Prepare the method for product of distillation and/or C2-C4 alkeneInvention field
The present invention relates to prepare the method for product of distillation and/or C2-C4 alkene.
Background of invention
Heavy hydrocarbon sulfuration catalytic pyrolysis (FCC) is well known in the art to produce compared with for example gasoline of low boiling hydrocarbon product.FCC method has existed since nineteen forties.Typically, FCC unit or method comprise at least one riser reactor, catalyst separator and revivifier.Raw material is incorporated in riser reactor, and wherein it contacts with the red-hot FCC catalyzer from revivifier.The mixture flow of raw material and FCC catalyzer is through riser reactor and enter into catalyst separator, in this hydrocarbon product and FCC catalyst separating.The hydrocarbon product separating flow to down-stream system for further separation from catalyst separator, flow in revivifier with the catalyzer separating,, in scission reaction process, burn from catalyzer at FCC coke deposited on catalyst charcoal at this, the catalyzer of regeneration is provided.The catalyzer of gained regeneration is used as aforementioned red-hot FCC catalyzer and mixes with the FCC raw material being incorporated in riser reactor.
Design many FCC method and systems, to provide FCC raw material the high product of boiling point in gasoline boiling range that change into.But, there is certain situation, in the time expecting to provide that FCC raw material is high changes into for example C2-C4 alkene of light alkene and/or product of distillation, described product of distillation may comprise boiling point in diesel boiling range product-this is contrary with the product of boiling point in gasoline boiling range.
The method of distillment and light alkene in the middle of US2006/0231461 discloses and prepared.In this method, between the catalyst regenerator in FCC method or unit and riser reactor, use dense phase reactor or fixed fluidized-bed reactor, so that the selectivity of improved middle distillment productive rate and the raising to production light alkene to be provided.Dense phase reactor is for providing gasoline stocks cracking to obtain light alkene and for the adjusting of catalyzer is provided, so that this catalyzer is more suitable in riser reactor with distillment product in the middle of producing.
Expect to produce this middle distillment product and this light alkene in continuable mode.
In the situation that being not wishing to be bound by theory, some can consider that carbon is with CO2be present in atmosphere, and ptotoautotroph for example plant, algae and some bacteriums utilize the energy of sunlight that this inorganic carbon is fixed into organic carbon (for example carbohydrate).At geology time frame (>106year) in, organic substance (vegetable material) is become fossilized, and oil, Sweet natural gas and coal are provided.According to stating, in the time that these fossil resources of consumption are prepared polymkeric substance, chemical and fuel, in the short period of time of 1-10 framework, carbon is with CO2form is released gets back in atmosphere.In this case, the speed imbalance that speed when Wood Adhesives from Biomass fossilation resource is overall and fossil resource is consumed and discharges.But, in the time using annual renewable farm crop or biomass as the raw material of preparation our carbon-based polymer, chemical and fuel, CO2fixing speed equals the speed that it is consumed and discharges.This article further shows, uses annual renewable carbon raw material to allow Sustainable Exploitation carbon-based material and controls and also even reduce CO2discharge, meets to assist the global CO formulating according to the Kyoto Protocol2emission standard.
Provide to assist and produce continuable CO2discharge or even reduce the CO from refinery2discharge method and/or provide at CO2catch with trade plan in may useful method be the progress of prior art.
WO2008/127956 discloses a kind of system, and it comprises the riser reactor containing gas oil feedstocks and the first catalyzer, under catalytic pyrolysis condition, obtains containing the gas oil product of cracking and the riser reactor product of the first used catalyst; Containing the gas oil product of at least a portion cracking and the intermediate reactor of the second catalyzer, under height exacting terms, obtain intermediate reactor product and second used catalyst of cracking; Wherein intermediate reactor feedstock comprises at least one in lipid acid and fatty acid ester.This lipid acid and/or fatty acid ester can be for example the vegetables oil obtaining, as plam oil, and cocounut oil, Semen Maydis oil, soybean oil, Thistle oil, sunflower oil, linseed oil, sweet oil and peanut oil and/or animal tallow.
But the shortcoming of the method for describing in WO2008/127956 is to use vegetables oil and/or animal tallow can compete as the purposes of food with them as FCC raw material.
More preferably use unedible renewable energy source for example some fibre cellulosic material (as timber) as FCC raw material.
Therefore, provide the FCC method of producing distillment and C2-C4 alkene by the progress that is this area, described method allow people use unedible renewable energy source for example cellulose materials as raw material.
Summary of the invention
Astoundingly, have now found that, can be by the appropriate position feeding cellulose materials in FCC technique, for example pyrolysis oil and/or timber, obtain this FCC method.
Therefore, the invention provides the method for preparing product of distillation and one or more C2-C4 alkene, the method comprises:
A) in riser reactor, at the temperature that is equal to or greater than 400 DEG C, FCC raw material is contacted with FCC catalyzer, to produce product of distillation and useless FCC catalyzer, wherein FCC raw material comprises cellulose materials and hydrocarbon raw material altogether;
B) by least a portion product of distillation and useless FCC catalyst separating;
C) the FCC catalyzer of regenerated, to produce the FCC catalyzer of regeneration;
D), in intermediate reactor, at the temperature that is equal to or greater than 500 DEG C, intermediate reactor feedstock is contacted, to produce one or more C2-C4 alkene and the FCC catalyzer with the regeneration of crossing with the FCC catalyzer of at least a portion regeneration;
E) catalyst separating with the regeneration of using by one or more C2-C4 alkene of at least a portion;
The FCC catalyzer of the regeneration that f) use at least a portion was used is as step FCC catalyzer a).
The in the situation that of being bound by any kind theory, think not wishing, for example, when catalytic pyrolysis cellulose materials (, solid fiber cellulosic material and/or pyrolysis oil), while forming with catalytic pyrolysis vegetables oil and/or animal tallow compared with much more coke.Therefore, if when for example solid fiber cellulosic material of cellulose materials and/or pyrolysis oil are fed in intermediate reactor-be similar to lipid acid in WO2008/127956 and/or fatty acid ester-will on catalyzer, form excessive coke, and used catalyst can not be used further in riser reactor to produce any product of distillation.
But, be surprisingly found out that, cellulose materials can be used as raw material in the method for preparing product of distillation and one or more C2-C4 alkene, in the time cellulose materials being fed in riser reactor instead of intermediate reactor in the time feeding together with cellulose materials and the common raw material of hydrocarbon.
With the advantage of producing the pattern of product of distillation and one or more C2-C4 alkene instead of further have with the pattern operation FCC method of production gasoline product be: can in riser reactor, use lesser temps, form thereby further reduce the coke causing because of cellulose materials raw material.Under this lesser temps, operation can cause lower C3 and/or C4 product hydrocarbon yields, for example, and propane, propylene, butane and/or butylene.In addition, under this lesser temps operation can cause more olefinic gasoline, described olefinic gasoline may more be difficult to fuel in other component blend.But easily, method of the present invention any olefinic gasoline that allows optionally to circulate, described olefinic gasoline is produced as product in riser reactor, as steps d in the method) raw material of interior intermediate reactor.In this intermediate reactor, this olefinic gasoline can advantageously change into C3 and/or C4 hydrocarbon product and gasoline that can blend.
Therefore, method of the present invention advantageously allow people use unedible renewable energy source for example cellulose materials as the raw material of preparing in the FCC method of product of distillation and one or more C2-C4 alkene.
Accompanying drawing summary
Fig. 1 is the process flow sheet that represents one embodiment of the invention.
Detailed Description Of The Invention
The step of the inventive method a) in, in riser reactor, at the temperature that is equal to or greater than 400 DEG C, FCC raw material is contacted with FCC catalyzer, to produce product of distillation and useless FCC catalyzer.
