CN103773407A

CN103773407A - Method for catalytic cracking biomass

Info

Publication number: CN103773407A
Application number: CN201210414204.0A
Authority: CN
Inventors: 王刚; 高金森; 毕研涛
Original assignee: China University of Petroleum Beijing
Current assignee: China University of Petroleum Beijing
Priority date: 2012-10-25
Filing date: 2012-10-25
Publication date: 2014-05-07
Also published as: US20140115952A1; WO2014064008A1

Abstract

The invention discloses a method for converting biomass. The method comprises the following step: enabling the biomass and a catalytic cracking catalyst to be in contact with each other in a catalytic cracking reactor at a temperature higher than 400 DEG C to produce a product stream containing one or more cracking products, wherein the catalytic cracking reactor comprises a first zone, a second zone, a third zone, a catalyst supply pipe and a feed nozzle, the second zone is connected with a fluid in the first zone, and is arranged at a downstream position of the first zone, the inner diameter of the first zone in the downstream direction decreases gradually, the third zone is connected with a fluid in the second zone and is arranged at a downstream position of the second zone, the catalyst supply pipe is connected with the first zone and is arranged between a first position surface and a second position surface, and is used for supplying the catalytic cracking catalyst to a downstream position of the first position surface, the feed nozzle is provided with a feed nozzle outlet and is used for supplying the biomass to the reactor, and the feed nozzle outlet is arranged between the second position surface and the fluid connection of the first zone and the second zone.

Description

For the method for catalytic cracking biomass

Technical field

The present invention relates to the method for catalytic cracking biomass.More specifically, the invention still further relates to the method for catalytic cracking pyrolysis oil.The most particularly, the present invention relates to make the method derived from the pyrolysis oil catalytic cracking of the material containing biomass.

Background technology

Along with the minimizing of petroleum crude oil supply, use production of renewable energy resources liquid fuel to become more and more important.From the so-called biofuel of these fuel of renewable energy source.

Preferably derived from the biofuel of non-edible renewable energy source, for example, derived from the cellulosic material of plant, because these are not competed with foodstuffs production.These biofuels are also referred to as the s-generation, reproducible or senior biofuel.

Existing method comprises that the such cellulosic material pyrolysis making derived from plant is to obtain a pyrolysis oil, and upgrading processing, and makes afterwards pyrolysis oil catalytic cracking to obtain chemical and fuel product.

The people such as A.A.Lappas are published in Fuel, vol.81 (2002), has described the method for the biomass flash pyrolysis of circulating fluidized bed (CFB) reactor in article " Biomass pyrolysis in a circulating fluid bed reactor for production of fuels and chemicals " by name in 2087-2095 page.This CFB reactor comprises vertical riser tube type of reactor (7.08mm ID).This riser tube height is 165cm.Design and structure integrated spiral feeder system are in order to effectively to introduce biomass this device.The bottom that uses the jet-mixing system of particular design biomass to be introduced to riser tube from this screw feeding.This system is made up of the major diameter bottom container being connected with riser reactor by conical section.

As described in the people such as Lappas, the shortcoming of method is that the special jet-mixing system that comprises integrated spiral feed may be difficult to be amplified to commercial size.In addition it may be difficult, using jet-mixing system as above to improve existing FCC apparatus.

EP2325281 has described a kind of for making the method derived from the pyrolysis oil catalytic cracking of the material of lignocellulose-containing, and the method comprises the following steps charging experience hydrogenation deoxidation step a) making containing pyrolysis oil to obtain the product logistics that comprises part deoxidation pyrolysis oil; B) separate with the product logistics of a) middle acquisition thering is the part deoxidation pyrolysis oil of 5-30wt% oxygen level; C) the part deoxidation pyrolysis oil obtaining in making b) contacts to obtain deoxidation and crackate logistics under the hydrocarbon charging derived from mineral crude oil exists under catalytic cracking condition with cracking catalyst; With d) by least one product cut with c) in obtain product logistics separate.EP2325281 has also described by before entering cracking unit, part deoxidation pyrolysis oil and hydrocarbon feed stream being mixed or alternatively, by add them can obtain the co-feeding of step in c) in different steps.

But for the method for EP2325281 is amplified to commercial size, the method may need to improve to meet present transformation efficiency, robustness, maintenance and/or safety requirements.

Provide one to allow to be amplified to commercial-scale method, the method is used for co-fed to part or all of deoxidation pyrolysis oil and the hydrocarbon of catalytic cracking unit; And/or providing a kind of method of improving existing business catalytic cracking unit that allows to be allowed for co-fed to part or all of deoxidation pyrolysis oil and hydrocarbon, this will be progressive in the art.

Summary of the invention

Recently, find, in the time that biomass examples is added in fluid catalytic cracking unit as partially or completely deoxidation pyrolysis oil, can in fluid catalytic cracking reactor, form coke.The formation of this coke and then can cause unsettled piston flow in fluid catalytic cracking reactor.Therefore, the wearing quality of fluid catalytic cracking unit reduces and may need more maintenance.

Have been found that now by utilizing concrete feed nozzle arrangement that biomass are added in fluid catalytic cracking unit, can reduce or even avoid this coking.

Therefore the present invention provides a kind of method for conversion of biomass, be included in catalyst cracker makes biomass contact with catalytic cracking catalyst at the temperature that is greater than 400 ℃, to produce the product logistics containing one or more crackates, wherein catalyst cracker comprises:

The-the first district;

-Second Region, has and is connected with the fluid in the firstth district and is positioned at the first downstream, district, and the internal diameter of Second Region reduces on downstream direction;

-San district, has and is connected with the fluid of Second Region and is positioned at downstream, Second Region;

-catalyzer supply pipe, is connected with the firstth district, and for catalytic cracking catalyst being supplied to described the firstth district between the first plane and the second plane, described the second plane is positioned at the first plane downstream; With

-feed nozzle, it has feed nozzle and exports for biomass are supplied to reactor, and feed nozzle exports between the fluid between the second plane and the firstth district and Second Region is connected.

Have been surprisingly found that, if the position of feed nozzle is higher, for example the fluid between the firstth district and Second Region connect on position time, may form more coke.Have been surprisingly found that, the position of feed nozzle is lower, for example, while being positioned under the second plane of catalyzer supply pipe, also may form more coke.

