CN104011177A

CN104011177A - A Process For Conversion Of A Cellulosic Material

Info

Publication number: CN104011177A
Application number: CN201280061527.4A
Authority: CN
Inventors: A·Q·M·博恩; L·埃斯皮诺萨阿隆索; J·W·高塞林克; J·W·哈里斯; A·H·杨森; J-P·朗格; C·J·斯查沃里恩; N·W·J·威
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2011-11-14
Filing date: 2012-11-14
Publication date: 2014-08-27
Also published as: CA2855584A1; AU2012338868A1; IN2014DN03435A; EP2780433A1; BR112014011506A2; WO2013072391A1; US20130118059A1

Abstract

Provided is a process for conversion of a cellulosic material comprising a liquefaction step, comprising contacting a cellulosic material with a liquid solvent at a temperature of equal to or more than 200 DEG C; or contacting a cellulosic material with a liquid solvent at a temperature of equal to or more than 100 DEG C in the presence of a catalyst, to produce a final liquefied product; a catalytic cracking step, comprising contacting at least part of the final liquefied product with a fluidized catalytic cracking catalyst at a temperature of equal to or more than 400 DEG C, to produce one or more cracked products.

Description

Transform the method for cellulose materials

Technical field

The purposes of the product that the present invention relates to transform the method for cellulose materials and produce in this method.

Background technology

Along with mineral oil supply reduces, use production of renewable energy resources liquid fuel to become more and more important.These fuel that are derived from renewable energy source are commonly referred to biofuel.

Due to not with foodstuff production competition, be preferred by edible renewable energy source biofuel as derivative in cellulose materials not.These biofuels are also referred to as the s-generation or senior biofuel.But these unedible cellulose materialss of great majority are solid materials, and they are difficult to be converted into biofuel.

WO2010/135734 has described the method for co-processing biomass material and refinery's raw material in refinery's device, described method is included in catalytic cracking biomass material and refinery's raw material in the refinery's device that comprises fluidized reactor, and wherein hydrogen is transferred to carbon and the oxygen of biomass material from refinery's raw material.In an embodiment of WO2010/135734, biomass material comprises that mean particle size is multiple solid biomass particles of 50-1000 micron.Wherein further mentioning can be by solid biomass particles pre-treatment, to increase fragility, to be easy to catalyzed conversion (for example, by baking, toast and/or curing) and/or to be easy to mix with petrochemical material.

But the shortcoming of the method for describing in WO2010/135734 is that, for fear of feeding line and/or the coking in fluidized catalytic cracker of unstable, the choked flow fluidized catalytic cracking unit of raw material, it is very crucial suitably processing containing the biomass material of solid biomass particles.

The people such as F.de Miguel Mercader are published in Journal of Applied Catalysis B:Environmental, 2010, volume96, the method for the high temperature pyrolysis oil of the hydrogenation deoxidation that catalytic cracking is derived by forestry resistates together with long residuum in catalyst cracker described in the article of pages57-66.Although described method has obtained good result, what show is that hydrogenation deoxidation reaction produces good product (for fluid catalytic cracking (FCC) co-processing) in the situation that consuming hydrogen.In addition, what show is in hydrogenation deoxidation process, is adapted at the further thermally-stabilised molecule of processing in FCC apparatus in order to obtain, and reaction conditions is very crucial.Fig. 9 of article has further described the competitive relation between hydrogenation (deoxidation) and (again) polymerization of high temperature pyrolysis oil.As what explain in article, rapid polymerization reaction can cause reactor plugs.

Therefore, provide a kind of method of not too dangerous conversion cellulose materials by the progress that is this area.

Summary of the invention

The inventive method has realized this progress.Therefore, the invention provides a kind of method that transforms cellulose materials, described method comprises:

A) liquefaction step, described liquefaction step is included in and at the temperature that is more than or equal to 200 DEG C, cellulose materials is contacted with liquid solvent or under catalyzer exists, be more than or equal at the temperature of 100 DEG C cellulose materials is contacted with liquid solvent, to produce final liquiefied product;

B) catalytic cracking step, described catalytic cracking step is included at the temperature that is more than or equal to 400 DEG C at least partly final liquiefied product is contacted with fluidized catalytic cracking catalyst, to produce one or more cracked product.

Do not wish to be limited to by any kind of theory, it is believed that final liquiefied product is because its composition is than pyrolysis oil and/or the more stable fluidized catalytic cracking method raw material of any solid biomass particles.

Have been found that in addition and can make in the method for the invention coking minimize.

Therefore the inventive method provides a kind of not too method of dangerous conversion cellulose materials.

One or more cracked product advantageously can be carried out to fractionation to produce one or more product cuts and optionally to carry out hydrotreatment to produce one or more product cuts through hydrotreatment.These one or more product cuts and/or one or more one or more products that derive through the product cut of hydrotreatment and/or by their can be advantageously used for biofuel component.Therefore the present invention also provides a kind of method for the production of biofuel, and described method comprises makes these biofuel components and one or more other component blending to produce biofuel.The biofuel producing can be advantageously used in carrier vehicle.

Embodiment

In liquefaction step, cellulose materials contacts with liquid solvent and produces final liquiefied product.This step also can be called cellulose materials liquefaction here.Liquefaction can be implemented by liquefaction reaction.

Liquefaction is understood to solid material to be converted into one or more liquiefied products as cellulose materials here.

Liquiefied product is understood to be in 20 DEG C of temperature here and pressure 1bar absolute pressure (0.1MPa) is lower for the product of liquid and/or by melting (for example, by using heat) or being dissolved in the product that can be converted into liquid in solvent.Liquiefied product is preferably at 80 DEG C of temperature and the lower liquiefied product for liquid of pressure 1bar absolute pressure (0.1MPa).The viscosity of liquiefied product can change and can be more tacky or not too sticky in wide range.

The liquefaction of cellulose materials can comprise the covalent linkage disconnecting in cellulose materials.The liquefaction of for example lignocellulose can comprise the covalent linkage disconnecting between covalent linkage and/or disconnection xylogen, hemicellulose and/or the Mierocrystalline cellulose existing in Mierocrystalline cellulose, hemicellulose and/or xylogen.

As applying here, cellulose materials refers to the material of cellulose.Cellulose materials is preferably lignocellulose.Lignocellulose comprises xylogen, Mierocrystalline cellulose and optional hemicellulose.

Liquefaction step advantageously makes not only liquified cellulosic become into energy, also makes liquefied wood quality and hemicellulose become possibility.

The material of any suitable cellulose can be as the cellulose materials in the inventive method.Can be obtained by the various plants or the vegetable material that comprise agricultural waste, forestry waste, sugared residual processing thing and/or their mixture for cellulose materials of the present invention.The example of suitable cellulose-containing material comprises: agricultural waste are if maize straw, soybean stalk, corn cob, straw, rice husk, oat shell, zein fiber, grain straw are as straw, Barley straw, rye stalk and/or oat straw; Grass; Forestry products is if timber and timber associated materials are as sawdust; Waste paper; Sugar residual processing thing is as bagasse, beet pulp; Or their mixture.

Dry, baking, steam explosion, the grain graininess that step a) may further include before cellulose materials contacts with liquid solvent cellulose materials reduces, densification and/or granulation.Dry, the baking of described cellulose materials, steam explosion, grain graininess reduce, densification and/or granulation can advantageously improve method operability and economy.

Before for the inventive method, preferably cellulose materials is treated to small-particle to promote liquefaction.Preferably, the average grain granularity that cellulose materials is treated to particle size distribution be more than or equal to 0.05 millimeter, more preferably greater than or equal 0.1 millimeter, be most preferably more than or equal to 0.5 millimeter and be preferably less than or equal to 20 centimetres, be more preferably less than or equal 10 centimetres and be most preferably less than or equal to the particle of 3 centimetres.For the object of implementing, centimetre and the grain graininess of millimeter in scope can determine by screening.

If cellulose materials is ligno-cellulosic materials, it also can stand pre-treatment to remove and/or lignin degrading and/or hemicellulose.This pretreated example comprises rectifying, slurrying and cures process.

Liquid solvent is here preferably interpreted as at pressure 1bar normal atmosphere (0.1MPa) and 80 DEG C of temperature or higher, more preferably 100 DEG C or solvent that more relative superiority or inferiority is liquid.Most preferably, liquid solvent is understood to be in the solvent for liquid under the temperature and pressure of implementing liquefaction step here.

In preferred embodiments, liquid solvent is water or comprises water.

In another preferred embodiment, liquid solvent is organic solvent or comprises organic solvent.Organic solvent is understood to the solvent containing one or more hydrocarbon compounds here.Hydrocarbon compound is understood to the compound that comprises at least one hydrogen atom and at least one carbon atom here, more preferably, hydrocarbon compound is here understood to containing at least one hydrogen atom being connected by least one covalent linkage each other and at least one carbon atom.