Fluidized catalytic cracking (FCC) raw material can comprise one or more cellulose materialss.Preferably, FCC raw material comprises solid cellulose material, pyrolysis oil, and/or its mixture.In particularly preferred embodiments, FCC raw material comprises and is selected from unedible solid fiber cellulosic material, one or more materials in pyrolysis oil and/or its mixture.Unedible material is appreciated that the material for being not suitable for human consumption herein.
" cellulose materials " is appreciated that herein as comprising Mierocrystalline cellulose, hemicellulose, the material of lignocellulose and/or xylogen; The material that it is derivative; And/or the mixture of these materials.For example, the fluent material that pyrolysis oil can be regarded as being derived by cellulose materials.More preferably, cellulose materials comprises lignocellulose or its derivative material.This material of lignocellulose-containing is also referred to as ligno-cellulosic materials.Preferably, cellulose materials is solid fiber cellulosic material, or material derived liquid or the gas material of this solid cellulose.Most preferably cellulose materials is solid fiber cellulosic material, the pyrolysis oil being derived by cellulose materials and/or its mixture.
Preferably, cellulose materials is not the material of producing for human food prods.The example of suitable cellulose materials comprises waterplant and algae, agricultural waste and/or forestry waste and/or paper refuse and/or the vegetable material being obtained by domesti refuse and/or carbohydrate process residues and/or its mixture.The example of suitable cellulose materials comprises agricultural waste, for example cornstalk, soybean stalk, corn cob, straw, rice husk, oat shell, zein fiber, such as wheat-straw of cereal rice straw, barley-straw, rye stalk and oat stalk; Grass; Forestry products and/or forestry residue, for example timber and the material relevant with timber, for example wood chip, sawdust, bark or tree pin; Waste paper is opened; Carbohydrate process residues, for example sugarcane and beet pulp; Or its mixture.
More preferably, cellulose materials is to be selected from timber, sawdust, straw, grass, bagasse, cornstalk, and/or solid fiber cellulosic material in its mixture.These solid fiber cellulosic material are favourable, because they do not produce competition with human food prods, and are therefore regarded as more sustainable.
Cellulose materials can be also the material being derived by above-mentioned materials, for example, by pyrolysis, (hydrogenation) liquefaction (sometimes also referred to as solvolysis), and baking or other processing, the liquids and gases material being derived by above-mentioned cellulose materials.More preferably, cellulose materials is solid fiber cellulosic material or the pyrolysis oil of optionally toasting.
" pyrolysis oil " is appreciated that the oil for obtaining by pyrolysis cellulose materials herein.Pyrolysis oil can promote grade (for example significantly reducing the oxygen level in pyrolysis oil) by hydrotreatment and/or hydrogenation deoxidation.But, preferably, use not or there is no the untreated pyrolysis oil substantially that promotes grade by hydrotreatment and/or hydrogenation deoxidation, because can advantageously avoid in the method for the invention this hydrotreatment and/or hydrogenation deoxidation.Pyrolysis oil can comprise " entirely " pyrolysis oil or its part.
" pyrolysis " is appreciated that the thermolysis at the temperature that is equal to or greater than 350 DEG C of cellulose materials for preferred solid herein.The concentration of oxygen is preferably less than the desired concentration of perfect combustion.More preferably, pyrolysis is carried out in the oxygen situation that does not substantially have non--on the spot-generation.Limited amount oxygen can be in the process of pyrolysis method in-situ generation.Preferably, at oxygen deprivation gas, in the atmosphere of preferred oxygen-free gas, carry out pyrolysis.More preferably, pyrolysis is equal to or less than 5 volume % oxygen containing, and is more preferably equal to or less than 1 volume % oxygen and is most preferably equal to or less than in the atmosphere of 0.1 volume % oxygen to carry out.In the most preferred embodiment, pyrolysis is carried out in the situation that substantially there is not oxygen.
Pyrolysis temperature is preferably equal to or greater than 350 DEG C, is more preferably equal to or greater than 400 DEG C, and is most preferably equal to or greater than 450 DEG C.Pyrolysis temperature is further preferably equal to or less than 800 DEG C, is more preferably equal to or less than 700 DEG C, and is most preferably equal to or less than 650 DEG C.Synthesis pressure can vary widely.For putting into practice object, be preferably 0.01-0.5MPa (MPa), more preferably the pressure of 0.1-0.2MPa.Most preferably normal atmosphere (about 0.1MPa).
" baking " is appreciated that herein as being equal to or greater than 200 DEG C to being equal to or less than at the temperature of 350 DEG C, substantially do not have catalyzer and in oxygen deprivation gas (atmosphere of preferred oxygen-free gas), processing solid fiber cellulosic material." atmosphere of oxygen deprivation gas " be appreciated that as containing and be equal to or less than 15 volume %, is preferably equal to or less than 10 volume % oxygen and is more preferably equal to or less than the atmosphere of 5 volume % oxygen." atmosphere of oxygen-free gas " is appreciated that as oxygen non-existent atmosphere substantially wherein.
Baking solid fiber cellulosic material preferably at the temperature that is greater than 200 DEG C, is more preferably equal to or greater than at the temperature of 210 DEG C, is still more preferably equal to or greater than at the temperature of 220 DEG C, is still more preferably equal to or greater than at the temperature of 230 DEG C and carries out.In addition, baking solid fiber cellulosic material, preferably being less than 350 DEG C, is more preferably equal to or less than the temperature of 330 DEG C, is still more preferably equal to or less than the temperature of 310 DEG C, is more more preferably equal to or less than at the temperature of 300 DEG C and carries out.
Toast any solid fiber cellulosic material preferably carries out in the situation that substantially there is not oxygen.More preferably, baking for example, under the inert atmosphere that contains for example rare gas element (nitrogen, carbonic acid gas and/or steam); And/or in reduction atmosphere, under for example for example methane of hydrogen, hydrocarbon gas of reducing gas and ethane or carbon monoxide existence, carry out.
Can under the pressure of wide region, carry out any baking.But, preferably, under normal atmosphere (about 0.1MPa), toast.In addition, can intermittently or toast continuously.
The solid fiber cellulosic material of toasting has higher energy density, higher mass density and larger mobility, thus make it than being easier to transport, granulation and/or storage.Due to fragility more, therefore it can be more prone to be reduced to less particle.
If cellulose materials comprises solid fiber cellulosic material, method of the present invention preferably includes extra step, wherein use this solid fiber cellulosic material as step a) in the part of FCC raw material reduce before its granularity.
Preferably, as step a) in any solid fiber cellulosic material of a part of FCC raw material solid fiber cellulosic material that is micronization." the solid fiber cellulosic material of micronization " is appreciated that for having mean particle size be to be equal to or greater than 5 microns to the solid fiber cellulosic material of size-grade distribution that is equal to or less than 5000 microns herein, and this adopts Laser Scattering Particle Size Distribution Analyzer to measure.
Can, before or after this solid fiber cellulosic material baking, optionally reduce the granularity of any solid fiber cellulosic material.When this solid fiber cellulosic material comprise timber or toasted timber time, it may be for example particularly advantageous that this granularity reduces.Can reduce any optionally granularity of the solid fiber cellulosic material of baking according to the well known by persons skilled in the art any mode that is suitable for this purpose.Suitable granularity reduction method comprises crushing, pulverizes, and/or grinds.Granularity reduces can for example pass through ball mill, hammer grinding machine, and (blade) shredding machine, knife mill, cutter grid (knife grid) or cutting machine are realized.
Preferably, step a) in, the any solid fiber cellulosic material using in FCC raw material has wherein mean particle size and is equal to or greater than 5 microns (μ m), more preferably be equal to or greater than 10 microns, even more preferably be equal to or greater than 20 microns, most preferably be equal to or greater than 100 microns to being equal to or less than 5000 microns, be more preferably equal to or less than 1000 microns, and be most preferably equal to or less than the size-grade distribution of 500 microns.
For the object of practice, can be ISO 13320 methods of " Particle size analysis-Laser diffraction methods " according to title, adopt Laser Scattering Particle Size Distribution Analyzer, preferably Horiba LA950, size-grade distribution and the mean particle size of mensuration solid fiber cellulosic material.
