bubbling bed reactor, a turbulent bed reactor, a fast bed reactor, a transport bed reactor and a dense phase fluidized One or more of the bed reactors.

The catalyst containing modified zeolite beta, based on the total weight of the catalyst, contains 1%-60% of zeolite mixture, 5%-99% of heat-resistant inorganic oxide and 0-70% of clay. Based on the total weight of the zeolite mixture, the zeolite mixture contains 1% to 75% of beta zeolite modified by phosphorus and transition metal M, 25% to 99% of zeolite with MFI structure and 0 to 74% % of large pore zeolites.

The zeolite beta modified by phosphorus and transition metal M can be prepared by various methods, such as introducing phosphorus and the transition metal M during the synthesis of zeolite beta, or using ammonium exchange and phosphorus modification after the synthesis of zeolite beta. Phosphorus and the transition metal M are introduced through steps such as properties, modification of the transition metal M, and roasting treatment. The transition metal M is selected from one or more of Fe, Co, Ni and Cu, more preferably Fe and/or Cu.

The zeolite with the MFI structure is a high-silica zeolite with a pentasil structure, selected from one or more of ZSM-5 and ZRP series zeolites, especially ZRP zeolites containing rare earths (CN1052290A, CN1058382A, US5232675), ZRP zeolite containing phosphorus (CN1194181A, US5951963), ZRP zeolite containing phosphorus and rare earth (CN1147420A), ZRP zeolite containing phosphorus and alkaline earth metal (CN1211469A, CN1211470A, US6080698) and ZRP zeolite containing phosphorus and transition metal (CN1465527A, CN1611299A ) in one or more.

The large-pore zeolite is a zeolite with a pore-like structure with ring openings of at least 0.7 nanometers, such as one or more selected from Y-type zeolite, L zeolite, beta zeolite, omega zeolite, mordenite and ZSM-18 zeolite, In particular, one or more selected from Y-type zeolite, phosphorus- and/or rare-earth-containing Y-type zeolite, ultra-stable Y-zeolite, and phosphorus- and/or rare-earth-containing ultra-stable Y-zeolite.

In addition, the zeolite with the MFI structure and the large-pore zeolite can be commercially available, or can be prepared by various methods known in the art, which will not be repeated here.

The heat-resistant inorganic oxide is selected from SiO ₂ and/or Al ₂ O ₃ ; the clay is selected from kaolin and/or halloysite.

In a preferred embodiment of the bio-grease and mineral oil combined catalytic conversion method of the present invention, based on the total weight of the bio-grease and mineral oil conversion catalyst, the bio-grease and mineral oil conversion catalyst contains 10% to 50% The zeolite mixture, 10%-70% of the heat-resistant inorganic oxide and 0-60% of the clay.

In the combined catalytic conversion method of bio-grease and mineral oil provided by the present invention, the operating conditions when carrying out the catalytic cracking reaction in the composite reactor are: the preheating temperature of bio-grease and mineral oil is 150-420°C, Preferably 200-400°C, the reaction temperature is 460-700°C, preferably 520-650°C, the pressure (absolute pressure) in the reaction zone is 0.15-0.3MPa, preferably 0.2-0.3MPa, the bio-oil and mineral oil raw materials The weight hourly space velocity is 0.2-40h ^-1 , preferably 3-30h ^-1 , and the ratio of the weight of the catalyst to the total weight of bio-oil and mineral oil raw materials (hereinafter referred to as the agent-oil ratio) is 4-30:1.

In the bio-grease and mineral oil combined catalytic conversion method provided by the invention, in order to reduce the partial pressure of oil and gas in the reactor, in the process of carrying out the catalytic cracking reaction, the reactor can be injected with water vapor, nitrogen and Among diluents such as C1-C4 alkanes, carbon dioxide, and carbon monoxide, water vapor is preferred, and the weight ratio of water vapor to hydrocarbon feedstock is preferably 0.01-2:1.

In an optional scheme in the combined catalytic conversion method of bio-grease and mineral oil provided by the present invention, in order to improve the yield of low-carbon olefins, especially propylene, the C4 hydrocarbons and light gasoline rich in olefins are separated and can be returned to the composite reaction for further conversion.

In an optional version of the combined catalytic conversion method of bio-grease and mineral oil of the present invention, the reaction product is drawn from the reactor together with the unborn catalyst (the acidic catalyst used) and separated by stripping The recovered catalyst is regenerated by burning and then returned to the composite reactor for recycling, while the separated reaction product is subjected to the fractional distillation to obtain the light olefins, gasoline, diesel, heavy oil and Other low molecular weight saturated hydrocarbons.