Except hydrogen and carbon, described hydrocarbon compound for example can comprise heteroatoms as sulphur, oxygen and/or nitrogen.The example of the hydrocarbon compound that can preferably exist in organic solvent comprises acetic acid, formic acid, levulinic acid and γ-valerolactone and/or their mixture.

Organic solvent can comprise polarity and/or non-polar hydrocarbon compound.In preferred embodiments, organic solvent comprises at least one or various polarity hydrocarbon compound.Preferably, organic solvent comprise be greater than one, more preferably greater than two kinds, more preferably greater than three kinds of dissimilar polarity hydrocarbon compounds.The tolerance of nonpolar hydrocarbon compound polarity is its log P value, and wherein P is defined as the partition ratio of compound in two-phase octanol-water system.Log P value can be by Handbook of Chemistry and Physics, 83 ^rdedition, pages16-43-16-47, the standard program of discussing in CRC Press (2002) experiment is determined or is calculated.

In one embodiment, organic solvent can preferably comprise one or more nonpolar hydrocarbon compounds, and wherein said one or more nonpolar hydrocarbon compounds are preferably its polarity logP and are less than+3, be more preferably less than+1 hydrocarbon compound.In another embodiment, nonpolar hydrocarbon compound is be less than+0.5 hydrocarbon compound of its polarity log P.In another embodiment, nonpolar hydrocarbon compound is the hydrocarbon compound that its polarity log P is less than 0.

In another embodiment, organic solvent can preferably comprise one or more non-polar hydrocarbon compounds, and it is+5 to+10, more preferably+7 to+8 hydrocarbon compound that wherein said one or more non-polar hydrocarbon compounds are preferably its polarity logP.

In preferred embodiments, organic solvent comprises one or more carboxylic acids.Carboxylic acid is understood to the hydrocarbon compound containing at least one carboxyl (CO-OH) here.This carboxylic acid can be nonpolar hydrocarbon compound mentioned above.More preferably, taking the gross weight of organic solvent as benchmark, organic solvent comprises the carboxylic acid that is more than or equal to 5wt%, more preferably greater than or equal the carboxylic acid of 10wt%, be most preferably more than or equal to the carboxylic acid of 20wt%.There is no the upper limit for carboxylic acid concentration, but for actual purpose, taking the gross weight of organic solvent as benchmark, organic solvent can comprise the carboxylic acid that is less than or equal to 90wt%, is more preferably less than or equals 80wt%.Organic solvent preferably at least comprises acetic acid, levulinic acid and/or valeric acid.Acetic acid may be useful especially, because it can be used as (part) organic solvent and acid catalyst simultaneously.

In another embodiment, organic solvent comprises alkanisation compound, naphthenic compound, olefinic compounds and/or aromatic compound.These compounds can exist in as gas oil, oil fuel and/or residual oil at refinery logistics.Therefore these refinery logistics can be also organic solvents suitable in liquefaction step.This will make an explanation hereinafter in more detail.

In another preferred embodiment, organic solvent comprises at least part of liquiefied product.Therefore partial liquefaction product (for example, in the middle of the final liquiefied product of part of describing hereinafter and/or part liquiefied product) preferred cycle to liquefaction step is used as organic solvent.In preferred embodiments, be more than or equal to 10wt%, more preferably greater than or the organic solvent that equals 20wt% obtained by middle and/or final liquiefied product.

In preferred embodiments, the liquiefied product weight that the circulation of any liquiefied product comprises is 2-100 times of cellulose materials weight, and more preferably the 5-20 of cellulose materials weight doubly.

In preferred embodiments, organic solvent is derivative by cellulose materials and preferred ligno-cellulosic materials at least partly.For example, in preferred embodiments, organic solvent can produce at cellulose materials liquefaction process situ at least partly.More preferably, organic solvent is obtained by cellulose materials and preferred ligno-cellulosic materials acidolysis at least partly.Can comprise acetic acid, formic acid and levulinic acid by the example of hydrocarbon compound possible in the organic solvent of cellulose materials and preferably ligno-cellulosic materials acidolysis acquisition.Also can apply suitably the hydrocarbon compound being obtained by described acidolysis hydrogenation of net product.The example of this hydrocarbon compound through hydrogenation comprises the γ-valerolactone that can obtain by levulinic acid hydrogenation, by furfural or the derivative tetrahydrofurfuryl of hydroxymethylfurfural and THP trtrahydropyranyl component, the list-and two-ol and ketone and the o-hydroxyanisole being derived by xylogen and syringol component that derived by sugar.Organic solvent preferably can comprise one, hydrocarbon compound described in two or more.In addition, above-claimed cpd also can become the final liquiefied product of part.Therefore, in preferred embodiments, that final liquiefied product or its part can comprise is a kind of, two or more are as listed above optional through hydrogenation compound, as the γ-valerolactone that can be obtained by levulinic acid hydrogenation, can be by furfural or the derivative tetrahydrofurfuryl of hydroxymethylfurfural and THP trtrahydropyranyl component, list-and/or two-ol and/or single-and/or two-one and/or the o-hydroxyanisole that can be derived by xylogen and syringol component that can be derived by sugar.

One or more hydrocarbon compounds in organic solvent can advantageously be obtained by cellulose materials liquefaction in liquefaction step.For example original position of described hydrocarbon compound produces and/or circulates and/or as supplementing organic solvent, significant economy be provided and process advantage.

In one embodiment, in liquefaction step, organic solvent does not produce by transforming cellulose materials original position at least partly.The organic solvent that this ex situ provides can coexist with the organic solvent that original position forms.Therefore not that original position produces but this solvent that ex situ provides is also known as " solubility promoter " here.

In preferred embodiments, organic solvent comprises at least one or hydrocarbons compound, and described hydrocarbon compound is at least partly by being used as in liquefaction step that for example petroleum source of source (here also referred to as fossil origin) beyond the cellulose materials of raw material obtains and/or derivative.Described one or more hydrocarbon compounds can be for example mix with cellulose materials or join in reaction mixture in liquefaction process before liquefaction starting.

As below explaining in more detail, in one embodiment, the organic solvent in liquefaction step comprises and is also adapted at being used as in catalytic cracking step one or more co-fed hydrocarbon compounds of fluid hydrocarbon.In another embodiment, the organic solvent of applying in liquefaction step comprises one or more hydrocarbon compounds that obtained by conventional crude (sometimes also referred to as oil or mineral oil), non-conventional crude oil (applying the technology extraction of non-traditional oil well method or the oil of extraction), renewable origin (as vegetables oil) or fischer-tropsch oil and/or their mixture.More preferably, the organic solvent of applying in liquefaction step comprises or by oil or renewable oils fractions consisting.Organic solvent preferably includes or by straight run (normal pressure) gas oil, flash distillation overhead product, vacuum gas oil (VGO), light cycle oil, heavy cycle oil, hydrogenation wax, coker gas oil, diesel oil, gasoline, kerosene, petroleum naphtha, liquefied petroleum gas (LPG), long residuum (" long residuum ") and vacuum resid (" vacuum residuum ") and/or their compositions of mixtures.Organic solvent most preferably comprises or is made up of long residuum.

Therefore the solubility promoter of mentioning, is preferably and comprises or by the organic solvent of oil or its fractions consisting.The advantage that application oil or its cut are made organic solvent or organic cosolvent is that this organic solvent or solubility promoter may be also the suitable feedstock of catalytic cracking step.When organic solvent or organic cosolvent comprises or during for oil or its cut, because may not need to separate this organic solvent or organic cosolvent, may cause more effectively and more cheap operation and hardware.

In preferred embodiments, therefore the present invention also provides a kind of method that transforms cellulose materials, and described method comprises:

A) liquefaction step, described liquefaction step is included under catalyzer existence and at the temperature that is more than or equal to 100 DEG C, cellulose materials is contacted with liquid solvent, and to produce final liquiefied product, wherein said organic solvent comprises petroleum fractions;

B) catalytic cracking step, described catalytic cracking step is included at the temperature that is more than or equal to 400 DEG C and in fluid catalytic cracking reactor, makes the mixture of at least partly final liquiefied product and petroleum fractions contact with fluidized catalytic cracking catalyst, to produce one or more cracked product.Those skilled in the art will be understood that the liquiefied product during step b) can become final liquiefied product or its any part suitably.

Petroleum fractions is preferably selected from straight run as above (normal pressure) gas oil, flash distillation overhead product, vacuum gas oil (VGO), light cycle oil, heavy cycle oil, hydrogenation wax, coker gas oil, diesel oil, gasoline, kerosene, petroleum naphtha, liquefied petroleum gas (LPG), long residuum (" long residuum ") and vacuum resid (" vacuum residuum ") and/or their mixture.At least part of this petroleum fractions or whole this petroleum fractions can contact with fluidized catalytic cracking catalyst in b) in step.