Except cellulose materials, FCC raw material also comprises hydrocarbon raw material (herein also referred to as hydrocarbon feed) altogether.Hydrocarbon altogether raw material comprises one or more materials except above-described cellulose materials.Therefore hydrocarbon altogether raw material comprises one or more materials except solid fiber cellulosic material, pyrolysis oil or its mixture.
" hydrocarbon feed " is appreciated that the raw material for containing one or more hydrocarbon compounds herein." hydrocarbon compound " is appreciated that herein as containing the two compound of hydrogen and carbon, and the compound being preferably made up of hydrogen and carbon.Preferably, the common raw material of hydrocarbon is fluid hydrocarbon raw material altogether." fluid hydrocarbon is raw material altogether " is appreciated that herein as be not solid-state hydrocarbon raw material altogether in the time contacting with FCC catalyzer.Hydrocarbon altogether raw material preferably with substantially liquid, with gaseous state substantially or be fed in riser reactor by feed nozzle with operative liquid-part gaseous state.For altogether raw material of highly viscous hydrocarbon, therefore advantageously can this raw material of preheating, enter into afterwards in feed nozzle.Hydrocarbon altogether raw material is preferably gaseous state in the time contacting with catalytic cracking catalyst.When with substantially or when operative liquid enters in riser reactor, once fluid hydrocarbon altogether raw material preferably enter, vaporize, and preferably under gaseous state, contact with FCC catalyzer and/or cellulose materials.
Hydrocarbon altogether raw material can be for example well known by persons skilled in the art be suitable for as catalytic pyrolysis unit raw material any non--the hydrocarbon raw material altogether of solid.Hydrocarbon altogether raw material can be for example available from conventional crude oil (sometimes also referred to as oil or mineral oil), unconventional crude oil (oil that, uses the technology except conventional oil well method to produce or extract) or fischer-tropsch oil (being sometimes referred to as synthetic oil) and/or its mixture.
Hydrocarbon altogether raw material can be also the hydrocarbon raw material altogether from for example vegetables oil of renewable resources.
In one embodiment, the common raw material of hydrocarbon is derived from the crude oil of preferred routine.The example of conventional crude 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.Therefore these oil are mineral hydrocarbon raw materials altogether also referred to as mineral oil and the common raw material of preferred hydrocarbons sometimes." mineral hydrocarbon is raw material altogether " is appreciated that to be the hydrocarbon raw material altogether that comprises or be derived from mineral oil.
More preferably, hydrocarbon is total to preferred conventional crude or the renewable oils that raw material comprises small portion.Preferred hydrocarbon altogether raw material comprises straight run (normal pressure) gas oil, flash distillation distilled oil, vacuum gas oil (VGO), coker gas oil, diesel oil, gasoline, kerosene, petroleum naphtha, liquefied petroleum gas (LPG), long residuum (" long residuum ") and vacuum residuum (" short boiling range residual oil ") and/or its mixture.Most preferably, the common raw material of hydrocarbon comprises long residuum and/or VGO.
The hydrocarbon altogether composition of raw material can vary widely.Hydrocarbon altogether raw material can for example contain paraffinic hydrocarbons, alkene and aromatic hydrocarbons." paraffinic hydrocarbons " is appreciated that and refers to n-, ring-and branching-paraffinic hydrocarbons.
In preferred embodiments, hydrocarbon altogether raw material comprises one or more paraffinic hydrocarbonss, for example, for to be equal to or greater than 20wt% to one or more paraffinic hydrocarbonss that are equal to or less than 100wt%, be preferably and be equal to or greater than one or more paraffinic hydrocarbonss of 50wt% and more preferably from being equal to or greater than one or more paraffinic hydrocarbonss of 70wt% and most preferably from being equal to or greater than 90wt% to one or more paraffinic hydrocarbonss that are equal to or less than 100wt%, based on the hydrocarbon gross weight of raw material altogether.Be total to raw material containing this hydrocarbon of one or more paraffinic hydrocarbonss and be total to raw material also referred to as the hydrocarbon of paraffinic hydrocarbons in this article.
For the object of practice, to play initial boiling point be at least 260 DEG C all hydrocarbon altogether in raw material the content of paraffinic hydrocarbons can be the ASTM method D2007-03 measurement of " Standard test method for characteristic groups in rubber extender and processing oils and other petroleum-derived oils by clay-gel absorption chromatographicmethod " by title, wherein the amount of saturates represents paraffinicity.For every other hydrocarbon raw material altogether, the paraffinicity that hydrocarbon is total in raw material can be measured by comprehensive multidimensional gas chromatography (GCxGC), as P.J.Schoenmakers, J.L.M.M.Oomen, J.Blomberg, W.Genuit, G.van Velzen, J.Chromatogr.A, described in 892 (2000) the 29th pages of grades.
The hydrocarbon of the paraffinic hydrocarbons altogether example of raw material comprises so-called Fisher-Tropsch derived hydrocarbon stream (described in WO2007/090884 and at this by reference to introducing) or hydrotreater product or hydrogenation wax." hydrogenation wax " is appreciated that the bottoms fraction into hydrocracking device.The example that can obtain the process for hydrocracking of hydrocarbonaceous of the bottoms fraction that can be used as the common raw material of hydrocarbon is disclosed in EP-A-699225, EP-A-649896, WO-A-97/18278, EP-A-705321, in EP-A-994173 and US-A-4851109, at this by reference to being introduced into.
In preferred embodiments, hydrocarbon altogether raw material comprises the element hydrogen that is equal to or greater than 11wt%, more preferably be equal to or greater than the element hydrogen (, hydrogen atom) of 12wt%, to be dried as basis (not moisture) based on the hydrocarbon gross weight of raw material altogether.Element hydrogen (being for example equal to or greater than the content of 12.2wt%) the permission hydrocarbon of high-content altogether raw material serves as cheap hydrogen donor in Deep Catalytic Cracking process.The common raw material of especially preferred hydrocarbon that element hydrogen content is equal to or greater than 12.5wt% is Fisher-Tropsch derived wax-like Raffinate.This Fisher-Tropsch derived wax-like Raffinate can for example comprise the elemental carbon of about 85wt% and the element hydrogen of 15wt%.
Cellulose materials and the hydrocarbon altogether weight ratio of raw material can vary widely.
Hydrocarbon altogether raw material is preferably equal to or greater than 50 to 50 (5:5) with the weight ratio of cellulose materials, more preferably be equal to or greater than 70 to 30 (7:3), still be more preferably equal to or greater than 80 to 20 (8:2), be even more preferably equal to or greater than 90 to 10 (9:1).For the object of practice, hydrocarbon altogether raw material is preferably equal to or less than 99.9 to 0.1 (99.9:0.1) with the weight ratio of cellulose materials, is more preferably equal to or less than 95 to 5 (95:5).Hydrocarbon is total to raw material and cellulose materials is preferably fed in catalytic cracking reaction device under the weight ratio in above-mentioned scope.If cellulose materials is solid fiber cellulosic material, the gross weight based on FCC raw material, the consumption of solid fiber cellulosic material is preferably equal to or less than 30wt%, is more preferably equal to or less than 20wt%, is most preferably equal to or less than 10wt% and is even more preferably equal to or less than 5wt%.For the object of practice, based on the gross weight of FCC raw material, the consumption of existing any solid fiber cellulosic material is preferably equal to or greater than 0.1wt%, is more preferably equal to or greater than 1wt%.
In the time that cellulose materials comprises pyrolysis oil, being fed to raw material in catalytic cracking reaction device can preferably include and be equal to or greater than 5wt% and be more preferably equal to or greater than 10wt% to being equal to or less than 99wt% and being more preferably equal to or less than this pyrolysis oil of 90wt%, based on the gross weight of FCC raw material.