In the combined catalytic conversion method of bio-grease and mineral oil of the present invention, after the reaction product and the spent catalyst are drawn out of the reactor, they are separated by a separator (such as a cyclone separator). The separated catalyst is passed through a stripping section, and the hydrocarbon products adsorbed on the catalyst are stripped with water vapor or other gases. The stripped catalyst is transported to the regenerator by fluidization technology, and is contacted with oxygen-containing gas at a temperature of 650-720°C, so that the coke and tar deposited on the catalyst are oxidized and burned to regenerate the catalyst , and then return the regenerated catalyst to the reactor for recycling. After fractionating the separated reaction products (optionally including the hydrocarbon products obtained in the stripping section), gas (including carbon dioxide, carbon monoxide, dry gas and liquefied gas), gasoline, diesel and heavy oil are obtained. The low-carbon olefins, including ethylene, propylene, butene and other components, can be separated from the gas by separation technology.

The advantage of the bio-grease and mineral oil combined catalytic conversion method provided by the invention is: by using the bio-grease and mineral oil conversion catalyst with specific modified β zeolite and zeolite with MFI structure as necessary active components, it shows higher Bio-oil conversion ability, higher yield of low-carbon olefins, especially higher yield of propylene. Through the combined conversion of bio-oil and mineral oil, the heat balance during the conversion process can be better maintained, and the flexibility of using bio-oil can be improved. The yield of C2-C4 olefins based on carbon balance exceeds 40% by weight, and the yield of propylene is as high as 21% by weight or more.

Description of drawings

Fig. 1 is a schematic flow diagram of the combined catalytic conversion method of bio-oil and mineral oil when a composite reactor composed of a single riser and a fluidized bed is adopted.

Fig. 2 is a schematic flow diagram of the combined catalytic conversion method of bio-grease and mineral oil when a composite reactor composed of double riser and fluidized bed is adopted.

Detailed ways

The method provided by the present invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereby.

Fig. 1 is a schematic flow diagram of the combined catalytic conversion method of bio-oil and mineral oil when a composite reactor composed of a single riser and a fluidized bed is adopted.

Among them, 1 is a riser reactor, 3 is a fluidized bed reactor, 4 is a stripping section, and 5 is a regenerator. This schematic diagram is a simplified process, but this does not affect the understanding of the present invention by those of ordinary skill in the art.

80% bio-grease and 20% mineral oil are preheated to 200-400°C, sprayed together with water vapor into riser reactor 1 through pipeline 11, at a temperature of 460-700°C, preferably 520-650°C, and a pressure of 0.15-0.3 MPa is preferably 0.2～0.3MPa (absolute pressure), the weight ratio of catalyzer and biogrease and mineral oil is 4～30, and under the condition of weight hourly space velocity 0.2～40h ^-1 preferably 3～30h ^-1 , with from pipeline 53 The hot regenerated catalyst is contacted and reacted, and the reaction product is in the fluidized bed reactor 3 at a temperature of 460-680°C, preferably 540-650°C, the weight ratio of the catalyst to bio-grease and mineral oil is 4-30, and the weight hourly space velocity is 0.2- Under the condition of 40h ^-1 , preferably 2-20h ^-1 , further reaction is performed to convert bio-grease and mineral oil into low-carbon olefins with high selectivity.

In an alternative of the present invention, 40% bio-grease and 20% mineral oil are preheated to 200-400°C, and then sprayed into the riser reactor 1 through pipeline 11 together with water vapor, and 40% by weight of bio-grease is preheated. After heating to 200-400°C, it is sprayed into the riser reactor 1 through the pipeline 11' together with water vapor.

In another alternative of the present invention, in order to improve the yield of low-carbon olefins, especially propylene, the separated olefin-rich C4 hydrocarbons and light gasoline components are sprayed into the fluidized bed reactor 3 through the pipeline 12. The temperature is 460-700°C, preferably 520-650°C, the pressure is 0.15-0.3MPa, preferably 0.2-0.3MPa (absolute pressure), the weight ratio of the catalyst to C4 hydrocarbons and light gasoline components is 4-50, and the weight hourly space velocity is 0.2-40h ^{- 1.} Preferably, under the condition of 3-30h ^-1 , contact and react with the thermally regenerated catalyst to generate low-carbon olefins mainly propylene.