In preferred embodiments, liquefaction step is included at the temperature that is more than or equal to 150 DEG C cellulose materials is contacted with petroleum fractions, hydrogen source, hydrogenation catalyst and optional acid catalyst simultaneously, to produce final liquiefied product.

Other is preferably by described in this paper other parts.

In one embodiment, organic solvent part derived from cellulose materials, preferably ligno-cellulosic materials and part derived from petroleum source.In preferred embodiments, organic solvent comprises following mixture: i) petroleum fractions and ii) can be by one or more hydrocarbon compounds of acidolysis cellulose materials, preferred ligno-cellulosic materials acquisition.

In preferred embodiments, organic solvent comprises that at least one or multiple carboxylic acid are as acidic acid, levulinic acid and/or valeric acid, wherein said carboxylic acid preferably just exists before beginning liquefaction reaction, that is to say, described carboxylic acid is not preferably in the acquisition of reaction situ and/or derived from cellulose materials.

Advantageously, organic solvent can be miscible with water under the temperature of reaction of liquefaction step.In preferred embodiments, liquefaction step comprises cellulose materials is contacted with the solvent mixture that comprises organic solvent and water.Therefore, in preferred embodiments, liquid solvent can comprise moisture and solvent mixture organic solvent.

Water in solvent mixture can for example produce at liquefaction step situ.Taking the gross weight of water and organic solvent as benchmark, the amount of organic solvent is preferably and is less than or equal to 95wt%, is more preferably less than or equals 90wt%, and being most preferably less than or equal to 80wt%.In addition, taking the gross weight of water and organic solvent as benchmark, the amount of organic solvent is preferably more than or equals 5wt%, more preferably greater than or equal 10wt%, and be most preferably more than or equal to 20wt%.Taking the gross weight of water and organic solvent as benchmark, the amount of organic solvent is preferably 20-60wt%.

Taking the gross weight of water and organic solvent as benchmark, the amount of water is preferably and is less than or equal to 95wt%, is more preferably less than or equals 90wt%, and being most preferably less than or equal to 80wt%.In addition, taking the gross weight of water and organic solvent as benchmark, the amount of water is preferably more than or equals 5wt%, more preferably greater than or equal 10wt%, most preferably be 20wt%.Taking the gross weight of water and organic solvent as benchmark, the amount of water is preferably 40-80wt%.Solvent mixture is preferably less than or equal to 9:1, is more preferably less than or equals 8:2 with the weight ratio of organic solvent and water and contains organic solvent and water.Solvent mixture more preferably with the weight ratio of organic solvent and water be more than or equal to 1:9, more preferably greater than or equal 2:8 and contain organic solvent and water.

If cellulose materials and organic solvent or comprise water and solvent mixture when the solvent mixture of organic solvent exists preferably mixes as the weight ratio of 3:1-15:1 and most preferred solvent mixture or organic solvent and cellulose materials as 4:1-10:1 with the weight ratio of cellulose materials taking the weight ratio of solvent mixture or organic solvent and cellulose materials as 2:1-20:1, more preferably solvent mixture or organic solvent.

Liquefaction step can or not exist under catalyzer in existence and implements.Applications catalyst advantageously allows people to reduce temperature of reaction.

Therefore, in one embodiment, liquefaction step can comprise optional under the acid catalyst that does not substantially exist outside to provide, temperature be more than or equal to 200 DEG C, more preferably greater than or equal 250 DEG C, still more preferably temperature be more than or equal to 300 DEG C and preferably temperature be less than or equal at 450 DEG C, cellulose materials is contacted with organic solvent.

In another embodiment, liquefaction step can be included under catalyzer, preferred acid existence, be more than or equal to 100 DEG C in temperature, more preferably temperature is more than or equal to 150 DEG C, still more preferably temperature is more than or equal to 200 DEG C and preferably temperature is less than or equal to 450 DEG C, more preferably temperature is less than or equal at 350 DEG C, and cellulose materials is contacted with organic solvent.

Catalyzer is preferably acid catalyst.Any acid catalyst that is suitable for liquefied fiber cellulosic material that can be known in the art for the acid catalyst of liquefaction step of the present invention.For example, acid catalyst can be acid or Lewis acid.Acid catalyst can be further homogeneous catalyst or heterogeneous catalyst.Acid catalyst is preferably the heterogeneous catalyst of homogeneous phase or careful dispersion, and acid catalyst most preferably is homogeneous catalyst.Acid catalyst preferably keeps liquid phase with stable under liquefaction condition, and preferably enough strong so that cellulose materials covalent linkage ruptures and cellulose materials is dewatered.

Acid catalyst is preferably acid and more preferably inorganic or organic acid, inorganic or organic acid preferably has the pKa lower than 5.0, more preferably less than 4.25, still more preferably less than 3.75, even more preferably less than 3.0, and most preferably lower than 2.5.

The example of suitable mineral acid comprises sulfuric acid, tosic acid, nitric acid, hydrochloric acid and phosphoric acid and their mixture.In preferred embodiments, the acid catalyst of applying in liquefaction step is sulfuric acid or phosphoric acid.

The suitable organic acid example that can apply in liquefaction step comprises levulinic acid, acetic acid, oxalic acid, formic acid, lactic acid, citric acid, trichoroacetic acid(TCA) and their mixture.If acid catalyst is organic acid, position that it can produce for original position suitably or non-produces the organic acid of (being that outside provides).The organic acid that original position produces is understood to be in the organic catalyst that cellulose materials liquefaction process situ produces here.The organic acid example that this original position produces can be acetic acid or formic acid.

If in organic solvent or the solvent mixture of application and the gross weight of acid catalyst, the amount of acid catalyst is preferably and is less than or equal to 35wt%, be more preferably less than or equal 20wt%, even be more preferably less than or equal 10wt%, still be more preferably less than or equal 5wt%, and being most preferably less than or equal to 1wt%.In addition, if in organic solvent or the solvent mixture of application and the gross weight of acid catalyst, the amount of acid catalyst is preferably more than or equals 0.01wt%, more preferably greater than or equal 0.1wt%, and be most preferably more than or equal to 0.2wt%.Will be understood that for given acid catalyst, required acid amount will be decided by sour intensity.In preferred embodiments, if in organic solvent or the solvent mixture of application and the gross weight of acid catalyst, the amount of acid catalyst is 1-10wt%, preferably 2-5wt%.

In preferred embodiments, make the rear at least part of liquiefied product hydrogenation obtaining of cellulose materials liquefaction.Liquefaction and hydrogenation can be implemented simultaneously or hydrogenation can liquefaction after enforcement.

In one embodiment, liquefaction step is included under acid catalyst existence and at the temperature that is more than or equal to 150 DEG C, cellulose materials is contacted with organic solvent, with liquiefied product in the middle of producing; Under existing, hydrotreating catalyst uses subsequently the middle liquiefied product of hydrogen source hydrotreatment, to produce final liquiefied product.In the middle of the hydrotreatment of middle liquiefied product preferably includes, hydrogenation and the described hydrotreating catalyst of liquiefied product are preferably hydrogenation catalyst.

In another embodiment, liquefaction step is included at the temperature that is more than or equal to 150 DEG C cellulose materials is contacted with organic solvent, hydrogen source, acid catalyst and hydrogenation catalyst simultaneously, to produce final liquiefied product.In this case, liquefaction step can advantageously comprise cellulose materials is hydrolyzed and hydrogenation simultaneously, causes Degree of Liquefaction to improve.Contact is simultaneously understood to be in the contact under residue character existence with the cellulose materials of one of regulation feature.By this way, can make cellulose materials be hydrolyzed and hydrogenation, because any hydrolysis prods all can original position hydrogenation simultaneously.

Hydrogenation catalyst is preferably tolerance organic solvent (if or solvent mixture of application) and if the hydrogenation catalyst of the combination of the acid catalyst existing.

For example, hydrogenation catalyst can comprise heterogeneous and/or homogeneous catalyst.In preferred embodiments, hydrogenation catalyst is homogeneous catalyst.In another preferred embodiment, hydrogenation catalyst is heterogeneous catalyst.Hydrogenation catalyst preferably includes the known hydrogenation metal that is suitable for hydrogenation reaction, as iron, molybdenum, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium, platinum and gold or their mixture.The hydrogenation catalyst that comprises this hydrogenation metal can cure.In another embodiment, the hydrogenation catalyst of sulfuration can be applied as the catalyzer based on moly-sulfide, cobalt and/or nickel can be comprised as promotor.