Preferably, preferably solid, cellulose materials and hydrocarbon altogether the binding substances of raw material have and be equal to or greater than 1.1 (1.1/1), more preferably be equal to or greater than 1.2 (1.2/1), be most preferably equal to or greater than 1.3 (1.3/1) hydrogen and total mol ratio (H/C) of carbon.For the object of practice, FCC raw material can for example have and is equal to or greater than 1.1 (1.1/1) to being equal to or less than 2.15 (2.15/1) hydrogen and total mol ratio (H/C) of carbon.
Can be before entering in riser reactor, hydrocarbon mixture is raw material and cellulose materials altogether, or they can add independently in the same position of riser reactor or different positions place.
In one embodiment, before entering in riser reactor, hydrocarbon mixture raw material and cellulose materials altogether not together.In this embodiment, hydrocarbon altogether raw material and cellulose materials simultaneously (a position) be fed in riser reactor, once and enter in riser reactor, optionally mix; Or the common raw material of hydrocarbon and cellulose materials independently (in different positions) add in riser reactor.Riser reactor can have multiple feed(raw material)inlets nozzle.Therefore the common raw material of cellulose materials and hydrocarbon can feed each component by independent feed(raw material)inlet nozzle and process in riser reactor, even these two kinds of component unmixings.
In the time that cellulose materials is solid fiber cellulosic material, preferably therein hydrocarbon altogether raw material supply to the upstream position of the position in riser reactor, by this solid cellulose materials supply in riser reactor.Think in the case of not wishing to be bound by any kind theoretical, this allows solid fiber cellulosic material first to contact with FCC catalyzer; Allow solid cellulose material converting to become at least part of and preferably vaporization completely with this middle oil product of permission of middle oil product, be total to raw material by interpolation hydrocarbon afterwards and carry out quencher FCC catalyzer.Altogether further supply the residence time that solid fiber cellulosic material provides solid fiber cellulosic material to grow (when with hydrocarbon altogether compared with residence time of raw material time) in raw material upstream at hydrocarbon, thereby make to use the solid fiber cellulosic material that there is mean particle size and be equal to or greater than the size-grade distribution of 2000 microns.
In another embodiment, before entering in riser reactor, be mixed together hydrocarbon raw material and cellulose materials altogether, to provide hydrocarbonaceous to be total to the raw mixture of raw material and cellulose materials.Can just before entering in riser reactor, prepare this raw mixture, or before advancing in riser reactor, it optionally can be remained in the material container of stirring.
Fluidized catalytic cracking (FCC) catalyzer preferably includes zeolite (sometimes also referred to as crystal aluminosilicate), the zeolite preferably disperseing in amorphous matrix component.For example, FCC catalyzer can comprise amorphous silicon oxide aluminum oxide and zeolite.In addition, FCC catalyzer preferably includes binding agent and/or filler.
In preferred embodiments, FCC catalyzer comprises so-called " macropore " zeolite." macropore " zeolite is appreciated that the zeolite for containing the porous crystalline silico-aluminate structure with the inner cell configuration of porous herein, and on the inner cell configuration of described porous, the major axis of hole is 0.62 nanometer-0.8 nanometer.The axle of zeolite is described in W.M.Meier, D.H.Olson, and Ch.Baerlocher ' 1996, Elsevier, in ISBN 0-444-10015-6 for Atlas of Zeolite Structure Types', the 4th revised edition.The example of this large pore zeolite comprises FAU or faujusite.
In preferred embodiments, FCC catalyzer comprises and is selected from Y zeolite, overstable Y zeolite (USY); X zeolite, zeolite beta, zeolite L, offretite, mordenite, faujusite (comprising synthetic faujasites) and zeolite omega, the zeolite in rare earth zeolite Y (=REY) and rare earth USY (REUSY).
If FCC catalyzer comprises Y-Shaped zeolite, this Y-Shaped zeolite preferably includes the silicon oxide and total mol ratio of aluminum oxide, the more preferably from about total mol ratio of 3.0 to approximately 6.0 silicon oxide and aluminum oxide that are greater than 3.0.
Except above-mentioned zeolite, FCC catalyzer also can comprise so-called mesopore zeolite." mesopore " zeolite is appreciated that to be the zeolite that comprises the porous crystalline silico-aluminate structure with the inner cell configuration of porous herein, and on the inner cell configuration of described porous, the major axis of hole is 0.45 nanometer-0.62 nanometer.
Therefore, except above-mentioned zeolite, FCC catalyzer also preferably includes and is selected from following zeolite: MFI type zeolite (for example ZSM-5); MTW type zeolite (for example ZSM-12); MTT type zeolite (for example ZSM-23); TON type zeolite (for example, zeolite θ 1 or ZSM-22); For example, with FER structure type, ferrierite.In the middle of these MFI type zeolites, ZSM-5 is most preferred.
In preferred embodiments, FCC catalyzer comprises that zeolite Y or super steady zeolite Y (USY) are in conjunction with such as ZSM-5 of MFI type zeolite.
If FCC catalyzer comprise simultaneously large pore zeolite and mesopore zeolite these two, in FCC catalyzer, large pore zeolite is preferably 99:1 to 70:30, more preferably 98:2 to 85:15 with the ratio of mesopore zeolite.
In preferred embodiments, can be by using hydrogen ion, ammonium ion, multivalent metal cation (for example containing the positively charged ion of rare earth, magnesium cation or calcium positively charged ion), or the combination of hydrogen ion, ammonium ion and multivalent metal cation exchanges the zeolite using in FCC catalyzer, increase stability and/or the acidity of this zeolite, thereby reduce sodium content, until it is less than about 0.8wt%, preferably be less than about 0.5wt% and or be less than about 0.3wt%, with Na2o form is calculated.
FCC catalyzer further preferably includes amorphous matrix component.The example of this amorphous matrix comprises amorphous silicon oxide-aluminum oxide, amorphous silicon oxide, amorphous alumina, amorphous oxidation titanium, amorphous oxidation zirconium and amorphous oxidation magnesium, or two or more these combination.
In addition, FCC catalyzer can comprise binding agent and/or filler.The example of binding agent is silicon sol.The example of filler comprises natural or synthesis of clay, column or delamination clay, or one or more mixture in these.The example that can be present in the clay in FCC catalyzer comprises kaolin, hectorite, sepiolite and attapulgite.
The total weight range of zeolite existing in FCC catalyzer is preferably 5-50wt%, more preferably 10-30wt%, even more preferably 10-25wt%, with respect to the total mass of FCC catalyzer, and preferably amorphous matrix component, binding agent and/or filler of rest part.
" riser reactor " is appreciated that the reactor of the tubulose substantially into extending herein.This reactor adapted is in carrying out catalytic cracking reaction.The reactor of the tubulose substantially extending is preferably orientated in the mode of perpendicular.
The example of suitable riser reactor is disclosed in title for " Fluid Catalytic Cracking technology and operations ", Joseph W.Wilson, published by PennWell Publishing Company (1997), the 3rd chapter, particularly in the handbook of 101-112 page, at this by reference to introducing.
Riser reactor can be so-called Promotion From Within pipe reactor described herein or so-called outside riser reactor.
Most preferably Promotion From Within pipe reactor is perpendicular, the reactor of tubulose substantially, and it can have the upstream extremity of the perpendicular that is positioned at external container and be positioned at the downstream end of the perpendicular of internal tank.This container is suitably for being suitable for the reaction vessel of catalytic cracking reaction and/or comprising one or more cyclonic separators and/or the container of coiling pipeline.In the time that at least a portion raw material comprises solid cellulose material or pyrolysis oil, Promotion From Within pipe reactor is particularly advantageous.Solid fiber cellulosic material can change into pyrolysis oil on the spot.The in the situation that of being bound by any kind theory, think not wishing, Promotion From Within pipe reactor can reduce the polymerization of formed any alkene, stops up risk and maintenance or maintenance requirement thereby reduce.