Except described method, think that concrete catalyst cracker is also novel.Therefore the present invention further provides a kind of catalyst cracker, comprising:

The-the first district;

-catalyzer supply pipe, is connected with the firstth district, and for fluidized catalytic cracking catalyst being supplied to described the firstth district between the first plane and the second plane, described the second plane is positioned at the first plane downstream; With

-feed nozzle, it has feed nozzle outlet, and for charging is supplied to reactor, feed nozzle exports between the fluid between the second plane and the firstth district and Second Region is connected.

Accompanying drawing explanation

By following indefiniteness accompanying drawing, method of the present invention is described:

Fig. 1 has shown the schematic diagram of the first method and catalyst cracker, and described method and reactor are according to the present invention.

Fig. 2 has shown the schematic diagram of the second method and catalyst cracker, and described method and reactor are not according to the present invention.

Fig. 3 has shown the schematic diagram of third method and catalyst cracker, and described method and reactor are not according to the present invention.

Embodiment

The present invention relates to the catalytic cracking of biomass, and preferably relate to the catalytic cracking of the pyrolysis oil that is derived from the material that comprises biomass.

Biomass are herein interpreted as the composition of biogenetic derivation material, from available from or to be derived from the composition of material of oil, Sweet natural gas or coal different.Do not wish to be bound by the theory of any type, think that this biomass can contain carbon 14 isotropic substances with approximately 0.0000000001% abundance, based on the total mole number of carbon.

The example of biomass comprises: waterplant and algae, agricultural waste and/or forestry waste and/or paper refuse and/or the vegetable material obtaining from domesti refuse.Other example of biomass can comprise animal tallow, fatty oil and the cooking oil by mistake.

Preferably biomass are solid biomass material.More preferably biomass are materials of cellulose and/or lignocellulose.This containing " Mierocrystalline cellulose " in this article, the material of " lignocellulose " is also called " cellulosic " " lignocellulose " material.Cellulose materials is interpreted as the material that contains Mierocrystalline cellulose and also optionally contain xylogen and/or hemicellulose herein.Lignocellulosic materials is interpreted as the material that contains Mierocrystalline cellulose and xylogen and optional hemicellulose herein.

In preferred embodiments, biomass can be also the pyrolysis oil being derived from containing the material of biomass, are more preferably derived from the pyrolysis oil of the material of cellulose and/or lignocellulose.Preferably, pyrolysis oil stems from Mierocrystalline cellulose or such as agricultural waste of lignocellulosic materials, as corn stalk, large beanstalk, corn ear, straw, rice husk, oat shell, zein fiber, millet straw for example wheat, barley, rye and oat bar; Grass; Forest product and/or for example timber of forest resistates and/or the material relevant to timber, for example sawdust; Waste paper; Sugar for example bagasse of residual processing thing and beet pulp; Or its mixture.More preferably, pyrolysis oil stems from the Mierocrystalline cellulose or the lignocellulosic materials that are selected from timber, sawdust, straw, grass, bagasse, corn stalk and/or its mixture.

Mierocrystalline cellulose or lignocellulosic materials in the method for the invention as before biomass or before pyrolysis, can experience dry, except mineral substance, roasting, vapor explosion, granularity reduces, and multiviscosisty and/or granulation, to allow improved method operability and economy.

If the biomass in method of the present invention are pyrolysis oil mentioned above, this pyrolysis oil can be compatibly by making the material pyrolysis that contains biomass.In preferred embodiments, therefore method of the present invention further comprises the step of preparation pyrolysis oil mentioned above, and described step comprises makes the material pyrolysis that contains biomass to produce pyrolysis product.

Pyrolysis be herein interpreted as catalyzer exist under or catalyzer substantially not in the presence of, at the temperature that is equal to or greater than 380 ℃, the decomposition of the material that comprises biomass.

Oxygen concn has preferably been less than the required concentration of burning.Preferably, in oxygen deprivation, preferably in the atmosphere of anaerobic, carry out pyrolysis.Oxygen-lean atmosphere is interpreted as to comprise and is equal to or less than 15vol.% oxygen, is preferably equal to or less than 10vol.% oxygen, and is more preferably less than or equals the atmosphere of 5vol.% oxygen.Oxygen-free atmosphere is interpreted as the atmosphere that does not wherein substantially have oxygen.More preferably, be equal to or less than 5vol.% oxygen containing, be more preferably equal to or less than 1vol.% oxygen, and be most preferably equal to or less than in the atmosphere of 0.1vol.% oxygen and carry out pyrolysis.In the most preferred embodiment, in the time substantially there is not oxygen, carry out pyrolysis.

Be equal to or greater than 400 ℃, be more preferably equal to or greater than 450 ℃, be even more preferably equal to or greater than 500 ℃, and be most preferably equal to or greater than under the pyrolysis temperature of 550 ℃ the material that comprises biomass is carried out to pyrolysis.Pyrolysis temperature is also preferably equal to or less than 800 ℃, is more preferably equal to or less than 700 ℃, and is most preferably equal to or less than 650 ℃.

Synthesis pressure can vary widely.For practical purposes, preferably 0.01-0.5MPa(MPa), the more preferably pressure of 0.1-0.2MPa.Most preferably normal pressure (about 0.1MPa).

In some method, can adopt chemical to be used for the pre-treatment of biomass, or can add catalyzer to pyrolysis product, referring to for example H Wang cs., " Effect of acid, alkali; and steam explosion pretreatment on characteristics of bio-oil produced from pinewood ", Energy Fuels (2011) 25, p.3758-3764. preferably, pyrolysis does not comprise the outside catalyzer adding.

In preferred pyrolytic process (being commonly referred to flash pyrolysis technique), substantially there is not under oxygen for example, by biomass rapid heating (in the 3 seconds) temperature to 400-600 ℃, and remaining on this temperature and continue the short time (for example equal or equal 3 seconds).This flash pyrolysis rule is as being known in A.Oasmaa etc.; " Fast pyrolysis of Forestry Residue 1.Effect of extractives on phase separation of pyrolysis liquids "; Energy & Fuels; volume 17; number 1; 2003, pages 1-12; With A.Oasmaa etc., Fast pyrolysis bio-oils from wood and agricultural residues, Energy & Fuels, 2010, vol.24, pages 1380-1388; US4876108; US5961786; And US5395455.

In this pyrolysis that comprises biological material, produce pyrolysis product.Pyrolysis product can contain gas, solid (charcoal), one or more oil phases, and optional water.Below oil phase is being called to pyrolysis oil.Those skilled in the art can separate pyrolysis oil by any known method that is applicable to this object from pyrolysis product.This comprises that conventional method is for example filtered, centrifugal, cyclonic separation, extraction, membrane sepn and/or be separated.