After the final reaction product is separated from the raw catalyst, the separated reaction product leaves the reaction system through the pipeline 14 for further separation to obtain products such as low-carbon olefins, and the separated raw catalyst is stripped in the stripping section 4 to strip the adsorbed hydrocarbons. The products are sent to the regenerator 5 through the pipeline 13 for regeneration. Hot air enters the regenerator through line 51, and flue gas leaves the regenerator through line 52. The regenerated catalyst is transported to the composite reactor through pipeline 53 for reuse.

Fig. 2 is a schematic flow diagram of the combined catalytic conversion method of bio-grease and mineral oil when a composite reactor composed of double riser and fluidized bed is adopted.

In Fig. 2, 1 and 2 are riser reactors, 3 is a fluidized bed reactor, 4 is a stripping section, and 5 is a regenerator.

80% bio-grease and 20% mineral oil are preheated to 200-400°C, sprayed together with water vapor into riser reactor 1 through pipeline 11, at a temperature of 460-700°C, preferably 520-650°C, and a pressure of 0.15-0.3 MPa is preferably 0.2～0.3MPa (absolute pressure), the weight ratio of catalyst and biogrease is 4～30, under the condition of weight hourly space velocity 0.2～40h ^-1 preferably 3～30h ^-1 , with the catalyst regenerated by heat from pipeline 54 Contact and reaction, the reaction product is in the bed reactor 3, at a temperature of 460-680°C, preferably 540-650°C, the weight ratio of the catalyst to bio-oil and mineral oil is 4-30, and the weight hourly space velocity is 0.2-40h ^-1 , preferably 2 Under the condition of ~20h ^-1 , further react to convert bio-oil into low-carbon olefins with high selectivity. In order to effectively control the bed temperature of the fluidized bed reactor, part of the hot regenerated catalyst from line 55 is supplemented to the fluidized bed reactor 3 through the riser 2 .

In an alternative of the present invention, part of the bio-grease and mineral oil are sprayed into the riser reactor 1 through the pipeline 11 together with water vapor after being preheated to 200-400° C. Spray into riser reactor 2 through pipeline 21, preferably 540～650 ℃ at temperature 460～680 ℃, the weight ratio of catalyst and bio-oil is 4～30, weight hourly space velocity 0.2～40h ^-1 , preferably 3～30h ^-1 Under the conditions, the reaction is carried out, and the reaction product enters the fluidized bed reactor together with the catalyst to continue the reaction. The weight ratio of the bio-grease to mineral oil is 0.1-10:1, preferably 0.2-8:1. The weight ratio of the bio-oil sprayed into the riser reactor 2 to the bio-oil sprayed into the riser reactor 1 is 0.1-5:1, preferably 0.2-4:1.

In another alternative of the present invention, in order to increase the yield of low-carbon olefins, especially propylene, the separated olefin-rich C4 hydrocarbons and light gasoline components can be injected into the riser reactor 2 through the pipeline 21, or Spray into fluidized bed reactor 3 through pipeline 12, preferably 520～650 ℃ at temperature 460～700 ℃, pressure 0.15～0.3MPa preferably 0.2～0.3MPa (absolute pressure), catalyst and C4 hydrocarbons, light gasoline component weight The ratio is 4-50, and the weight hourly space velocity is 0.2-40h ^-1 , preferably 3-30h ^-1 , it contacts and reacts with the thermally regenerated catalyst to produce low-carbon olefins mainly propylene.

After the final reaction product is separated from the raw catalyst, the separated reaction product leaves the reaction system through the pipeline 14 for further separation to obtain products such as low-carbon olefins, and the separated raw catalyst is stripped in the stripping section 4 to strip the adsorbed hydrocarbons. The products are sent to the regenerator 5 through the pipeline 13 for regeneration. Hot air enters the regenerator through line 51, and flue gas leaves the regenerator through line 52. The regenerated catalyst is transported to the composite reactor through pipeline 53 for reuse. By adjusting the flow rate of the regenerated catalyst in the lines 54, 55, the catalyst-to-oil ratio in the riser reactors 1, 2 is controlled.

The following examples will further illustrate the method, but the method is not limited thereby. The tests were carried out on a medium-scale test facility.

The biogrease and mineral oil in the examples and comparative examples are palm oil and atmospheric residue oil respectively, and the properties of palm oil and atmospheric residue oil are shown in Table 1 and Table 2 respectively.

Embodiment 1-4

Examples 1 to 4 illustrate the effect of using the combined catalytic conversion method of bio-grease and mineral oil provided by the present invention.

The catalyst (containing 7% by weight of USY zeolite, 8% by weight of zeolite beta, 20% by weight of ZSM-5 zeolite, and the balance as a carrier, all based on the total weight of the catalyst) was aged at 800°C with 100% steam for 10 hours, Using a medium-scale pilot plant, the catalyst loading in the composite reactor was 60 kg.