In the time using outside riser reactor, advantageously use the outside riser reactor in the top with curve or low regime, for example, if title is " Fluid Catalytic Cracking technology and operations ", Joseph W.Wilson, publish (1997) by PennWell Publishing Company, the 3rd chapter, sets forth in the handbook of Fig. 3-7, at this by reference to introducing.Advantageously find, a part of catalytic cracking catalyst can be deposited in curve or low regime, thereby forms the corrosion that protective layer prevents any residual solid cellulose material granule and/or is included in any oxygen-containing hydrocarbon in pyrolysis oil.
Advantageously can add lift gas in the bottom of riser reactor.The example of this lift gas comprises steam, vaporizing oil and/or oil distillate, and/or these any mixture.Consider from the angle of practice, steam is most preferably as lift gas.But the advantage that uses vaporizing oil and/or oil distillate (the preferably liquefied petroleum gas (LPG) of vaporization, gasoline, diesel oil, kerosene or petroleum naphtha) can have as lift gas is: lift gas can serve as hydrogen donor and can prevent or reduce coke formation simultaneously.In particularly preferred embodiments, steam and vaporizing oil and/or vaporizing oil cut (preferably liquefied petroleum gas (LPG), gasification gasoline, diesel oil, kerosene or petroleum naphtha) are as lift gas.
When cellulose materials is solid fiber cellulosic material and while introducing this solid fiber cellulosic material in riser reactor bottom, advantageously can be increased in by increasing the diameter of bottom place riser reactor the residence time of the riser reactor place cellulose materials of this part.Therefore, in preferred embodiments, riser reactor comprises riser reactor pipeline and base section, and described base section has the diameter larger than riser reactor pipeline, and wherein solid fiber cellulosic material is supplied in the base section in riser reactor.
There is larger-diameter base section and can for example there is lift pot form.
Preferably, the total mean residence time of cellulose materials in riser reactor is for being equal to or greater than 1.0 seconds, more preferably be equal to or greater than 1.5 seconds, still be more preferably equal to or greater than 2.0 seconds to being equal to or less than 5.0 seconds, preferably, to being equal to or less than 4.0 seconds, optimum is chosen and is equal to or less than 2.5 seconds.In present patent application, mention the stop of the residence time based on steam under exit condition, that is, the residence time comprises not only the residence time of regulation raw material (for example, FCC raw material) and the residence time of its converted product.
Preferably, temperature in the riser reactor that FCC raw material contacts with FCC catalyzer is therein for being equal to or greater than 400 DEG C, more preferably be equal to or greater than 450 DEG C, still be more preferably equal to or greater than 480 DEG C to being equal to or less than 800 DEG C, more preferably to being equal to or less than 700 DEG C, still more preferably to being equal to or less than 600 DEG C, and optimum is chosen and is equal to or less than 550 DEG C.
Preferably, the pressure in riser reactor, for being equal to or greater than 0.05MPa to being equal to or less than 1MPa, is more preferably equal to or greater than 0.1MPa to being equal to or less than 0.6MPa.
The weight ratio ratio (catalyzer: raw material ratio) with raw material also referred to as catalyzer in this article of FCC catalyzer and FCC raw material (being cellulose materials and hydrocarbon whole FCC raw materials of raw material altogether).The weight ratio scope of this catalyzer and raw material is preferably and is equal to or greater than 1:1, is more preferably equal to or greater than 2:1, and is most preferably equal to or greater than 3:1 to being equal to or less than 150:1, and more preferably to being equal to or less than 100:1, optimum is chosen and is equal to or less than 50:1.
Step a) in, preferably can produce one or more hydrocarbon product and useless FCC catalyzer.One or more hydrocarbon product comprise at least product of distillation, but also can comprise one or more other products." hydrocarbon product " is appreciated that as the product containing one or more hydrocarbon compounds herein.
Step b) in, such one or more hydrocarbon product-described hydrocarbon product comprise at least a portion product of distillation-can with useless FCC catalyst separating.
Preferably under one or more cyclonic separators and/or one or more spiral tube auxiliary, carry out b) (herein also referred to as separating step) of step.It is " Fluid Catalytic Cracking that the suitable method that carries out separating step is for example described in title; Design, Operation, and Troubleshooting of FCC Facilities "; Reza Sadeghbeigi; by Gulf Publishing Company; Houston Texas publishes (1995); the particularly handbook of 219-223 page and " Fluid Catalytic Cracking technology and operations "; Joseph W.Wilson, publishes (1997), the 3rd chapter by PennWell Publishing Company, particularly 104-120 page, in the 6th chapter, the particularly handbook of 186-194 page, at this by reference to introducing.Cyclonic separator preferably, under the speed of 18-80 m/s, more preferably operates under the speed for 25-55 m/s.
Step b) can further comprise the FCC catalyzer that stripping is useless.In this stripping step, useless FCC catalyzer can be by stripping, to be recovered in the spawn absorbing on useless FCC catalyzer, makes afterwards useless FCC catalyzer advance in the regeneration of step in c).These products can be recycled and/or join in one or more hydrocarbon product that a) obtained by step.
In preferred embodiments, rectifying subsequently step a) and/or step b) in obtain one or more hydrocarbon product, to produce one or more product cuts.
Can be suitable for rectifying and carry out rectifying from any mode of the product of catalytic cracking reaction device according to well known by persons skilled in the art.For example, can be " Fluid Catalytic Cracking technology and operations " as title, Joseph W.Wilson, publish (1997) by PennWell Publishing Company, the 8th chapter, particularly, described in the handbook of 223-235 page, carry out rectifying, at this by reference to being introduced into.
One or more hydrocarbon product preferably obtain with the hydrocarbon gas product form from step (a) and/or step (b).These hydrocarbon gas products can be separated into various gas and product liquid subsequently in one or more rectification cells.
Preferably, use water cooler and/or rectifier, cooling hydrocarbon gas product any heavy liquid product of condensation obtaining from step (a).Rectifier preferably includes distillation tower, and described distillation tower is included in the base section (being sometimes referred to as flash zone) of tower bottom; Heavy ring oil (HCO) part, lightweight ring oil (LCO) part and top section.
In lightweight ring oil (LCO) part of distillation tower, product of distillation can separate with the rest part of hydrocarbon product." product of distillation " is preferably interpreted as the composition containing hydrocarbon compound herein, wherein 80wt% at least, more preferably at least the boiling point of 90wt% under 0.1MPa for being equal to or greater than 221 DEG C to being equal to or less than 370 DEG C.
Naphtha products (herein also referred to as the product containing gasoline) and so-called dry gas can be drawn from the top section of distillation tower." naphtha products or containing the product of gasoline " is preferably interpreted as the composition containing hydrocarbon compound herein, wherein 80wt% at least, more preferably at least the boiling point of 90wt% under 0.1MPa for being equal to or greater than 30 DEG C to being less than 221 DEG C.
Step c) (herein also referred to as regeneration step) is preferably included in the FCC catalyzer of regenerated in revivifier, to produce the FCC catalyzer of regeneration.More preferably, step c) is included in revivifier and at the temperature that is equal to or greater than 550 DEG C, makes useless FCC catalyzer contact with oxygen-containing gas, to produce FCC catalyzer, heat and the carbonic acid gas of regeneration.In regenerative process, as step a) and/or steps d) in the result of catalytic cracking reaction be possible be burnt at FCC coke deposited on catalyst charcoal, to recover the activity of catalyzer.
Preferably, catalyst regenerator comprises the substantially vertically arranged columniform container substantially that defines breeding blanket, and wherein useless FCC catalyzer is maintained as fluidized-bed by for example air of upwards mobile oxygen-containing gas.
Preferably, useless FCC catalyzer is being equal to or greater than 575 DEG C, is more preferably equal to or greater than 600 DEG C to being equal to or less than 950 DEG C, more preferably regenerates to being equal to or less than at the temperature of 850 DEG C.In the most preferred embodiment, the temperature in breeding blanket preferably maintains and is equal to or greater than 620 DEG C to being equal to or less than in the scope of 780 DEG C, and more preferably maintains and be equal to or greater than 670 DEG C to being equal to or less than in the scope of 750 DEG C.Preferably, useless FCC catalyzer is being equal to or greater than 0.05MPa to being equal to or less than 1MPa, is more preferably equal to or greater than 0.1MPa to the interior regeneration of the pressure range that is equal to or less than 0.6MPa.