Pyrolysis oil for example can comprise carbohydrate, alkene, paraffinic hydrocarbons (paraffin), oxygenate (oxygenate) and/or optional some residual water.Oxygenate is interpreted as the compound that contains at least one or more carbon atom, one or more hydrogen atom and one or more Sauerstoffatoms in this article.Oxygenate can for example comprise aldehyde, carboxylic acid, alkanol, phenol and ketone.

Preferably, the amount that pyrolysis oil comprises carbon, for being equal to or greater than 25 % by weight, is more preferably equal to or greater than 35 % by weight, most preferably be equal to or greater than 40 % by weight, preferably be equal to or less than 70 % by weight, be more preferably equal to or less than 60 % by weight, based on the gross weight of pyrolysis oil.

Pyrolysis oil also preferably comprises the amount of hydrogen for being equal to or greater than 1 % by weight, is more preferably equal to or greater than 5 % by weight, and is preferably equal to or less than 15 % by weight, is more preferably equal to or less than 10 % by weight, the gross weight (butt) based on pyrolysis oil.

Pyrolysis oil is also preferably wrapped oxygen containing amount for being equal to or greater than 25 % by weight, is more preferably equal to or greater than 35 % by weight, and is preferably equal to or less than 70 % by weight, is more preferably equal to or less than 60 % by weight, based on the gross weight of pyrolysis oil.Preferably define this oxygen level with butt.Butt is interpreted as eliminating water.

Pyrolysis oil can also comprise nitrogen and/or sulphur.

If there is nitrogen, preferably, the amount that pyrolysis oil comprises nitrogen, for being equal to or greater than 0.001 % by weight, is more preferably equal to or greater than 0.1 % by weight, and is preferably equal to or less than 1.5 % by weight, is more preferably equal to or less than 0.5 % by weight, based on the gross weight of pyrolysis oil.

If there is sulphur, preferably, the amount that pyrolysis oil comprises sulphur, for being equal to or greater than 0.001 % by weight, is more preferably equal to or greater than 0.1 % by weight, and is preferably equal to or less than 1 % by weight, is more preferably equal to or less than 0.1 % by weight, based on the gross weight of pyrolysis oil.

If present, preferably, the amount that pyrolysis oil comprises water is equal to or greater than 0.1 % by weight, is more preferably equal to or greater than 1 % by weight, is more preferably and is equal to or greater than 5 % by weight, and be preferably equal to or less than 55 % by weight, more preferably be equal to or less than 45 % by weight, be more preferably and be equal to or less than 35 % by weight, be more preferably and be equal to or less than 30 % by weight, most preferably be equal to or less than 25 % by weight, based on the gross weight of pyrolysis oil.

Preferably, the total acid value of pyrolysis oil can be 250mg KOH/g at the most, more preferably 5-200mg KOH/g, for example 10-150mg KOH/g.As used herein, measure carbon content, hydrogen richness and nitrogen content by ASTMD5291, and measure sulphur content by ASTM D2622.Calculate oxygen level by difference, the summation that makes carbon content, hydrogen richness, oxygen level, nitrogen content and sulphur content is 100 % by weight.Water-content is measured by ASTM E203.As used herein, total acid value is by using ASTM D664 to measure.

Water, containing oxygen-, nitrogen-and/or sulphur-compound and the existence of high total acid value (TAN) make pyrolysis product not be suitable for so the processing in catalytic cracking unit.

Further experience hydrogenation deoxidation step of pyrolysis oil in preferred embodiments.In hydrogenation deoxidation step, can produce the product that comprises at least part of deoxidation pyrolysis oil.This step is further called hydrogenation deoxidation (HDO) reaction.

Hydrogenation deoxidation is preferably interpreted as the concentration that reduces oxygenatedchemicals under hydrogenation deoxidation catalyst exists by means of hydrogen herein.

Hydrogenation deoxidation step is preferably incorporated under hydrogenation deoxidation catalyst existence, be equal to or greater than 200 ℃, more preferably be equal to or greater than 250 ℃, most preferably be equal to or greater than 280 ℃, to being equal to or less than 450 ℃, more preferably be equal to or less than 400 ℃, and be most preferably equal to or less than at the temperature of 350 ℃ the charging that comprises pyrolysis oil is contacted with hydrogen.The hydrogenation deoxidation temperature of mentioning is herein the maximum temperature occurring in hydrogenation deoxidation step.Total pressure during hydrogenation deoxidation step can change, for example, depend on the amount of the water that may exist in charging.Preferably, in hydrogenation deoxidation step, total pressure, for being more than or equal to 1.0 MPas, is more preferably equal to or greater than 5.0 MPas to being equal to or less than 35.0 MPas, is more preferably equal to or less than 30.0 MPas.Preferably, the hydrogen dividing potential drop in hydrogenation deoxidation step, for being equal to or greater than 0.2 MPa, is more preferably equal to or greater than 2.0Mpa to being equal to or less than 35.0 MPas, is more preferably equal to or less than 30.0 MPas.

Hydrogenation deoxidation catalyst can be the hydrogenation deoxidation catalyst that is applicable to any type of this object known to those skilled in the art.Hydrogenation deoxidation catalyst preferably comprises one or more hydrogenation deoxidation metals, and it is preferably carried in support of the catalyst.One or more hydrogenation deoxidation metals are preferably selected from VIII family and/or the group vib element in the periodic table of elements.Hydrogenation deoxidation metal can for example exist with the form of mixture, alloy or organometallic compound.Preferably, one or more hydrogenation deoxidation metals are selected from nickel (Ni), chromium (Cr), molybdenum (Mo), tungsten (W), cobalt (Co), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium (Os), copper (Cu), iron (Fe), zinc (Zn), gallium (Ga), indium (In), vanadium (V) and composition thereof.One or more metals can exist with simple substance form; Form with alloy or mixture exists; And/or exist with oxide compound, sulfide or other metal-organic form.Preferably, hydrogenation deoxidation catalyst is the catalyzer that comprises tungsten, ruthenium, rhodium, cobalt, nickel, copper, molybdenum and alloy thereof and/or mixture.