If hydrogenation catalyst is heterogeneous catalyst, described catalyzer preferably is contained in the hydrogenation metal of carrier band on carrier.Suitable carrier comprises for example carbon, aluminum oxide, titanium dioxide, zirconium dioxide, silicon-dioxide and their mixture.The example of preferred heterogeneous hydrogenation catalyst is included in ruthenium, platinum or the palladium of carrier band on carbon support.Other preferred example of heterogeneous hydrogenation catalyst is included in titanium dioxide (TiO ₂) upper carrier band ruthenium, on titanium dioxide carrier band platinum and at zirconium dioxide (ZrO ₂) ruthenium of upper carrier band.Heterogeneous catalyst and/or carrier can have any suitable form, comprise that the form of mesoporous powder, particle or extrudate or macroporous structure are as foam, honeycomb, mesh or fabric.Heterogeneous catalyst can exist in the liquefying reactor that comprises fixed bed or boiling slurries.Heterogeneous catalyst preferably exists in the liquefying reactor of fixed bed form.

If hydrogenation catalyst is homogeneous hydrogenation catalyzer, catalyzer preferably comprises the organic or inorganic salt of hydrogenation metal, as the acetate of ruthenium, platinum or palladium, acetyl pyruvate, nitrate, vitriol or muriate.Homogeneous catalyst is preferably the organic or inorganic hydrochlorate of hydrogenation metal, and wherein said acid is the acid having existed as acid catalyst or product in method.

Hydrogen source can be the known any hydrogen source that is suitable for hydrogenation object.For example, it can comprise hydrogen, also can comprise that hydrogen donor is as formic acid.Preferred hydrogen source is hydrogen.Described hydrogen can with preferred 2-200 bar absolute pressure (0.1-20 MPa), more preferably 10-170 bar absolute pressure (1-17 MPa) and most preferably the hydrogen dividing potential drop of 30-150 bar absolute pressure (3-15 MPa) apply in the methods of the invention.Can be by hydrogen to offer liquefying reactor with the mode of cellulose materials stream, cross-flow or adverse current.Hydrogen is preferably to provide with the mode of cellulose materials adverse current.

Can under the known any stagnation pressure that is suitable for liquifying method, implement liquefaction step.Described method can be in preferred 2-200 bar absolute pressure (0.1-20 MPa), more preferably 10-170 bar absolute pressure (1-17MPa) and most preferably implementing under the stagnation pressure of 30-150bar absolute pressure (3-15MPa).

Liquifying method of the present invention can be intermittently, semi-batch and implementing continuously.

In liquefaction step, make cellulose materials liquefaction, be converted into one or more liquiefied products by cellulose materials, to produce final liquiefied product.

Final liquiefied product is understood to prepare to enter the liquiefied product of catalytic cracking step here.Final liquiefied product can be by hydrogenation (as below explaining) or not by hydrogenation.In addition, final liquiefied product can be separated from reaction effluent or do not separate.Preferably, make final liquiefied product hydrogenation and/or obtain through one or many after separating as described below.

The reaction effluent that liquefaction step produces can comprise that so-called soil ulmin, liquiefied product and for example water, solubility promoter, acid catalyst and/or hydrogenation catalyst and/or gas products are as hydrogen.In preferred embodiments, step a) may further include the reaction effluent producing from liquefaction step and separates final liquiefied product.

Soil ulmin is understood to the rear insoluble material of remaining solid of liquefaction.Sometimes be also known as coke.

Liquiefied product can be included in the monomer and/or oligomeric compound and the optional excessive water that in liquifying method, produce.Can separate the product containing monomer and oligomeric compound by liquiefied product.In addition, can be by partial liquefaction product separation out to loop back liquefaction step as organic solvent.

Reaction effluent preferably enters disengaging zone.In disengaging zone, can from reaction effluent, isolate insoluble soil ulmin, monomer and/or oligomeric compound and/or water, solubility promoter and/or acid catalyst.

In one embodiment, can from reaction effluent, isolate soil ulmin in the known mode that is suitable for this object.Preferably by filtering or settlement separate this soil ulmin.Any soil ulmin forming in liquefaction step all can be converted into diesel oil, kerosene and gasoline fraction in the refining step of the catalytic cracking step of the inventive method or other routine.

In another embodiment, in the known mode that is suitable for this object, liquiefied product and/or any solubility promoter are separated from reaction effluent.Preferably by liquid/liquid isolation technique as being separated, (solvent) extraction and/or membrane filtration or (vacuum) rectifying separates liquiefied product and/or any solubility promoter.

If need, can apply easily one or more films monomer product and low dimerization product are separated from each other.For example,, for example, by ceramic membrane (TiO ₂film) or polymeric membrane (for example Koch MPF34 (plain film) or Koch MPS-34 (spiral winding) film) can be by monomeric compound and/or optional water and any C ₉-C ₂₀oligomeric compound and C ₂₀+ oligomeric compound separates.C ₉-C ₂₀oligopolymer and C ₂₀+ oligopolymer can be used for example polymer graft ZrO easily ₂film is separated from each other.Separate for these, application film can advantageously improve the energy efficiency of method.

In another embodiment, remove by rectifying, pervaporation and/or reverse osmosis the excessive water producing in liquefaction step.

In preferred embodiments, incite somebody to action at least partly water, solubility promoter, acid catalyst and/or hydrogenation catalyst arbitrarily and advantageously reclaim, be reused in liquefaction step to circulate.In another preferred embodiment, this strand of recycle stream also comprises at least partly monomeric compound and/or low dimerization product arbitrarily.Preferably discharge excessive water, solubility promoter, acid catalyst, hydrogenation catalyst and/or monomeric compound arbitrarily by effluent streams.In liquefaction step, preferably greater than or equal to 50wt%, more preferably greater than or equal 60wt% and be most preferably more than or equal to the cellulose materials of 70wt% can be to be advantageously liquefied as liquiefied product being preferably less than in 3 hours.

When solubility promoter is organic cosolvent during as oil or petroleum fractions, maybe advantageously do not circulate solubility promoter but by solubility promoter together with final liquiefied product co-fed enter catalytic cracking step.If comprising, liquefaction step makes one or more liquiefied product hydrogenation, also hydrogenation suitably of oil or petroleum fractions.In catalytic cracking step, this may be favourable.

Described catalytic cracking step is included at the temperature that is more than or equal to 400 DEG C at least partly final liquiefied product is contacted with fluidized catalytic cracking catalyst, to produce one or more cracked product.

In one embodiment, final liquiefied product or its part can comprise and be selected from following one, two or more compounds: γ-valerolactone and/or levulinic acid; Tetrahydrofurfuryl and/or THP trtrahydropyranyl; Furfural and/or hydroxymethylfurfural; Single-and/or two-ol and/or single-and/or two-one; And/or o-hydroxyanisole and/or syringol component.

In another embodiment, final liquiefied product or its part are the cut of the reaction effluent that obtained by liquefaction step, it comprise or substantially by one or more containing being less than or equal to 9 carbon atoms, preferably the compound that is less than or equal to 6 carbon atoms and is most preferably less than or equal to the preferred monomers of 5 carbon atoms forms.In this embodiment, final liquiefied product more preferably comprise one or more containing be less than or equal to 9 carbon atoms, be preferably less than or equal to 6 carbon atoms and be most preferably less than or equal to 5 carbon atoms and/or molecular weight is less than or equal to 200 dalton and/or under 0.1MPa definite atmospheric boiling point be less than or equal to the compound of 200 DEG C.

This final liquiefied product preferably includes hydrocarbon compound and/or oxygenatedchemicals as alcohol.For example this final liquiefied product can comprise or can by the list derived from sugared-and/or two-ol and/or single-and/or two-one form.This final liquiefied product more preferably contains the final liquiefied product of butanone, butanols and/or furfural.

In another embodiment, final liquiefied product or its part are the cut of the reaction effluent that obtained by liquefaction step, it comprise or substantially by one or more containing being more than or equal to 9 carbon atoms, forming preferably greater than or equal to 10 carbon atoms and the compound that is most preferably more than or equal to the preferred monomers of 11 carbon atoms.In this embodiment, final liquiefied product more preferably comprise one or more containing be more than or equal to 9 carbon atoms, preferably greater than or equal to 10 carbon atoms and be most preferably more than or equal to 11 carbon atoms and/or molecular weight is more than or equal to 200 dalton and/or under 0.1MPa definite atmospheric boiling point be more than or equal to the compound of 200 DEG C.

Final liquiefied product or its part can be by above-mentioned generations.Can optionally after above-mentioned separating step, obtain until the final liquiefied product contacting with fluidized catalytic cracking catalyst or its any part.Final liquiefied product or its part can enter fluid catalytic cracking reactor with substantially liquid, basic gaseous state or operative liquid-part gaseous state.In the time entering fluid catalytic cracking reactor with basic or operative liquid, the preferably evaporation in the time entering of final liquiefied product or its any part, and preferably contacts with fluidized catalytic cracking catalyst with gaseous form.