In embodiment 1, 80% palm oil and 20% atmospheric residue only enter riser reactor 1;

In embodiment 2, 40% palm oil and 20% atmospheric residue enter the bottom of riser reactor 1, and 40% palm oil enters the middle and lower part of riser reactor 1;

In Example 3, 80% palm oil and 20% atmospheric residual oil enter the riser reactor 1, and the riser 2 supplies the regenerant to the fluidized bed reactor.

In Example 4, 50% palm oil and 20% atmospheric residual oil enter riser reactor 1, and 30% palm oil enter riser reactor 2.

The agent-to-oil ratio in the examples refers to the weight ratio of the catalyst to the fresh feed (palm oil+atmospheric residue).

The evaluation results are shown in Table 3. In Table 3, A refers to riser reactor 1, B refers to riser reactor 2, and C refers to fluidized bed reactor 3.

Comparative example 1

Comparative Example 1 illustrates the effect of using a riser reactor to carry out the combined catalytic conversion method of bio-oil and mineral oil, and the raw materials are 80% palm oil and 20% atmospheric residue. The results are shown in Table 3.

As can be seen from Table 3, based on the carbon balance, the yields of ethylene, propylene, ethylene+propylene+butene of comparative example 1 using a single riser reactor are respectively lower than 5, 20, 40% by weight, while using the composite reaction The yields of ethylene, propylene, and ethylene+propylene+butene in Examples 1 to 4 of the device were as high as 6, 21, and 40% by weight or more, respectively.

Table 1

project palm oil Density (20℃), g/ ^cm3 0.9107 Refraction (70℃) 1.4464 Kinematic viscosity, mm ² /s 80°C 12.95 100°C 8.561 freezing point, ℃ 26 Aniline point, ℃ <25 Carbon residue, wt% 0.26 Elemental composition C, weight % 76.48 H, weight % 11.92 O, weight % 10.56 S, mg/L 3.5 N, mg/L /

Table 2

Raw oil name atmospheric residue Density (20℃), g/ ^cm3 0.8906 Viscosity, ^mm2 /sec 24.84 Asphaltenes, % 0.8 Kang's carbon residue, % 4.3 Distillation range, ℃ IBP 282 10% (volume) 370 30% (volume) 482 50% (volume) 553 70% (volume) - 90% (volume) -

table 3

Claims (12)

1. a bio-oil and mineral oil combined catalytic conversion method, it is characterized in that the method comprises: bio-oil contacts carry out catalytic cracking reaction with the catalyzer of the β zeolite that contains modification with mineral oil in compound reactor, 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; 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 is consisted of by riser reactor and downstriker transfer limes reactor, or the compound reactor that is consisted of by two or more riser reactors, or the compound reactor that is consisted of by two or more fluidized-bed reactors, or the compound reactor that is consisted of by two or more downstriker transfer limes reactors, or the compound reactor that is consisted of by two or more moving-burden bed reactors; The β zeolite of described modification is that described transition metal M is selected from one or more among Fe, Co, Ni and the Cu by the β zeolite of phosphorus and transition metal M modification; The described catalyzer that contains the β zeolite of modification, take the gross weight of catalyzer as benchmark, it contains 1%～60% zeolite mixture, 5%～99% heat-resistant inorganic oxide and 0～70% clay, and described heat-resistant inorganic oxide is selected from SiO ₂And/or Al ₂O ₃Take the gross weight of described zeolite mixture as benchmark, contain 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 large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening.

2. in accordance with the method for claim 1, it is characterized in that described bio-oil is selected from Vegetable oil lipoprotein, animal grease, microbial oil, discarded edible oil, one or more the mixture in the nigre of vegetable oil, and comprise one or more the mixture in tri-glyceride, the free lipid acid.

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. the weight ratio that in accordance with the method for claim 1, it is characterized in that described bio-oil and described mineral oil is 0.1～10: 1.

6. the weight ratio that in accordance with the method for claim 1, 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 two riser reactors and fluidized-bed reactor.

8. in accordance with the method for claim 1, it is characterized in that the described catalyzer that contains the β zeolite of modification, take the gross weight of catalyzer as benchmark, it contains 10%～50% zeolite mixture, 10%～70% heat-resistant inorganic oxide and 0～60% clay, and described transition metal M is selected from one or more among Fe, Co, Ni and the Cu.

9. in accordance with the method for claim 1, it is characterized in that described transition metal M is Fe and/or Cu.

10. 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.

11. 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

12. 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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