If hydrogenation deoxidation catalyst comprises support of the catalyst, this support of the catalyst can be shaped to the extrudate of ball, ring or other shape.Support of the catalyst can comprise refractory oxide or its mixture, preferential oxidation aluminium, soft silica-aluminum oxide, titanium oxide, silicon-dioxide, cerium oxide, zirconium white; Or it can comprise for example carbon of inert component or silicon carbide.Support of the catalyst can also comprise zeolite compound for example zeolite Y, zeolite beta, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, SAPO-11, SAPO-41 and ferrierite.

Except hydrogenation deoxidation step, pyrolysis oil can experience other step, if need or must so talk about.For example, while needs, pyrolysis oil can further experience hydrogenating desulfurization and/or the hydrodenitrification containing the charging of pyrolysis oil.Hydrogenating desulfurization can reduce the concentration of any sulfur-bearing hydrocarbon.Hydrodenitrification can reduce the concentration of any nitrogen-containing hydrocarbons.This hydrogenating desulfurization and/or hydrodenitrification can be before hydrogenation deoxidations, carry out afterwards and/or simultaneously.

After this hydrogenation deoxidation of pyrolysis oil, can obtain the product containing at least part of deoxidation pyrolysis oil.This product can contain gas phase, solid, one or more oil phases and optional water.In this case, can make gaseous product separate with whole product liquid, this whole product liquid can preferable separation become the water of containing water-soluble compound to contain the organic phase of (hydrogenation) deoxidation pyrolysis oil at least partly with at least one.Any solid can be for example by removing by filter.

May partly or entirely make pyrolysis oil deoxidation.The oxygen level (butt) of one or more organic phases (being below referred to as at least part of deoxidation pyrolysis oil) is preferably the 0.0wt% that is equal to or greater than of one or more organic phase gross weights, more preferably be equal to or greater than 0.5wt%, be more preferably and be equal to or greater than 5wt%, and be most preferably equal to or greater than 8wt%, to being equal to or less than 30wt%, more preferably be equal to or less than 20wt%, and be most preferably equal to or less than 15wt%(butt).

Biomass in the inventive method are at least part of deoxidation pyrolysis oil that are derived from containing the material of biomass in preferred embodiments.

Unless otherwise prescribed, " pyrolysis oil " conventionally mentioned herein below should be understood and refer to non-hydrogenation deoxidation pyrolysis oil and deoxidation pyrolysis oil at least partly.

In preferred embodiments, the biomass in the inventive method with together with other hydrocarbon charging, jointly give and enter catalyst cracker.One or more other hydrocarbon feed streams can be fed to catalyst cracker.One or more other hydrocarbon feed streams can be used as the logistics that comprises the mixture that contains biomass and other hydrocarbon charging, as the logistics separating with biomass or the two simultaneously, are added into catalyst cracker.Other hydrocarbon charging can compatibly be fed to any district of catalyst cracker, but is preferably supplied to the first Huo 3rd district.If the part supply using other hydrocarbon charging as the mixture containing biomass and other hydrocarbon charging, is compatibly fed to it the firstth district of catalyst cracker.If using other hydrocarbon charging as one or more independent logistics supplies, it can be supplied to expediently to the firstth district, San district or the two while.

Hydrocarbon charging is interpreted as the charging that comprises one or more hydrocarbon compounds in this article.Hydrocarbon compound is preferably interpreted as the compound being made up of hydrogen and carbon in this article.The example of hydrocarbon compound comprises paraffinic hydrocarbons (comprising naphthenic hydrocarbon), alkene and aromatic hydrocarbons.

Hydrocarbon charging can be the known any hydrocarbon chargings that are suitable for the charging of making catalytic cracking unit of those skilled in the art.Hydrocarbon charging can for example stem from conventional crude (sometimes also referred to as oil or mineral oil), unconventional crude oil (oil that uses the technology outside conventional oil well method to produce or extract) or Fischer-Tropsch oil (sometimes also referred to as synthetic oil) and/or any these mixture.

Preferably, hydrocarbon charging is the hydrocarbon charging that partly or entirely stems from petroleum crude oil.More preferably, hydrocarbon charging is the hydrocarbon charging that stems from oil substantially completely, and this is different from the hydrocarbon charging that stems from biomass.The example of conventional crude (also referred to as oil) comprises West Texas Intermediate crude oil, Brent crude oil, Dubai-Oman crude oil, Arabian Light crude oil, Midway Sunset crude oil or Tapis crude oil.

More preferably, the cut that hydrocarbon charging comprises petroleum crude oil, non-conventional crude oil or synthetic crude.Preferred cut comprises straight run (normal pressure) gas oil, flash distillation distillate, vacuum gas oil (VGO), coker gas oil, diesel oil, gasoline, kerosene, petroleum naphtha, liquefied petroleum gas (LPG), atmospheric resids (" long residuum ") and decompression residual oil (" short boiling range Residual oil ") and/or its mixture.Most preferably, hydrocarbon charging comprises atmospheric resids, decompression residual oil and/or vacuum gas oil.

In one embodiment, hydrocarbon charging preferably has and is equal to or greater than 100 ℃ under the pressure of 0.1 MPa, more preferably be equal to or greater than the 5 % by weight boiling points of 150 ℃, as measured by the distillation of ASTM D86 based on being entitled as " Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure ", respectively as measured by being entitled as the ASTM D1160 of " Standard Test Method for Distillation of Petroleum Products at Reduced Pressure ".The example of this hydrocarbon charging is vacuum gas oil.

In the second embodiment, hydrocarbon charging preferably has and is equal to or greater than 200 ℃ under the pressure of 0.1 MPa, more preferably be equal to or greater than 220 ℃, most preferably be equal to or greater than the 5 % by weight boiling points of 240 ℃, as measured by the distillation of ASTM D86 based on being entitled as " Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure ", respectively as measured by the ASTM D1160 that is entitled as " Standard Test Method for Distillation of Petroleum Products at Reduced Pressure ".The example of this hydrocarbon charging is long residuum.

In another preferred embodiment, under 0.1 MPa pressure, be equal to or greater than 70wt%, preferably be equal to or greater than 80wt%, more preferably be equal to or greater than 90wt% and be more preferably the hydrocarbon charging that is equal to or greater than 95wt% and be equal to or greater than 150 ℃ to being equal to or less than boiling at 600 ℃, as measured by the distillation of ASTM D86 based on being entitled as " Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure ", respectively as measured by the ASTM D1160 that is entitled as " Standard Test Method for Distillation of Petroleum Products at Reduced Pressure ".