In breeding blanket, the residence time scope of useless FCC catalyzer is preferably and is equal to or greater than 1 minute to being equal to or less than 6 minutes, and is more preferably equal to or greater than 2 minutes to being equal to or less than 4 minutes.Coke content on the FCC catalyzer of regeneration is less than the coke content on useless FCC catalyzer.Preferably, the coke content on the FCC catalyzer of regeneration is equal to or less than 0.5wt%, the gross weight of the FCC catalyzer based on regeneration.More preferably, the coke content on the FCC catalyzer of regeneration is for being equal to or greater than 0.01wt% to being equal to or less than 0.5wt%, the gross weight of the FCC catalyzer based on regeneration.Most preferably, the coke concentration on the FCC catalyzer of regeneration is for being equal to or greater than 0.01wt% to being equal to or less than 0.1wt%, the gross weight of the FCC catalyzer based on regeneration.
In preferred embodiments, the side logistics of fresh FCC catalyzer is added in revivifier, to make up the possible loss of FCC catalyzer in this technique, for example possible loss of FCC catalyzer in any optional cyclonic separator in any cyclonic separator after reactor and/or after revivifier.In addition, can use fresh FCC catalyzer to substitute the useless FCC catalyzer of a part by the side logistics of fresh FCC catalyzer, to make up any loss of catalyst activity in this technique.If the useless FCC catalyzer of a part is substituted by fresh FCC catalyzer, the useless FCC catalyzer of this part is preferably equal to or less than 10wt%, more preferably be equal to or less than 5wt%, and be most preferably equal to or less than 1wt%, the gross weight of the catalyzer based on existing in revivifier.
" fresh FCC catalyzer " is appreciated that the FCC catalyzer using in fluidized catalytic cracking reaction into not yet herein.
Oxygen containing gas can be the known any oxygen containing gases that are suitable for using in revivifier of those skilled in the art.For example, oxygen containing gas can be air or oxygen-rich air." oxygen-rich air " is appreciated that herein as containing and is greater than 21 volume % oxygen (O2) air, more preferably containing being equal to or greater than the air of 22 volume % oxygen, based on the cumulative volume of air.
Any heat producing in the regeneration step of heat release be preferably used to step a) and/or steps d) in provide energy to feed vaporization and endothermic catalytic cracking.In addition, can use produced heat heating water and/or generating steam.Can use elsewhere steam, for example, as the lift gas in riser reactor.
In preferred embodiments, step c) further comprises the FCC catalyzer of produced regeneration and the such as carbon dioxide separation of any by product producing in regeneration.Preferably, under one or more cyclonic separation separators and/or spiral tube are auxiliary, carry out this separation.
The FCC catalyzer of regeneration advances to steps d at least partly) in.
In steps d) in, the FCC catalyzer of at least a portion regeneration is contacted in intermediate reactor at the temperature that is equal to or greater than 500 DEG C, to produce one or more C2-C4 alkene and the FCC catalyzer with the regeneration of crossing with intermediate reactor feedstock.
Intermediate reactor feedstock preferably contains the raw material of one or more hydrocarbon compounds, at least 80wt% of described one or more hydrocarbon compounds, and more preferably at least the boiling point of 90wt% under 0.1MPa is equal to or less than 221 DEG C, is more preferably equal to or less than 204 DEG C.More preferably, intermediate reactor feedstock is the raw material containing one or more hydrocarbon compounds, the at least 80wt% of described hydrocarbon compound, more preferably at least the boiling point of 90wt% under 0.1MPa, for being equal to or greater than 30 DEG C to being less than 221 DEG C, is more preferably equal to or greater than 32 DEG C to being equal to or less than 204 DEG C.
The example that can be used as the purification stream of intermediate reactor feedstock comprises so-called naphtha products described above herein.This naphtha products can be for example forms by one or more cuts of fluidized catalytic cracking reactor product, at least 80wt% of described cut, and more preferably at least 90wt% seethes with excitement to being less than in the scope of 221 DEG C being equal to or greater than 30 DEG C.
The example of naphtha products comprises lightweight-lightweight-ring oil (light-light-cycle oil) (LLCO, sometimes also referred to as heavy-catalytic cracking gasoline (HCCG) or heavy catalytic pyrolysis petroleum naphtha); Catalytic cracking gasoline (CCG, sometimes also referred to as middle runnings gasoline or catalytic pyrolysis petroleum naphtha); With lightweight catalytic cracking gasoline (LCCG, sometimes also referred to as the petroleum naphtha of catalytic pyrolysis tops or lightweight catalytic pyrolysis).
The further example that can be used as the purification stream of intermediate reactor feedstock comprises coker gasoline, visbreaking gasoline, lightweight straight-run spirit, heavy straight-run spirit, Raffinate, hydrogenation wax, fischer-tropsch wax and/or these mixture.
In particularly preferred embodiments, intermediate reactor feedstock is included in the product that step is produced in a) in riser reactor, for example, containing the product of gasoline, or the naphtha products of production step riser reactor a) in.Therefore, preferably, step a) is included in riser reactor, makes FCC raw material contact with FCC catalyzer at the temperature that is equal to or greater than 400 DEG C, to produce the product containing gasoline, and product of distillation and useless FCC catalyzer; With at least a portion containing the product of gasoline in steps d) in be used as intermediate reactor feedstock.
In preferred embodiments, intermediate reactor feedstock comprises one or more alkene, for example comprise one or more alkene that are equal to or greater than 20wt%, more preferably be equal to or greater than one or more alkene of 45wt% to one or more alkene that are equal to or less than 65wt%, more preferably to one or more alkene that are equal to or less than 55wt%, based on the gross weight of intermediate reactor feedstock." alkene " is appreciated that, into hydrocarbon compound, wherein two or more carbon atoms are bonded on another carbon atom by two keys herein.Preferably, these alkene that comprise in intermediate reactor feedstock are C5+-alkene." C5+-alkene " be appreciated that the alkene that is equal to or greater than 5 carbon atoms for having herein.This C5+the example of-alkene comprises amylene, pentadiene, hexene and hexadiene.The example of this intermediate reactor feedstock containing alkene is the naphtha products (for example, the gasoline of catalytic pyrolysis) containing alkene.Preferably, therefore intermediate reactor feedstock is to comprise to be equal to or greater than 20wt% to the naphtha products (herein also referred to as the product containing gasoline) of one or more alkene that is equal to or less than 65wt%, based on the gross weight of naphtha products.
This naphtha products containing one or more alkene may be difficult to and other fuel element blend.Method of the present invention can be easily by this, the naphtha products containing alkene changes into gasoline component and one or more C2-C4 alkene that can blend.
In preferred embodiments, therefore the present invention also provides the method for preparing biofuel and/or biochemicals, and the method comprises:
A), in riser reactor, at the temperature that is equal to or greater than 400 DEG C, FCC raw material is contacted with FCC catalyzer, to produce product of distillation, useless FCC catalyzer, and optionally first containing the product of gasoline, wherein FCC raw material comprises cellulose materials and hydrocarbon raw material altogether;
B) by least a portion product of distillation and useless FCC catalyst separating;
C) the FCC catalyzer of regenerated, to produce the FCC catalyzer of regeneration;
D) in intermediate reactor, at the temperature that is equal to or greater than 500 DEG C, intermediate reactor feedstock is contacted with the FCC catalyzer of at least a portion regeneration, to produce FCC catalyzer, one or more C2-C4 alkene and second product containing gasoline of the regeneration of using, wherein said intermediate reactor feedstock optionally comprises the first product containing gasoline, described second comprises one or more hydrocarbon compounds containing the product of gasoline, and wherein at least described in 80wt% the boiling point of one or more hydrocarbon compounds under 0.1MPa for being equal to or greater than 30 DEG C to being less than 221 DEG C;
E) by least a portion second containing the product of gasoline and one or more C2-C4 alkene of at least a portion the catalyst separating with the regeneration of using;
F) the FCC catalyzer that uses the regeneration used of at least a portion is the FCC catalyzer in a) as step;
Wherein blend at least a portion first is product and one or more other components containing gasoline containing the product of gasoline or at least a portion second, to prepare biofuel and/or biochemicals.