In preferred embodiments, catalytic cracking step is included at the temperature that is more than or equal to 400 DEG C and preferably in fluid catalytic cracking reactor, makes at least partly final liquiefied product contact with fluidized catalytic cracking catalyst with fluid hydrocarbon is co-fed, to produce one or more cracked product.That is to say, in preferred embodiments, can in fluid catalytic cracking reactor, also add the fluid hydrocarbon except at least partly final liquiefied product co-fed.

Hydrocarbon is co-fed is understood to co-fed containing one or more hydrocarbon compounds here.The co-fed hydrocarbon charging that is understood to non-solid-state form here of fluid hydrocarbon.Fluid hydrocarbon is co-fed is preferably that liquid hydrocarbon is co-fed, hydrocarbon gas is co-fed or their mixture.Fluid hydrocarbon co-fed can with substantially liquid, basic gaseous state or or operative liquid-part gaseous feed to catalyst cracker.In the time entering catalyst cracker with basic or operative liquid, the co-fed preferably evaporation in the time entering of fluid hydrocarbon, and preferably contacts with fluidized catalytic cracking catalyst with gaseous state.

Fluid hydrocarbon is co-fed can for known being suitable for of those skilled in the art, to make the co-fed any non-solid hydrocarbons of catalytic cracking unit co-fed.Fluid hydrocarbon is co-fed for example can be obtained by conventional crude (sometimes also referred to as oil or mineral oil), non-conventional crude oil (applying the technology extraction of non-traditional oil well method or the oil of extraction) or fischer-tropsch oil and/or their mixture.

Fluid hydrocarbon is co-fed can be even as co-fed in the fluid hydrocarbon of vegetables oil from renewable origin.

In one embodiment, fluid hydrocarbon is co-fed derived from preferably conventional crude oil.The example of conventional crude 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.

Co-fed preferred conventional crude or the renewable oil fraction of more preferably comprising of fluid hydrocarbon.Preferred co-fed straight run (normal pressure) gas oil, flash distillation overhead product, vacuum gas oil (VGO), light cycle oil, heavy cycle oil, hydrogenation wax, coker gas oil, diesel oil, gasoline, kerosene, petroleum naphtha, liquefied petroleum gas (LPG), long residuum (" long residuum ") and vacuum resid (" vacuum residuum ") and/or their mixture of comprising of fluid hydrocarbon.The co-fed long residuum that most preferably comprises of fluid hydrocarbon.

The co-fed composition of fluid hydrocarbon can change in wide range.Fluid hydrocarbon is co-fed can for example comprise paraffinic hydrocarbons, alkene and aromatic hydrocarbons.

Co-fed in total fluid hydrocarbon, the co-fed paraffinic hydrocarbons that is more than or equal to 1wt% that preferably comprises of fluid hydrocarbon, more preferably greater than or equal the paraffinic hydrocarbons of 5wt%, most preferably be more than or equal to the paraffinic hydrocarbons of 10wt%, preferably be less than or equal to the paraffinic hydrocarbons of 100wt%, be more preferably less than or equal the paraffinic hydrocarbons of 90wt%, and be most preferably less than or equal to the paraffinic hydrocarbons of 30wt%.That paraffinic hydrocarbons is understood to is n-, ring-and branching-paraffinic hydrocarbons.

In preferred embodiments, fluid hydrocarbon is co-fed comprised or by paraffinic hydrocarbons fluid hydrocarbon co-fed composition.Paraffinic hydrocarbons fluid hydrocarbon is co-fed is understood to the gross weight co-fed in fluid hydrocarbon here, containing 50wt% paraffinic hydrocarbons at least, preferably at least 70wt% paraffinic hydrocarbons fluid hydrocarbon is co-fed.For actual purpose, initial boiling point is that the ASTM method D2007-03 that the co-fed paraffinicity of whole fluid hydrocarbon of at least 260 DEG C can be " Standard test method for characteristic groups in rubber extender and processing oils and other petroleum-derived oils by clay-gel absorption chromatographic method " by title measures, and wherein the amount of saturates will represent paraffinicity.Co-fed for all other fluid hydrocarbon, the co-fed paraffinicity of fluid hydrocarbon can be measured by comprehensive multidimensional gas chromatographic (GCxGC), as P.J.Schoenmakers, J.L.M.M.Oomen, J.Blomberg, W.Genuit, G.van Velzen, J.Chromatogr.A, 892 (2000) p.29 and later.

The co-fed example of paraffinic hydrocarbons fluid hydrocarbon comprises so-called Fisher-Tropsch derived hydrocarbon stream, here quote as a reference, or rich hydrogen raw material is as hydrotreater product or hydrogenation wax described at WO2007/090884 with the document.Hydrogenation wax is understood to the bottom fraction of hydrocracker.The example that can produce the method for hydrogen cracking that can be used as the co-fed bottom fraction of fluid hydrocarbon is stated in EP-A-699225, EP-A-649896, WO-A-97/18278, EP-A-705321, EP-A-994173 and US-A-4851109, and these documents are here quoted as a reference.

In preferred embodiments, co-fed in the total fluid hydrocarbon of butt (being moisture-free basis), the co-fed element hydrogen that is more than or equal to 8wt% that comprises of fluid hydrocarbon, more preferably greater than the element hydrogen (being hydrogen atom) of 12wt%.High element hydrogen content, as be more than or equal to the content of 8wt%, allow hydrocarbon charging in catalyst cracking method, to be used as cheap hydrogen donor.Fluid hydrocarbon that a kind of particularly preferred element hydrogen content is more than or equal to 8wt% is co-fed is Fisher-Tropsch derived wax residual solution.This Fisher-Tropsch derived wax residual solution can for example comprise the elemental carbon of about 85wt% and the element hydrogen of 15wt%.

In the time existing fluid hydrocarbon co-fed, the co-fed weight ratio with liquiefied product (or its part) of fluid hydrocarbon is preferably greater than or equal to 50:50 (5:5), more preferably greater than or equal 70:30 (7:3), still more preferably greater than or equal 80:20 (8:2), even still more preferably greater than or equal 90:10 (9:1).For actual purpose, fluid hydrocarbon is co-fed is preferably less than or equal to 99.9:0.1 (99.9:0.1) with weight ratio liquiefied product (or its part), is more preferably less than or equals 95:5 (95:5).Co-fed and the final liquiefied product (or its part) of fluid hydrocarbon is preferably fed to fluid catalytic cracking reactor in the weight ratio of above-mentioned scope.

To offer liquiefied product and the co-fed gross weight of fluid hydrocarbon of fluid catalytic cracking reactor, the amount of liquiefied product is preferably less than or equal to 50wt%, be more preferably less than or equal 30wt%, be most preferably less than or equal to 20wt% and be even more preferably less than or equal 10wt%.For actual purpose, to offer liquiefied product and the co-fed gross weight of fluid hydrocarbon of fluid catalytic cracking reactor, the amount of liquiefied product is preferably greater than or equal to 0.1wt%, more preferably greater than or equal 1wt%.

Catalytic cracking step is preferably implemented in fluid catalytic cracking reactor.Fluid catalytic cracking reactor can be known in the art any fluid catalytic cracking reactor that is suitable for this object, comprises for example fluidisation dense bed reactor or riser reactor.Most preferably, catalytic cracking step is implemented in riser reactor.A part for preferably fluid catalytic cracking of this fluid catalytic cracking reactor (FCC) device.

In one embodiment, in the time that the organic solvent in liquefaction step comprises one or more and may also be suitable as the co-fed hydrocarbon compound of fluid hydrocarbon, preferably the mixture of liquiefied product and any organic solvent can be offered to fluid catalytic cracking reactor.For example, in the time that oil or its cut are used as the solubility promoter in liquefaction step, fluid hydrocarbon described herein is co-fed can be comprised or be made up of this solubility promoter.In another embodiment, it is co-fed that the organic solvent of applying in liquefaction step is selected from above-mentioned fluid hydrocarbon.For co-fed preferably the pressing as mentioned above of fluid hydrocarbon.

In another preferred embodiment, fluid catalytic cracking reactor is riser reactor and the downstream position that liquiefied product is offered to riser reactor, by the co-fed fluid hydrocarbon riser reactor that offers.

In another one embodiment, at first location place, the mixture of co-fed to liquiefied product and the first hydrocarbon (when organic solvent is selected from above-mentioned fluid hydrocarbon it can be for example organic solvent when co-fed) is offered to riser reactor, and at the second position place in first location downstream by the co-fed second fluid hydrocarbon riser reactor that offers.For the first and second fluid hydrocarbon co-fed preferably as mentioned above.

Riser reactor is understood to be suitable for the reactor of the elongated basic tubulose of implementing catalytic cracking reaction here.The reactor of elongated basic tubulose is preferably orientated in substantially vertical mode.

The example of suitable riser reactor is the 3rd chapter of the handbook of " Fluid Catalytic Cracking technology and operations " at the title of being published by PennWell Publishing Company (1997) of Joseph W.Wilson, particularly in 101-112 page, state, the document is here quoted as a reference.