The composition of hydrocarbon charging can vary widely.Preferably, the amount that hydrocarbon charging comprises the compound being only made up of carbon and hydrogen, for being equal to or greater than 50wt%, is more preferably equal to or greater than 75wt%, and is most preferably equal to or greater than 90wt%, to being equal to or less than 100wt%, and the gross weight meter based on hydrocarbon charging.

In a preferred embodiment, hydrocarbon charging comprises and is equal to or greater than 1wt%, more preferably be equal to or greater than 5wt%, and be most preferably equal to or greater than 10wt%, and be preferably equal to or less than 100wt%, more preferably be equal to or less than 90wt%, be most preferably equal to or less than the paraffinic hydrocarbons of 30wt%, based on total hydrocarbon feed charging meter.Paraffinic hydrocarbons is interpreted as all n-, rings-and the paraffinic hydrocarbons of branch.For practical purposes, the paraffinicity with all hydrocarbon chargings that play initial boiling point of at least 260 ℃ can be measured by the ASTM method D2007-03 that is entitled as " Standard test method for characteristic groups in rubber extender and processing oils and other petroleum-derived oils by clay-gel absorption chromatographic method ", and wherein the amount of saturates will represent the content of paraffinic hydrocarbons.For all other hydrocarbon chargings, the paraffinicity of hydrocarbon charging can by as be recorded in P.J.Schoenmakers, J.L.M.M.Oomen, J.Blomberg, W.Genuit, G.van Velzen, J.Chromatogr.A, 892 (2000) p.29 wait in comprehensive multidimensional gas chromatographic (GCxGC) measure.

Preferably hydrocarbon charging is heated to be equal to or greater than 50 ℃-be equal to or less than the temperature of 140 ℃ with the hydrocarbon charging of preparation preheating.More preferably hydrocarbon charging is heated to be equal to or greater than the temperature of 70 ℃, is more preferably equal to or greater than the temperature of 90 ℃, and more preferably hydrocarbon charging is heated to be equal to or less than the temperature of 130 ℃, be more preferably equal to or less than 120 ℃.

Preferably, the hydrocarbon charging of preheating is in liquid state, gaseous state or operative liquid-part gaseous state.

The heating of hydrocarbon charging can be carried out with the known applicable any-mode of those skilled in the art.For example, hydrocarbon charging can be heated in one or more interchanger.

In particularly preferred embodiments, at least part of deoxidation pyrolysis oil is mixed with other hydrocarbon charging as herein described, to prepare incoming mixture, be included in catalyst cracker and at the temperature that is greater than 400 ℃, this incoming mixture contacted with catalytic cracking catalyst with method of the present invention, to produce the product logistics containing one or more crackates.Preferably can in feed nozzle as herein described, make the hydrocarbon charging other with this of this at least part of deoxidation pyrolysis oil mix.Or, make the hydrocarbon charging that this at least part of deoxidation pyrolysis oil can be other with this before entering feed nozzle, mix to prepare incoming mixture, and this incoming mixture can be supplied to catalyst cracker by feed nozzle as herein described.

Preferably, biomass and other hydrocarbon charging arbitrarily arbitrarily can be respectively with 0.5/99.5 at least, more preferably at least 1/99, still more preferably the weight ratio of at least 2/98 biomass and hydrocarbon charging combines.Preferably, biomass and other hydrocarbon charging arbitrarily arbitrarily can be respectively with at the most 75/25, more preferably at the most 50/50, even more preferably at the most 20/80, and most preferably at the most the weight ratio of 15/85 biomass and hydrocarbon charging combine.

Containing in the incoming mixture of biomass and other hydrocarbon charging arbitrarily the amount of biomass be preferably equal to or less than 30wt%, more preferably be equal to or less than 20wt%, most preferably be equal to or less than 10wt% and be even more preferably equal to or less than 5wt%, based on the gross weight of incoming mixture.For the object of practice, containing in the incoming mixture of biomass and other hydrocarbon charging arbitrarily the amount of biomass be preferably equal to or greater than 0.1wt%, be more preferably equal to or greater than 1wt%, based on the gross weight of incoming mixture.

This incoming mixture can be compatibly in feed nozzle atomization with the incoming mixture of preparation atomization.Atomization in feed nozzle can compatibly utilize dispersion (dispersion) or atomizing gas to carry out.Preferred gas comprises steam and nitrogen.The incoming mixture of atomization can compatibly contact in catalyst cracker with catalytic cracking catalyst at the temperature that is greater than 400 ℃, to produce the product logistics containing one or more crackates.

Catalyst cracker comprises:

The-the first district;

In preferred embodiments, each of the firstth district as herein described, Second Region He 3rd district is arranged around the identical longitudinal axis is coaxial substantially.More preferably the firstth district as herein described and Second Region are tubuloses around this same longitudinal axis substantially, and Second Region as herein described is conical around this same longitudinal axis substantially.Preferred axes is the axle of basic vertical arrangement.In preferred embodiments, catalyst cracker is vertical arrangement substantially, and wherein the firstth district is positioned at reactor bottom, and Second Region is positioned at the first top, district, and He 3rd district are positioned at top, Second Region.The wall in each district is preferably interconnection, makes to basically form a reactor wall.

Preferred catalytic cracking case is fluid catalytic cracking reactor.Fluid catalytic cracking reactor herein should be understood the reactor that is suitable for carrying out fluidized catalytic cracking method.In such fluidized catalytic cracking method, use fluidized catalytic cracking catalyst.In preferred embodiments, therefore method of the present invention is fluidized catalytic cracking method, and wherein catalyst cracker is that fluid catalytic cracking reactor and catalytic cracking catalyst are fluidized catalytic cracking catalysts.

More preferably, catalyst cracker is riser reactor.This riser reactor is particularly suitable for as the fluid catalytic cracking reactor in fluidized catalytic cracking method.

In such riser reactor, fluidized catalytic cracking catalyst can be expediently flows to downstream end from the upstream extremity of reactor, that is to say in this case, upwards arrives riser reactor top from riser reactor bottom.In the handbook that it is " Fluid C atalytic Cracking technology and operations " that the example of suitable riser reactor is described in by the exercise question of the Joseph W.Wilson of PennWell Publishing Company (1997) publication, the 3rd chapter, particularly 101 to 112 pages, this handbook is hereby incorporated by.For example, riser reactor can be so-called Promotion From Within pipe reactor or the so-called outside riser reactor of wherein describing.