In addition, intermediate reactor feedstock can comprise further biological raw material component, for example vegetables oil, the cooking oil of using, animal tallow and/or its mixture.This vegetable oil, with the cooking oil of crossing and/or animal tallow optionally by hydrotreatment (comprising for example hydrogenation and/or hydrogenation deoxidation) lifting grade or pre-treatment.Suitable vegetables oil comprises for example rapeseed oil, plam oil, Oleum Cocois, Semen Maydis oil, soybean oil, Thistle oil, sunflower oil, linseed oil, sweet oil and peanut oil.Suitable animal tallow comprises for example lard, beef fat, suet fat and chicken fat.If there is any biological raw material component, this biological raw material component is preferably to be equal to or greater than 1wt% to being equal to or less than 40wt%, more preferably be equal to or greater than 5wt% to being equal to or less than 30wt%, most preferably be equal to or greater than 10wt% and be present in intermediate reactor feedstock to the consumption that is equal to or less than 20wt%, based on the gross weight of intermediate reactor feedstock.
Intermediate reactor preferably contains the intermediate reactor of fluidized catalyst.More preferably intermediate reactor is fluidized-bed reactor or riser reactor.In the situation that intermediate reactor is riser reactor, steps d) in intermediate reactor can be described as the second riser reactor because the riser reactor in a) will form the first riser reactor in step.In the time that intermediate reactor is fluidized-bed reactor, it is so-called dense phase reactor preferably, fine and close bed bioreactor or fixing fluidized-bed reactor.
If intermediate reactor is fluidized-bed reactor, this fluidized-bed reactor can for example comprise the container that defines fluidized bed reaction zone.Regeneration FCC catalyzer can be included in this reaction zone, at this it can by introduce intermediate reactor feedstock and optionally steam carry out fluidisation.
If intermediate reactor is riser reactor, this riser reactor can be for example a) middle any type or the riser reactor of describing of step, comprising for example inside or outside riser reactor and/or the riser reactor containing lift pot.If use lift gas, can use any lift gas of a) mentioning for step, but steam can be most preferably as lift gas.
Preferably, temperature in the intermediate reactor that intermediate reactor feedstock contacts with the FCC catalyzer of regeneration is therein for being equal to or greater than 500 DEG C, more preferably be equal to or greater than 520 DEG C, most preferably be equal to or greater than 550 DEG C to being equal to or less than 900 DEG C, more preferably to being equal to or less than 850 DEG C, still more preferably to being equal to or less than 800 DEG C, and optimum is chosen and is equal to or less than 750 DEG C.
In preferred embodiments, in steps d) in temperature in intermediate reactor higher than step a) in temperature in riser reactor.
Preferably, the pressure in intermediate reactor, for being equal to or greater than 0.05MPa (MPa) to being equal to or less than 1MPa, is more preferably equal to or greater than 0.1MPa to being equal to or less than 0.6MPa.
In preferred embodiments, intermediate reactor feedstock and steam simultaneously by feeding in the reaction zone of intermediate reactor, to contact with the FCC catalyzer of regeneration.Use steam can advantageously improve the selectivity to C2-C4 alkene as common raw material or lift gas.In the time using steam, the weight ratio scope of steam and intermediate reactor feedstock is preferably and is equal to or greater than 0.1:1 to being equal to or less than 15:1.More preferably the weight ratio scope of steam and intermediate reactor feedstock is preferably 0.2:1 to 10:1.
In steps d) in, preferably, can produce one or more hydrocarbon product and the FCC catalyzer with the regeneration of crossing.One or more hydrocarbon product comprise at least one or multiple C2-C4 alkene, but also can comprise one or more other hydrocarbon product.
In step (e), can be according to any mode well known by persons skilled in the art, separate the FCC catalyzer of one or more such hydrocarbon product and the regeneration used.For example, can be identical with the mode of the useless FCC catalyst separating in the mode of one or more hydrocarbon product separation and such one or more hydrocarbon product (described hydrocarbon product can comprise at least a portion distillment) and step (b) with the FCC catalyzer of the regeneration of crossing.For example, can under one or more cyclonic separators and/or one or more spiral tube are auxiliary, carry out this separation.In addition, can step e) in introduce stripping step, the FCC catalyzer of the regeneration of wherein can stripping using, to be recovered in the spawn absorbing with on the FCC catalyzer of regeneration of crossing, the FCC catalyzer that uses afterwards the regeneration that at least a portion used is the FCC catalyzer in a) as step.These products can be recycled and/or join in steps d) in obtain one or more hydrocarbon product in.
In preferred embodiments, cooling and/or rectifying is subsequently in steps d) in one or more hydrocarbon product of obtaining, to produce one or more product cuts, one of described product cut will be one or more C2-C4 alkene.
" alkene " is appreciated that the hydrocarbon compound for having one or more unsaturated link(age)s herein." C2-C4 alkene " is appreciated that herein as having for being equal to or greater than 2 to the alkene that is equal to or less than 4 carbon atoms.Preferably, C2-C4 alkene is to be selected from ethene, propylene, 1-butylene, 2-butylene, divinyl, and alkene in methacrylic.Most preferred alkene is ethene and propylene.
Step f) in, at least a portion is recycled with the FCC catalyzer of regeneration of crossing and is used as FCC catalyzer in step in a).
Advantageously, before the FCC catalyzer of the regeneration of using in riser reactor in a) in step, the FCC catalyzer of regeneration is in steps d) during part inactivation.The implication of " part inactivation " is will to contain than the high coke concentration of FCC catalyzer of regeneration with the FCC catalyzer of the regeneration of crossing.
Use the catalyzer (comprising the catalyzer of part coking) of this part inactivation advantageously to allow people to operate at lesser temps with under compared with low catalyst activity in step in a), make under higher yields, to prepare required product of distillation.
Coke concentration on the FCC catalyzer of regeneration with crossing is greater than the coke concentration on the FCC catalyzer of regeneration, but lower than the coke concentration of the useless FCC catalyzer having separated.Preferably, for being equal to or greater than 0.1wt% to being equal to or less than 1wt%, and be more preferably equal to or greater than 0.1wt% to being equal to or less than 0.6wt% by the coke content in the FCC catalyzer of regeneration of crossing.
Being provided to steps d) amount of FCC catalyzer of the regeneration producing in c) in step of interior intermediate reactor can vary widely, and scope can be to be for example equal to or greater than 1wt% to being equal to or less than 100wt%, the gross weight of FCC catalyzer of the regeneration based on producing in c) in step.More preferably, being provided to steps d) scope of amount of the FCC catalyzer of the regeneration producing in c) in step of interior intermediate reactor can be to be equal to or greater than 10wt%, still be more preferably equal to or greater than 50wt% to being equal to or less than 100wt%, be equal to or less than possibly 90wt%, the gross weight of FCC catalyzer of the regeneration based on producing in c) in step.
For assisted Extraction for step a) in riser reactor processing condition control and/or required product mixtures is provided, the FCC catalyzer of regeneration producing in c) in step can be divided into flow to steps d) intermediate reactor at least first part and flow to a) second section in middle riser reactor of step.In this case, second section preferably includes and is equal to or less than 50wt%, the gross weight of FCC catalyzer of the regeneration based on producing in c) in step.If there is second section, the scope of second section is more preferably equal to or greater than 10wt% to being equal to or less than 50wt%, based on the gross weight of FCC catalyzer producing in c) in step.