Riser reactor can be so-called interior riser reactor or the so-called outer riser reactor of describing therein.

Most preferably, interior riser reactor is the reactor of basic vertical basic tubulose, and it may have the substantially vertical upstream extremity and the basic vertical downstream end that is positioned at internal tank that are positioned at external container.Described container is the container for being suitable for the reaction vessel of catalytic cracking reaction and/or comprising one or more cyclonic separators and/or vortex tube suitably.Interior riser reactor may be particularly advantageous in catalytic cracking step, because it may more difficult obstruction, thereby has increased the globality of safety and hardware.

The length of riser reactor can change in wide range.For actual purpose, the length of riser reactor is preferably greater than or equal to 10 meters, more preferably greater than or equal 15 meters, and be most preferably more than or equal to 20 meters, to being less than or equal to 65 meters, being more preferably less than or equaling 55 meters, and being most preferably less than or equal to 45 meters.

In preferred embodiments, the liquiefied product producing in liquefaction step is offered to riser reactor in the bottom of riser reactor.This may advantageously cause forming water in the bottom of reactor original position.Original position forms water and can reduce hydrocarbon partial pressure and reduce secondary hydrogen transfer reactions, thereby causes higher olefin yields.It is 0.7-2.8bar absolute pressure (0.07-0.28MPa) that hydrocarbon partial pressure is preferably down to pressure, more preferably 1.2-2.8bar absolute pressure (0.12-0.28MPa).

Also it may be favourable adding lifting gas in riser reactor bottom.The example of this lifting gas comprises oil and/or oil distillate and their mixture of steam, gasification.From practical standpoint, steam is most preferred as promoting gas.But the oil of application gasification and/or oil distillate (preferably liquefied petroleum gas (LPG), gasoline, diesel oil, kerosene or the petroleum naphtha of gasification) do to promote advantage that gas may have be promote gas can be simultaneously as hydrogen donor with can prevent or reduce the formation of coke.In addition, if the co-fed organic solvent being used as in liquefaction step of fluid hydrocarbon, the organic solvent of gasification also can be as promoting gas.

Fluidized catalytic cracking catalyst can be the known any catalyzer that is applicable to cracking method of those skilled in the art.Fluidized catalytic cracking catalyst preferably comprises zeolite component.In addition, fluidized catalytic cracking catalyst can contain amorphous caking agent compound and/or filler.The example of amorphous adhesive component comprises two or more combination of silicon-dioxide, aluminum oxide, titanium dioxide, zirconium white and magnesium oxide or they.The example of filler comprises clay (as kaolin).

Zeolite is preferably large pore zeolite.Large pore zeolite comprises that wherein said aluminosilicate has porous internal cellular structure containing the zeolite of the crystalline aluminosilicate structure of porous, and the main axle in wherein said hole is 0.62-0.8 nanometer.The axle of zeolite is at W.M.Meier, D.H.Olson and Ch.Baerlocher " Elsevier, states in ISBN0-444-10015-6 for Atlas of Zeolite Structure Types', the 4th revised edition of 1996.The example of this large pore zeolite comprises FAU or faujusite, is preferably synthetic faujusite, 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.

Fluidized catalytic cracking catalyst also can comprise mesopore zeolite.The mesopore zeolite that can apply is in the present invention the zeolite of the crystalline aluminosilicate structure that comprises porous, and wherein said aluminosilicate has porous internal cellular structure, and the main axle in wherein said hole is 0.45-0.62 nanometer.The example of this mesopore zeolite has MFI structure class if ZSM-5, MTW class are if ZSM-12, TON structure class are if θ 1 and FER structure class are as ferrierite.According to the present invention, ZSM-5 is preferably used as mesopore zeolite.

According to another embodiment, can apply the blend of macropore and mesopore zeolite.In cracking catalyst, large pore zeolite is preferably 99:1 to 70:30, more preferably 98:2 to 85:15 with the ratio of mesopore zeolite.

With respect to the total mass of fluidized catalytic cracking catalyst, the large pore zeolite existing in cracking catalyst and/or the total amount of mesopore zeolite are preferably 5-40wt%, more preferably 10-30wt%, and 10-25wt% even more preferably.

Liquiefied product and any fluid hydrocarbon feed are preferably along identical direction concurrent flow.Fluidized catalytic cracking catalyst can be so that also stream, adverse current or cross-flow structure contact with optional fluid hydrocarbon feed stream with liquiefied product.Catalytic cracking catalyst preferably contacts with optional fluid hydrocarbon feed with the liquiefied product of concurrent flow also to flow structure.

In preferred embodiments, catalytic cracking step comprises:

Fluid catalytic cracking step, described fluid catalytic cracking step is included at the temperature that is more than or equal to 400 DEG C at least partly final liquiefied product is contacted with fluidized catalytic cracking catalyst, to produce one or more cracked product and useless fluidized catalytic cracking catalyst;

Separating step, described separating step comprises one or more cracked product and waste stream fluidized catalytic cracking catalyst separating;

Regeneration step, described regeneration step comprises makes waste stream fluidized catalytic cracking catalyst regeneration, to produce fluidized catalytic cracking catalyst, heat and the carbonic acid gas after regeneration; With

Circulation step, described circulation step comprise by regeneration after fluidized catalytic cracking catalyst be circulated to fluid catalytic cracking step.

Fluid catalytic cracking step is preferably by enforcement mentioned above.

Separating step is preferably implemented by means of one or more cyclonic separators and/or one or more vortex tube.The appropriate method of implementing separating step for example has and states in following article: the title of Reza Sadeghbeigi is " Fluid Catalytic Cracking; Design, Operation, and Troubleshooting of FCC Facilities " handbook, by Gulf Publishing Company, Houston Texas (1995) publishes, particularly 219-223 page; Handbook " Fluid Catalytic Cracking technology and operations " with Joseph W.Wilson, published by PennWell Publishing Company (1997), the 3rd chapter, particularly 104-120 page and the 6th chapter, particularly 186-194 page, these documents are here quoted as a reference.

Except separating step, can also comprise air lift step.In this air lift step, can be by useless fluidized catalytic cracking catalyst air lift to be recovered in the product absorbing on useless fluidized catalytic cracking catalyst before regeneration step.Can and join containing in the logistics of one or more cracked product of being obtained by catalytic cracking step by these product circulations.

Regeneration step is preferably included at the temperature that is more than or equal to 550 DEG C and in revivifier, makes useless fluidized catalytic cracking catalyst contact with oxygen-containing gas, to produce fluidized catalytic cracking catalyst, heat and the carbonic acid gas through regeneration.In regenerative process, because fluid catalytic cracking reaction may can be burnt to recover catalyst activity at coke deposited on catalyst charcoal.

Oxygen-containing gas can be the known any oxygen-containing gas that is adapted at applying in revivifier of those skilled in the art.For example oxygen-containing gas can be air or oxygen-rich air.Oxygen-rich air is understood to the cumulative volume in air here, comprises and is greater than 21vol% oxygen (O ₂) air, more preferably comprise the air that is more than or equal to 22vol% oxygen.

The heat producing in the regeneration step of heat release is preferably used to provide the energy of the catalytic cracking step for absorbing heat.In addition, the heat producing can and/or produce steam for heating water.Described steam can be for other place of refinery, for example, as the lifting gas in riser reactor.Useless fluidized catalytic cracking catalyst preferably temperature be more than or equal to 575 DEG C, more preferably greater than or equal 600 DEG C to being less than or equal to 950 DEG C, more preferably to being less than or equal at 850 DEG C regeneration.Useless fluidized catalytic cracking catalyst preferably pressure be more than or equal to 0.5bar absolute pressure to be less than or equal to 10bar absolute pressure (0.05-1MPa), more preferably greater than or equal 1.0bar absolute pressure to being less than or equal under 6bar absolute pressure (0.1-0.6MPa) regeneration.

Fluidized catalytic cracking catalyst after regeneration can be circulated to fluid catalytic cracking step.In preferred embodiments, add the side-stream of supplementing fluidized catalytic cracking catalyst to recycle stream, with the loss of fluidized catalytic cracking catalyst in postreaction district and revivifier.

Produce in the method for the invention one or more cracked product.In preferred embodiments, subsequently by described one or more cracked product fractionation, to produce one or more product cuts.

Fractionation can be implemented by the known any mode that is suitable for rectifying catalytic cracking unit product of those skilled in the art.For example rectifying can be the handbook of " Fluid Catalytic Cracking technology and operations " by the title of Joseph W.Wilson, published by PennWell Publishing Company (1997), 14-18 page and the 8th chapter, the mode of particularly describing in 223-235 page is implemented, and the document is here quoted as a reference.