Preferably the firstth district is firstth district with substantially constant internal diameter.The first preferred maximum inner diameter in district, for being equal to or greater than 0.05 meter, is more preferably equal to or greater than 0.4 meter, is even more preferably equal to or greater than 0.8 meter, most preferably be equal to or greater than 1 meter, preferably be equal to or less than 5 meters with this maximum inner diameter, be more preferably equal to or less than 4 meters, be most preferably equal to or less than 2 meters.The height in the firstth district preferably in be equal to or greater than 0.5 meter-be equal to or less than 5 meters.

In fluid catalytic cracking reactor, particularly, in riser reactor, this firstth district is sometimes also referred to as bottom zone or lift pot.

In the firstth district, catalytic cracking catalyst, biomass and/or optional other hydrocarbon is arbitrarily co-fed can pass through fluidizing medium fluidisation, described fluidizing medium preferably flows to San district from the firstth district along downstream direction.Compatibly, this fluidizing medium is supplied to the firstth district by one or more feed nozzles.Preferably fluidizing medium is gas.In riser reactor, this fluidizing medium can be sometimes also referred to as lift gas, and described lift gas flows to riser reactor top from riser reactor bottom zone.For the fluidizing medium that makes catalytic cracking catalyst fluidisation can be for example by be positioned at catalyzer supply pipe more the ring-type gas distributor of upstream provide.For example, in riser reactor, can be by being for example positioned at the ring-type gas distributor supply of lift pot bottom for the lift gas that promotes catalytic cracking catalyst.For making biomass and/or optional the fluidizing medium of the other co-fed fluidisation of hydrocarbon can be expediently by one or more bottom inlet feed nozzles and/or the supply of one or more sidepiece entrance feed nozzle arbitrarily.

The example of this fluidizing medium or lift gas comprises: steam, nitrogen, gasification oil and/or oil distillate for example liquefied petroleum gas (LPG), gasoline, diesel oil, kerosene or petroleum naphtha, and their mixture.More preferably fluidizing medium contains steam and/or nitrogen or is made up of steam and/or nitrogen.

Second Region has the downstream that is connected and is positioned at the firstth district with the fluid in the firstth district.The internal diameter of Second Region reduces along downstream direction.Preferably Second Region has the shape of so-called flat-top cone substantially.In riser reactor, Second Region can be connecting zone, and so-called lift pot is connected with so-called riser reactor standpipe.Second Region also can be called " circular cone district " sometimes.

San district has the downstream that is connected and is positioned at Second Region with the fluid of Second Region.

In a preferred embodiment, the internal diameter that San district has substantially invariable internal diameter He 3rd district is less than the minimum diameter in the firstth district.

In a further preferred embodiment, the internal diameter in San district increases along downstream direction, and the upstream internal diameter in Qie 3rd district is less than the minimum diameter in the firstth district.

The preferred maximum inner diameter in San district is for being equal to or greater than 0.01 meter, more preferably be equal to or greater than 0.3 meter, even more preferably be equal to or greater than 0.6 meter, still more preferably be equal to or greater than 1 meter and preferably maximum inner diameter for being equal to or less than 3 meters, more preferably be equal to or less than 2.5 meters, be even more preferably equal to or less than 2 meters and be most preferably equal to or less than 1.8 meters.

Preferably be interpreted as for the maximum inner diameter in concrete district the maximum inner diameter existing in this district herein.

In riser reactor, San district is sometimes also referred to as riser reactor standpipe.

Catalyst cracker also comprises the catalyzer supply pipe being connected with the firstth district, and for catalytic cracking catalyst being supplied to the firstth described district between the first plane and the second plane, described the second plane is positioned at the first plane downstream.More preferably, catalyzer supply pipe is connected to the fluid channel in first district's sidewall.Catalyzer supply pipe can compatibly be supplied to fluidized catalytic cracking catalyst the firstth district.In riser reactor, this catalyzer supply pipe also can be called catalyzer standpipe.In such a case, the second plane can refer to the border of the topmost of stand-pipe output, and the first plane can refer to the border of the bottommost of stand-pipe output.

Catalyst cracker also comprises that having feed nozzle exports for biomass being supplied to the feed nozzle of reactor, and this feed nozzle exports between the fluid between the second plane and the firstth district and Second Region is connected.In riser reactor, therefore this feed nozzle can have the feed nozzle outlet between the horizontal plane on border and the plane of connecting zone beginning mentioned above of topmost of aiming at stand-pipe output.The latter can be preferably the plane of the beginning, district of flat-top cone shape wherein.

As described herein, feed nozzle can be advantageously used in and not only add biomass, and adds the co-fed and/or medium that liquefies arbitrarily of other arbitrarily hydrocarbon.In addition, feed nozzle also can be used as mixing tank, so that biomass and other arbitrarily co-fed mixing of hydrocarbon arbitrarily.Feed nozzle can be suitable for making biomass arbitrarily and/or the other co-fed atomization of hydrocarbon arbitrarily in addition.

Or catalyst cracker can comprise that one or more other nozzles are to provide other arbitrarily hydrocarbon the co-fed and/or medium that liquefies arbitrarily.

Catalyst cracker can comprise that one or more feed nozzles are for supplying biomass.If be used for supplying biomass by two or more feed nozzles, preferably at least one but more preferably all such for the feed nozzle of supplying biomass between the fluid between the second plane and the firstth district and Second Region is connected.

One or more feed nozzles can be the known applicable feed nozzles arbitrarily of those skilled in the art.Preferred feedstock nozzle is bottom inlet feed nozzle or sidepiece entrance feed nozzle.If use two or more feed nozzles, also can use the combination of one or more bottom inlet feed nozzles and/or one or more sidepiece entrance feed nozzles.Bottom inlet feed nozzle herein is preferably interpreted as from bottom to the outstanding feed nozzle of catalyst cracker.Sidepiece entrance feed nozzle herein is preferably interpreted as by sidewall to the outstanding feed nozzle of catalyst cracker.Preferred catalytic cracking case comprises at least one bottom inlet feed nozzle.More preferably this bottom inlet feed nozzle is the unique feed nozzle that biomass is supplied to the firstth district.

Preferably biomass and catalytic cracking catalyst are being equal to or greater than 450 ℃, more preferably be equal to or greater than 480 ℃, be most preferably equal to or greater than 500 ℃, to being equal to or less than 800 ℃, more preferably be equal to or less than 750 ℃, be most preferably equal to or less than at the temperature of 680 ℃ and contact.If temperature variation spreads all over catalyst cracker, mean the top temperature in catalyst cracker arbitrarily.