The for example product of distillation of one or more hydrocarbon product obtaining in the method for the invention and/or one or more C2-C4 alkene can be advantageously used in produces one or more biofuel components and/or one or more biochemicals components.
For example, C2-C4 alkene produced according to the invention can be advantageously used in production biological polymer, biological example polypropylene and/or biological polyethylene.
Product of distillation produced according to the invention can be advantageously used for biofuel component or it and can experience further processing step and change into biofuel component.
Biofuel component and/or the biochemicals component of producing according to the inventive method will have the carbon-14 isotropic substance of increase level and advantageously more sustainable than their conventional counterpart.
In one embodiment, before being used as biofuel component, at least a portion product of distillation that hydrotreatment is produced in the method for the invention.This hydrotreatment can comprise for example hydrogenating desulfurization, hydrogenation deoxidation, hydrodenitrification and/or hydrogenation.In preferred embodiments, the product of distillation of producing is by hydrogenation deoxidation.
Hydrotreatment (for example hydrogenation deoxidation) is preferably included in hydrotreating catalyst (for example hydrogenation deoxidation catalyst) and is being equal to or greater than 200 DEG C and be preferable over or be greater than 250 DEG C to being equal to or less than 450 DEG C and be preferably equal to or less than at the temperature within the scope of 400 DEG C under existing, be equal to or greater than 1MPa under the total pressure being equal to or less than within the scope of 35MPa, and/or under the hydrogen partial pressure being equal to or less than within the scope of 35MPa, product of distillation contacted with hydrogen being equal to or greater than 0.2MPa.
Any hydrogenation deoxidation catalyst using can be the hydrogenation deoxidation catalyst of any type that is suitable for this purpose well known by persons skilled in the art.Hydrogenation deoxidation catalyst preferably includes support of the catalyst and one or more active elements.This active element can comprise the alloy of element form, one or more these elements or the metal of form of mixtures, for example nickel (Ni), chromium (Cr), molybdenum (Mo), and 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) and vanadium (V).
Preferably, hydrogenation deoxidation catalyst is containing ruthenium, rhenium, and cobalt, nickel, copper, tungsten and/or ruthenium, rhenium, cobalt, nickel, tungsten, and/or the alloy of copper or the catalyzer of mixture, for example, be Rh-Co-and/or Ni-Cu in the support of the catalyst of inertia under reaction conditions.Carrier preferably can comprise refractory oxide or its mixture, preferential oxidation aluminium, and amorphous silicon oxide-aluminum oxide, titanium oxide or silicon oxide, cerium oxide, zirconium white, or it can comprise inert component, for example carbon or silicon carbide or carbon.The carrier of finding inertia is ZrO2, CeO2, CeO2and/or such as CeO of its mixture2-ZrO2, silicon carbide and/or carbon.In some cases, can advantageously use the hydrogenation deoxidation catalyst of sulfuration.If use the hydrogenation deoxidation catalyst of sulfuration, this catalyzer can be on the spot or strange land sulfuration.The in the situation that of vulcanization in situ, in the operating process of hydrogenation deoxidation technique, sulphur source (normally hydrogen sulfide or hydrogen sulphide precursor) is preferably supplied in catalyzer.Most preferred rhodium (the Rh/Al being included on aluminum oxide2o3), the rhodium (Rh/Si0 on silicon oxide2), the rhodium (Rh/ZrO on zirconium white2), the rhodium-cobalt (RhCo/Al on aluminum oxide2o3), the rhodium-cobalt (RhCo/Si0 on silicon oxide2), the rhodium-cobalt (RhCo/ZrO on zirconium white2), the nickel (Ni/Al on aluminum oxide2o3), the nickel (Ni/Si0 on silicon oxide2), the nickel (Ni/ZrO on zirconium white2), the ambrose alloy (NiCu/Al on aluminum oxide2o3), the ambrose alloy (NiCu/Si0 on silicon oxide2), the ambrose alloy (NiCu/ZrO on zirconium white2), the nickel-tungsten (NiW/Al on aluminum oxide2o3), the nickel-tungsten (NiW/Si0 on silicon oxide2), the nickel-tungsten (NiW/ZrO on zirconium white2), the cobalt (Co/Al on aluminum oxide2o3), the cobalt (Co/Si0 on silicon oxide2), the cobalt (Co/ZrO on zirconium white2), the cobalt-molybdenum (CoMo/Si on silicon oxide2o3), the cobalt-molybdenum (CoMo/ZrO on zirconium white2), the cobalt-molybdenum (CoMo/Al on aluminum oxide2o3) hydrogenation deoxidation catalyst.
Can blend biofuel component and/or biochemicals component and one or more other components, to produce biofuel and/or biochemicals.Biofuel component and/or biochemicals the component with it example of one or more other components of blend comprise oxidation inhibitor, corrosion inhibitor, ashless detergent, demisting agent, dyestuff, lubrication modifier and/or mineral fuel component, and comprise gasoline, diesel oil and/or the kerosene(oil)fraction of conventional petroleum derivation.
In this article, " biofuel " and " biochemicals " is appreciated that respectively fuel or the chemical for being derived from least partly renewable energy source.
One embodiment of the invention in Fig. 1, are set forth.In Fig. 1, the FCC raw material (102) of the common raw material of cellulose-containing material and hydrocarbon and steam (104) are introduced in the bottom of the first riser reactor (106).In the bottom of the first riser reactor (106), the FCC catalyzer (108) of FCC raw material (102) and steam (104) and " fresh " regeneration and the FCC catalyzer (110) with the regeneration of mistake mix.In the first reactor riser (106), catalytic pyrolysis FCC raw material (102), to produce containing the distillment of one or more hydrocarbon product and useless FCC catalyzer.The mixture of the FCC raw material of one or more hydrocarbon product, useless FCC catalyzer, steam and any residual non-cracking enters in reactor vessel (112) from the top row of the first riser reactor (106), and described reactor vessel (112) comprises and closely first cyclonic separator (114) of coupling of the second cyclonic separator (116).By the top of the second cyclonic separator (116), reclaim one or more products (118) and optionally advance in rectifier (not shown).Reclaim useless FCC catalyzer from the bottom of cyclonic separator (114 and 116) and advance to stripper (120), falling at this further hydrocarbon product gas from useless FCC catalyzer.
Useless and stripped FCC catalyzer (122) advances in revivifier (124), and at this, useless and stripped FCC catalyzer contact with air (126), the FCC catalyzer (108) that generation is regenerated.The FCC catalyzer (108a) of the regeneration of circulation first part is to the bottom of the first riser reactor (106).Make the FCC catalyzer (108b) of the regeneration of second section advance to the bottom of middle riser reactor (130).In the bottom of middle riser reactor (130), the FCC catalyzer (108b) of the regeneration of second section is contacted with the intermediate reactor feedstock (132) being made up of with the second steam stream (134) gasoline.In middle riser reactor (130), catalytic pyrolysis intermediate reactor feedstock (132), to produce containing one or more hydrocarbon product of C2-C4 alkene with the FCC catalyzer of regeneration of crossing.One or more hydrocarbon product, with the FCC catalyzer, steam of the regeneration of crossing and any residual non--intermediate reactor feedstock of cracking enters in the second reactor vessel (136) from the top row of middle riser reactor (130), described the second reactor vessel (136) comprises and closely first cyclonic separator (138) of coupling of the second cyclonic separator (140).By the top of the second cyclonic separator (140), reclaim one or more products (142), and optionally advance in rectifier (not shown).Reclaim with the FCC catalyzer of the regeneration of crossing from the bottom of cyclonic separator (138 and 140) and advance to stripper (144), stripping from the FCC catalyzer with regeneration excessively at this further hydrocarbon product.Subsequently, the FCC catalyzer of the stripped regeneration with crossing is recycled to the first riser reactor (106) bottom as FCC catalyst stream (110).