In another embodiment, at least one of one or more product cuts that obtain by rectifying preferably used hydrogen source hydrotreatment subsequently under hydrotreating catalyst exists, to produce the product cut through hydrotreatment.Described hydrotreating step can for example comprise hydrogenation deoxidation, hydrodenitrification and/or hydrogenating desulfurization.

One or more product cuts and/or one or more can be easily used as to biofuel component through the product cut of hydrotreatment and/or by its derivative any cut.This biofuel component can be easily with one or more other component blending to produce biofuel.The example of described this one or more other components comprises antioxidant, sanitas, ashless detergent, demisting agent, dyestuff, lubricity improver and/or mineral fuel component, also comprises gasoline, diesel oil and/or the kerosene(oil)fraction of conventional petroleum derivation.

Biofuel is understood to the fuel derived from renewable energy source at least partly here.Biofuel can advantageously be applied in the engine of carrier vehicle.

Embodiment

Embodiment 1

By approximately 30 grams of birch and 1.70 grams of acid chloride (Pd (OAc) ₂) pack into be furnished with electrically heated, in the 300ml Premex Batch autoclave of agitator, injected system, pressure warning unit and thermograph.

Start stir (300rpm) and close autoclave.Stir speed (S.S.) is increased to the solution of 750rpm and injected water (84g), acetic acid (36g) and sulfuric acid (0.86g).With hydrogen (H ₂) autoclave is forced into 4MPa (40bar) and in 70 minutes, is heated to 200 DEG C subsequently.Subsequently by adding H ₂and reactor pressure is increased to 8MPa (80bar).Reaction continues 60 minutes, adds once in a while H ₂to maintain pressure as 8MPa.By being cooled to rapidly room temperature (20 DEG C), reaction is stopped, discharging subsequently H ₂, and collect 143.2g the first total product (comprising liquid, tar, insoluble soil ulmin and catalyzer).At repeating in experiment of application the same terms, preparation the second total product (143.7g).

The first and second total products are mixed.In the total product mixing, add methyl-tetrahydrofuran (THF) (m-THF, 400 grams).The mixture of methyl-tetrahydrofuran (THF) and total product is stirred 10 minutes under room temperature (20 DEG C), and filter to produce filtrate and filter cake with P3 glass filter subsequently.

By filtrate storage spend the night (approximately 12 hours) be separated promoting, and produce the organic layer at top and the waterbearing stratum of bottom.Collect the organic layer at top.

With the filter cake on m-THF (300g) washing P3 strainer to produce m-THF solution.M-THF solution is mixed with top organic layer.By removing m-THF at 80 DEG C, the rectification under vacuum of 20mbar (2KPa) from the mixture of top organic layer and m-THF solution, to produce 25.1 grams of liquiefied products.In this liquiefied product, add again 200g m-THF, and use subsequently the NaHCO of 10wt% ₃(25g) and water (25g) wash this solution.Again by removing m-THF at 80 DEG C, the rectification under vacuum of 20mbar (2KPa), to produce the thickness liquiefied product of 23.4 grams of brownish blacks.

With SEC (RI/UV) (with the exclusion chromatography of UV and RI-detector), gas-chromatography and ¹³c-nucleus magnetic resonance ( ¹³c-NMR) characterize the thick liquid of described brownish black.The results of elemental analyses of carbon, hydrogen and oxygen: C:63.5w% (± 0.3), H:7.89w% (± 0.1), O (being calculated by surplus): 27.3w% (± 0.5).The H/Ceff of brownish black thickness liquiefied product is 0.85.Total acid value (TAN) is defined as (± 5) mg KOH/g.Above-mentioned brownish black thickness liquiefied product is used as to final liquiefied product.The heavier feedstocks mixture that comprises long residuum is co-fed as fluid hydrocarbon.Make final liquiefied product and the co-fed blend of fluid hydrocarbon, to prepare the raw mixture containing the final liquiefied product of 20wt% with final liquiefied product and the co-fed gross weight of fluid hydrocarbon.Raw mixture is injected to the fluidized catalyst bed of MAT-5000 fluidized catalytic cracker.Fluidized catalyst bed contains 10 grams of FCC equilibrium catalysts containing super steady zeolite Y.Fluidized catalyst bed is kept with about 1bar absolute pressure (about 0.1MPa) is lower at 520 DEG C.Experiment comprises 7 tests that utilize 7 catalyzer and raw material weight ratio, and the weight ratio of catalyst/feed is respectively 3,4,5,6,6.5,7 and 8.

When with compared with the co-fed raw material forming of 100wt% fluid hydrocarbon time, final liquiefied product and the co-fed raw mixture of fluid hydrocarbon have more reactivity.When compared with reference raw material, final liquiefied product and the co-fed raw mixture of fluid hydrocarbon show the similarly similar yield of yield and coke of valuable product (gasoline, light cycle oil and LPG).Detailed results provides in following table 1.

The normalization method of result in table 1 and wherein application be (there is no H with butt ₂o) value of calculating.

Calculate for the transformation efficiency in table 1, first the correcting weight of total raw material is not converted into CO or CO by deducting from raw material for each Sauerstoffatom ₂the weight of a water molecules calculate.Subsequently transformation efficiency is defined as to the weight in grams of dry gas+LPG+ gasoline+coke divided by the correcting weight gram of total raw material.Therefore, transformation efficiency=[weight of dry gas+LPG+ gasoline+coke]/[total raw material weight-(weight-CO of oxygen and CO in raw material ₂the weight of middle oxygen) * 18/16] * 100%.

Calculate for the product yield in table 1, first the correcting weight of total raw material is not converted into CO or CO by deducting from raw material for each Sauerstoffatom ₂the weight of a water molecules calculate.Subsequently the yield of product is defined as to the weight in grams of specific product divided by the correcting weight gram of total raw material.In other words, the yield of product distributes in alkyl standard.Therefore, the product yield of product X=[weight of X]/[total raw material weight-(weight-CO of oxygen and CO in raw material ₂the weight of middle oxygen) * 18/16] * 100%.

Because can not experiment measuring water in the bench-scale testing of the present embodiment, the oxygen level that it is measured by raw material in table 1 and for formed CO and CO ₂measuring vol proofread and correct and calculate.Suppose the oxygenatedchemicals that there is no Partial Conversion in product, this " the water yield of supposition " provided the surplus of oxygen.Therefore, water=[(weight-CO of oxygen and CO in raw material ₂the weight of middle oxygen) * 18/16]/[weight of total raw material] * 100%.

The product of table 1:100wt% fluid hydrocarbon co-fed reference raw material after fluid catalytic cracking (FCC) and by the final liquiefied product of 20wt% and the co-fed raw mixture forming of 80wt% fluid hydrocarbon the product (at 520 DEG C of the constant ratio that is 3.0 in catalyst/oil and temperature) after FCC

FHCF=fluid hydrocarbon is co-fed, LCO=light cycle oil, HCO=heavy cycle oil, LPG=liquefied petroleum gas (LPG).

Embodiment 2

Furfural and furfuryl alcohol are used separately as to the artificial substituent of final liquiefied product.In addition, co-fed as fluid hydrocarbon by thering is the heavier feedstocks mixture forming described in table 2a and 2b.

Table 2a: the boiling Range Distribution Analysis of pressing the definite fluid hydrocarbon feed of ASTM D2887-06a gas-chromatography

wt％	℃	wt％	℃	wt％	℃
						IBP	240	34	410	68	476
2	281	36	414	70	481
						4	306	38	417	72	486
6	321	40	421	74	492
						8	333	42	425	76	498
10	342	44	428	78	504
						12	351	46	432	80	511
14	358	48	435	82	519
						16	365	50	438	84	527
18	371	52	442	86	548
						20	377	54	445	88	563
22	382	56	449	90	585
						24	387	58	453	92	n.d.
26	392	60	458	94	n.d.
						28	397	62	462	96	n.d.
30	401	64	467	98	n.d.
						32	405	66	471	FBP	n.d.

N.d: do not determine

Table 2b: the ultimate analysis that fluid hydrocarbon is co-fed

Raw material is described	[C]	[H]	[O]	[S]	[N]
						?	[wt％]	[wt％]	[wt％]	[ppm]	[ppm]
Fluid hydrocarbon is co-fed	86.65％	12.65％	0.00％	3360	2220

Furfural and furfuryl alcohol are mixed to prepare by the gross weight of raw mixture containing the furfural of 20wt% or the raw mixture of furfuryl alcohol with fluid hydrocarbon is co-fed respectively.Raw mixture is injected to the fluidized catalyst bed of MAT-5000 fluidized catalytic cracker.Fluidized catalyst bed contains 10 grams of FCC equilibrium catalysts containing super steady zeolite Y.Fluidized catalyst bed is kept with about 1bar absolute pressure (about 0.1MPa) is lower at 520 DEG C.The weight ratio of catalyst/feed is 3.Effective mol ratio (H/C of the hydrogen of furfural and furfuryl alcohol and carbon _eff) be respectively 0.0 and 0.4.Effective mol ratio (H/C of hydrogen and carbon _eff) be not understood to be in when supposition has nitrogen or sulphur and pass through to produce water with the hydrogen of original existence, remove after the whole mole oxygen that exist in butt the mol ratio (H/C of hydrogen and carbon in oil in theory _eff=(H-2*O)/C).