Preferably biomass and catalytic cracking catalyst are being equal to or greater than 0.05 MPa-be equal to or less than 1.0 MPas, are more preferably equal to or greater than under the pressure of 0.1 MPa-be equal to or less than, 0.6 MPa and contact.

In catalyst cracker, the overall average residence time of biomass is preferably and is equal to or greater than 1 second, more preferably be equal to or greater than 1.5 seconds and be even more preferably equal to or greater than 2 seconds to being equal to or less than 10 seconds, be preferably equal to or less than 5 seconds and be more preferably equal to or less than 4 seconds.The residence time of mentioning in this patent application stops based on the steam under exit condition, that is, the residence time not only comprises the residence time of regulation charging, and comprises the residence time of its converted product.

Weight ratio-this paper of catalyzer and charging (it is biomass and the optional other co-fed combined feed total feed of hydrocarbon arbitrarily) is also referred to as catalyzer: charge ratio-be preferably is equal to or greater than 1:1, more preferably be equal to or greater than 2:1 and be most preferably equal to or greater than 3:1 to being equal to or less than 150:1, more preferably to being equal to or less than 100:1, most preferably to being equal to or less than 50:1.

Catalytic cracking catalyst can be the known any catalyzer that are applicable to cracking method of those skilled in the art.Preferably, catalytic cracking catalyst comprises zeolite component.In addition, catalytic cracking catalyst can comprise amorphous binder compound and/or filler.The example of amorphous binder component comprises silicon-dioxide, aluminum oxide, titanium oxide, zirconium white and magnesium oxide, or two or more combination in them.The example of filler comprises clay (as kaolin).

Zeolite is large pore zeolite preferably.Large pore zeolite comprises the zeolite with porous crystalline aluminosilicate structure, and this porous crystalline aluminosilicate structure has the inner foam structure of porous, and the main shaft in hole is 0.62 nanometer to 0.8 nanometer thereon.The axle of zeolite is described in ' Atlas of Zeolite Structure Types ', W.M.Meier, D.H.Olson, and Ch.Baerlocher, the 4th revised edition in 1996, Elsevier, ISBN 0-444-10015-6.The example of large pore zeolite comprises FAU or faujusite like this, preferably synthetic faujasites, for example, zeolite Y or X, super steady zeolite Y (USY), rare earth zeolite Y (=REY) and rare earth USY (REUSY).According to the present invention, USY is preferably used as large pore zeolite.

Catalytic cracking catalyst also can comprise mesopore zeolite.According to the present invention, operable mesopore zeolite is to comprise the zeolite with porous crystalline aluminosilicate structure, and this porous crystalline aluminosilicate structure has the inner foam structure of porous, and the main shaft in hole is 0.45 nanometer to 0.62 nanometer thereon.The example of mesopore zeolite has MFI structure type like this, for example, and ZSM-5; MTW type, for example, ZSM-12; TON structure type, for example, θ type; With FER structure type, for example, ferrierite.According to the present invention, ZSM-5 is preferably used as mesopore zeolite.

According to another embodiment, can use the mixture of large pore zeolite and mesopore zeolite.In cracking catalyst, large pore zeolite is preferably 99:1 to 70:30 to the ratio of intermediate pore size zeolites, more preferably 98:2 to 85:15.

In the method for the invention, catalytic cracking catalyst compatibly with and stream mode contact with biomass.

Preferably catalytic cracking catalyst is separated with one or more crackates after using; In revivifier, regenerate; Be used further to catalyst cracker.

Preferred catalytic cracking case is a part for catalytic cracking unit.More preferably catalyst cracker is fluid catalytic cracking reactor, and described fluid catalytic cracking reactor is a part for so-called fluid catalytic cracking (FCC) unit.

In preferred embodiments, therefore method of the present invention provides a kind of fluidized catalytic cracking method, and described method comprises:

A) fluid catalytic cracking step, be included in fluid catalytic cracking reactor makes biomass contact with fluidized catalytic cracking catalyst at the temperature that is greater than 400 ℃, to produce product logistics and the useless fluidized catalytic cracking catalyst containing one or more crackates, wherein fluid catalytic cracking reactor comprises:

The-the first district;

B) separating step, comprises and makes one or more crackates and waste stream fluidized catalytic cracking catalyst separating;

C) regeneration step, comprises and makes waste stream fluidized catalytic cracking catalyst regeneration to produce the fluidized catalytic cracking catalyst of regeneration, heat and carbonic acid gas; With

D) recirculation step, comprises and makes the fluidized catalytic cracking catalyst of regeneration be recycled to fluid catalytic cracking step.

Fluid catalytic cracking step is preferably carried out as described earlier in this article.

Separating step preferably utilizes one or more cyclonic separators and/or one or more vortex tube to carry out.In addition, separating step may further include stripping step.In this stripping step, can the product of the useless fluidized catalytic cracking catalyst of stripping to absorb on the useless fluidized catalytic cracking catalyst of recovery before regeneration step.These products can recirculation and are added the crackate logistics obtaining from fluid catalytic cracking step.

Regeneration step is preferably included at the temperature that is equal to or greater than 550 ℃ and in regenerator column, makes useless fluidized catalytic cracking catalyst contact with oxygen-containing gas, to produce the catalytic cracking catalyst of regeneration, heat and carbonic acid gas.At regeneration period, the result that burning-off can be used as catalytic cracking reaction is deposited on the coke on catalyzer, thereby recovers the activity of catalyzer.

The fluidized catalytic cracking catalyst of regeneration can be recycled to fluid catalytic cracking step.

Produce in the method according to the invention the product logistics that comprises one or more crackates.In preferred embodiments by this product logistics with aftercut to produce one or more product cuts.

These one or more product cuts can be advantageously used for biofuel component and/or biochemicals component.

Further illustrate method of the present invention and reactor by following indefiniteness accompanying drawing.

Fig. 1 has shown fluid catalytic cracking reactor (102), comprises the firstth district (104), He 3rd district, Second Region (106) (108).The firstth district (104), He 3rd district, Second Region (106) (108) are around substantially vertical axle (109) coaxial arranging substantially.In addition, the firstth district (104), the wall in He 3rd district, Second Region (106) (108) connects, for example, form a fluidized reaction wall.The firstth district (104) has substantially invariable internal diameter.Second Region (106) is connected with the firstth district (104) fluid and is positioned at downstream, the firstth district (104).Second Region (106) has flat-top cone shape.The internal diameter of Second Region (106) reduces along downstream direction.San district (108) is connected with Second Region (106) fluid and is positioned at downstream, Second Region (106).San district has substantially invariable internal diameter, and described internal diameter is less than the internal diameter of the firstth district (104).Catalyzer supply pipe (110) is by outstanding the firstth district (104) of the firstth district (104) sidewall (112) and between the first plane (114) and the second plane (116), fluidized catalytic cracking catalyst is supplied to described the firstth district (104), and described the second plane (116) is positioned at the first plane (114) downstream.Logistics (124) is supplied to fluid catalytic cracking reactor (102) by the feed nozzle (120) with feed nozzle outlet (122), and described logistics comprises by partial hydrogenation deoxidation pyrolysis oil and the other co-fed incoming mixture forming of hydrocarbon.The fluid that feed nozzle outlet (122) is positioned between the second plane (116) and the firstth district (104) and Second Region (106) is connected between (105).In addition, by feed nozzle (120), nitrogenous logistics (126) is supplied to fluid catalytic cracking reactor (102) to assist the fluidisation of incoming mixture.

Fig. 2 and 3 has illustrated respectively similar fluid catalytic cracking reactor and method, has been expressed as feature (202) to (226) and feature (302) to (326) for the feature (102) to (126) of Fig. 1 name.

The difference of Fig. 2 and Fig. 1 is that the position of the feed nozzle (220) with feed nozzle outlet (222) is positioned under the second plane (216) feed nozzle outlet (222).

Fig. 3 is that with the difference of Fig. 1 the fluid that the position of the feed nozzle (320) with feed nozzle outlet (322) is positioned between the firstth district (304) and Second Region (306) feed nozzle outlet (322) is connected on (305).

Embodiment 1 and comparative example A and B

In embodiment 1 and comparative example A and B, use fluid catalytic cracking reactor by the incoming mixture catalytic cracking of the part deoxidation pyrolysis oil that contains the biomass-derived material of 5 weight part and 95 weight part petroleum derivation vacuum gas oils.

The length of fluid catalytic cracking reactor is approximately 5.5 meters.In addition, fluid catalytic cracking reactor comprises: San district, has the substantially invariable internal diameter (also referred to as riser reactor standpipe) of about 16mm; The second conical district, connects San district and the firstth district (also referred to as circular cone district); With the firstth district, there is the substantially invariable internal diameter (also referred to as lift pot) of about 26mm.These districts are around identical substantially vertical coaxial the arranging of axle.Incoming mixture is supplied to fluid catalytic cracking reactor.

In fluid catalytic cracking reactor, at the temperature of approximately 520 ℃, incoming mixture is contacted with the equilibrium catalyst that contains hyperastable Y-type RE zeolite (ReUSY).The feeding rate of incoming mixture is approximately 2.0 kgs/hr.Use approximately 8 catalyzer and the weight ratio of incoming mixture, the catalyzer delivery rate obtaining be approximately 16 kg catalyst/hour.By fluid catalytic cracking reactor operate fixed number hour.For each embodiment, in fluid catalytic cracking reactor, the residence time of incoming mixture is approximately 2 seconds.

By naked eyes with by the degree that checks that pressure reduction is observed coking.

For embodiment 1, nozzle is arranged as shown in fig. 1, observes a small amount of coking in for example nozzle and reactor.

For comparative example A, nozzle is arranged as shown in Figure 2, observes serious coking in for example nozzle and reactor.

For comparative example B, nozzle is arranged as shown in Figure 3, still observes a large amount of coking in for example nozzle and reactor.

Claims

1. for a method for conversion of biomass, be included in catalyst cracker and at the temperature that is greater than 400 ℃, biomass contacted with catalytic cracking catalyst, to produce the product logistics containing one or more crackates, wherein catalyst cracker comprises:

The-the first district;

-feed nozzle, it has feed nozzle outlet, and for biomass are supplied to reactor, feed nozzle exports between the fluid between the second plane and the firstth district and Second Region is connected.

2. the method for claim 1, wherein biomass are pyrolysis oil of biomass-derived material, described method is included in catalyst cracker and at the temperature that is greater than 400 ℃, pyrolysis oil is contacted with catalytic cracking catalyst, to produce the product logistics containing one or more crackates.

3. the method for claim 2, wherein pyrolysis oil is the pyrolysis oil that is derived from Mierocrystalline cellulose or lignocellulosic materials.

4. the method for claim 2 or 3, wherein pyrolysis oil is at least part of deoxidation pyrolysis oil.

5. the method for claim 1-4 any one, wherein the firstth district is firstth district with substantially constant internal diameter.

6. the method for claim 1-5 any one, wherein San district have substantially invariable internal diameter and wherein the internal diameter in San district be less than the minimum diameter in the firstth district.

7. the method for claim 1-5 any one, wherein San district has the internal diameter increasing on downstream direction, and wherein the upstream internal diameter in San district is less than the minimum diameter in the firstth district.

8. the method for aforementioned claim any one, wherein catalyzer supply pipe is connected to the fluid channel in first district's sidewall.

9. the method for aforementioned claim any one, wherein said method is fluidized catalytic cracking method, catalyst cracker is that fluid catalytic cracking reactor and catalytic cracking catalyst are fluidized catalytic cracking catalysts.

10. the method for aforementioned claim any one, wherein catalyst cracker is riser reactor.

The method of 11. aforementioned claim any one, wherein by co-fed other hydrocarbon firstth district that is supplied to.

The method of 12. aforementioned claim any one, wherein make catalytic cracking catalyst, biomass and/or the optional other co-fed fluidisation of hydrocarbon arbitrarily by fluidizing medium, described fluidizing medium is supplied to the firstth district and flows to San district from the firstth district along downstream direction.

The method of 13. claims 12, wherein fluidizing medium is steam, nitrogen, liquefied petroleum gas (LPG), gasoline, diesel oil, kerosene or petroleum naphtha and/or arbitrarily their mixture.

14. 1 kinds of catalyst crackers, comprising:

The-the first district;

The reactor of 15. claims 14, further comprises

-there is the fluidizing medium supply of the outlet in the firstth district and/or the other co-fed supply of hydrocarbon.