When compared with reference raw material, demonstrate valuable product (gasoline, light cycle oil and LPG) containing the raw mixture of furfural or furfuryl alcohol and slightly reduce slightly to increase with coking yield.Detailed results provides in table 2c.Show the normalization method of result in 2c and wherein (there is no H with butt ₂o) calculate.

Calculate for transformation efficiency, first the correcting weight of total raw material is not converted into CO or CO by deducting from raw material for each Sauerstoffatom ₂the weight of a water molecules calculate.Subsequently transformation efficiency is defined as to the weight in grams of dry gas+LPG+ gasoline+coke divided by the correcting weight gram of total raw material.Therefore, transformation efficiency=[weight of dry gas+LPG+ gasoline+coke]/[total raw material weight-(weight-CO of oxygen and CO in raw material ₂the weight of middle oxygen) * 18/16] * 100%.

Calculate for product yield, first the correcting weight of total raw material is not converted into CO or CO by deducting from raw material for each Sauerstoffatom ₂the weight of a water molecules calculate.Subsequently the yield of product is defined as to the weight in grams of specific product divided by the correcting weight gram of total raw material.In other words, the yield of product distributes in alkyl standard.Therefore, the product yield of product X=[weight of X]/[total raw material weight-(weight-CO of oxygen and CO in raw material ₂the weight of middle oxygen) * 18/16] * 100%.

Because can not experiment measuring water in the bench-scale testing of the present embodiment, the oxygen level that it is measured by raw material and for formed CO and CO ₂measuring vol proofread and correct and calculate.Suppose the oxygenatedchemicals that there is no Partial Conversion in product, this " the water yield of supposition " provided the surplus of oxygen.Therefore, water=[(weight-CO of oxygen and CO in raw material ₂the weight of middle oxygen) * 18/16]/[weight of total raw material] * 100%.

The product of table 2c:100wt% fluid hydrocarbon co-fed reference raw material after fluid catalytic cracking (FCC) and by 20wt% furfural or furfuryl alcohol and the product (the constant ratio that in catalyst/oil be 3.0 and temperature 520 DEG C at) of the co-fed raw mixture forming of 80wt% fluid hydrocarbon after FCC

Embodiment 2 further shows that described all final liquiefied products are mixtures of several components to the co-fed all final liquiefied products of FCC apparatus instead of only containing the advantage of the raw material of furfural or furfuryl alcohol.

Embodiment 3

Apply respectively tetrahydrofuran (THF) (THF), butanone and 2-butanols and do the artificial substituent of final liquiefied product.In addition that vacuum gas oil (VGO) is co-fed as fluid hydrocarbon.

Tetrahydrofuran (THF) (THF), butanone or 2-butanols are mixed to prepare by the gross weight of raw mixture the raw mixture containing tetrahydrofuran (THF) (THF), butanone or the 2-butanols of 20wt% weight percent with fluid hydrocarbon is co-fed respectively.Raw mixture is injected to the fluidized catalyst bed of MAT-5000 fluidized catalytic cracker.Fluidized catalyst bed contains 10 grams of FCC equilibrium catalysts containing super steady zeolite Y.Fluidized catalyst bed is kept with about 1bar absolute pressure (about 0.1MPa) is lower at 550 DEG C.The weight ratio of catalyst/feed is 3.

Effective mol ratio (H/C of the hydrogen of tetrahydrofuran (THF) (THF), butanone and 2-butanols and carbon _eff) be respectively 1.5,1.5 and 2.0.Than reference raw material, the raw mixture that comprises respectively tetrahydrofuran (THF) (THF), butanone or 2-butanols demonstrates the similar yield of valuable product (gasoline, light cycle oil and LPG), and even aspect coking yield, can reduce for butanone and 2-butanols.Detailed results provides in table 3.

The product of table 3:100wt% fluid hydrocarbon co-fed reference raw material after fluid catalytic cracking (FCC) and by 20wt%THF, butanone or 2-butanols the product after FCC (at 550 DEG C of the constant ratio that is 3.0 in catalyst/oil and temperature) with the co-fed raw mixture forming of 80wt% fluid hydrocarbon respectively

Normalization method of the above results in table 3 and (there is no H by butt ₂o) calculate.

Claims

1. the method that transforms cellulose materials, described method comprises:

2. the process of claim 1 wherein that described liquid solvent comprises water and/or organic solvent.

3. the method for claim 1 or 2, wherein said liquefaction step is included at the temperature that is more than or equal to 150 DEG C cellulose materials is contacted with organic solvent, hydrogen source, acid catalyst and hydrogenation catalyst simultaneously, to produce final liquiefied product.

4. the method for claim 1 or 2, wherein said liquefaction step is included under acid catalyst existence and at the temperature that is more than or equal to 150 DEG C, cellulose materials is contacted with organic solvent, with liquiefied product in the middle of producing; Under existing, hydrotreating catalyst uses subsequently the middle liquiefied product of hydrogen source hydrotreatment, to produce final liquiefied product.

5. the method for claim 1 or 2, wherein said liquid solvent is that organic solvent and wherein said method also comprise separating step, the final liquiefied product that wherein at least partly liquefaction step produces separates with at least part of organic solvent, and wherein optionally the part organic solvent separating is circulated and is contacted with cellulose materials.

6. the method for claim 1 or 2, wherein said catalytic cracking step is included at the temperature that is more than or equal to 400 DEG C at least partly final liquiefied product is contacted with fluidized catalytic cracking catalyst with fluid hydrocarbon is co-fed, to produce one or more cracked product.

7. the method for claim 6, co-fed straight run (normal pressure) gas oil, flash distillation overhead product, vacuum gas oil (VGO), light cycle oil, heavy cycle oil, hydrogenation wax, coker gas oil, gasoline, petroleum naphtha, diesel oil, kerosene, long residuum and vacuum resid and/or their mixture of comprising of wherein said fluid hydrocarbon.

8. the method for the conversion cellulose materials of claim 1 or 2, described method comprises:

A) liquefaction step, described liquefaction step is included under catalyzer existence and at the temperature that is more than or equal to 100 DEG C, cellulose materials is contacted with organic solution, and to produce final liquiefied product, wherein said organic solvent is stone oil fraction;

B) catalytic cracking step, described catalytic cracking step is included at the temperature that is more than or equal to 400 DEG C and in fluid catalytic cracking reactor, makes the mixture of at least partly final liquiefied product and petroleum fractions contact with fluidized catalytic cracking catalyst, to produce one or more cracked product.

9. the method for claim 8, wherein said liquefaction step is included at the temperature that is more than or equal to 150 DEG C cellulose materials is contacted with petroleum fractions, hydrogen source and hydrogenation catalyst simultaneously, to produce final liquiefied product.

10. the method for claim 8, wherein in the liquefaction process of cellulose materials, also original position produces organic solvent.

The method of the conversion cellulose materials of 11. claims 1 or 2, described method comprises:

A) liquefaction step, described liquefaction step is included at the temperature that is more than or equal to 150 DEG C cellulose materials is contacted with liquid solvent, hydrogen source, acid catalyst and hydrogenation catalyst simultaneously, to produce final liquiefied product;

The method of 13. claims 12, wherein said liquid solvent is water or comprises organic solvent and the solvent mixture of water.

The method of 14. aforementioned claim any one, wherein final liquiefied product or its part comprise a kind of, two or more are selected from following compound: γ-valerolactone and/or levulinic acid; Tetrahydrofurfuryl and/or THP trtrahydropyranyl; Furfural and/or hydroxymethylfurfural; Single-and/or two-ol and/or single-and/or two-one; And/or o-hydroxyanisole and/or syringol component.

The method of 15. aforementioned claim any one, wherein said method also comprises rectification step, described rectification step comprises one or more cracked product described in rectifying, to produce one or more product cuts.

The method of 16. claims 15, wherein said method also comprises hydrotreating step, described hydrotreating step comprises with one or more product cuts of hydrogen source hydrotreatment, to produce one or more product cuts through hydrotreatment.

Any product that one or more product cuts that 17. claims 15 produce, one or more one or more product cuts through hydrotreatment that produce through product cut, one or more product cuts that produced by claim 15 or the claim 16 of hydrotreatment that claim 16 produces derive and/or these any mixture are as the purposes of biofuel component.

Produce the method for biofuel for 18. 1 kinds, comprise by the biofuel component of claim 17 and one or more other component blending, to produce biofuel.