CN104471144A

CN104471144A - Biomass conversion systems providing integrated stabilization of a hydrolysate using a slurry catalyst and methods for use thereof

Info

Publication number: CN104471144A
Application number: CN201380034071.7A
Authority: CN
Inventors: J·B·鲍威尔
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2012-06-28
Filing date: 2013-06-27
Publication date: 2015-03-25
Anticipated expiration: 2033-06-27
Also published as: US20160237359A1; CN104471144B; AU2013280239A1; EP2867404A1; CA2877497A1; BR112014032113A2; IN2014DN10536A; WO2014004842A1; AU2013280239B2; US20140000154A1; AU2013280239C1

Abstract

Digestion of cellulosic biomass solids to form a hydrolysate may be conducted with integrated catalytic reduction during digestion to transform soluble carbohydrates in the hydrolysate into a more stable reaction product. Such integrated catalytic reduction may be conducted using a slurry catalyst. Biomass conversion systems for performing integrated catalytic reduction can comprise: a hydrothermal digestion unit that contains a slurry catalyst capable of activating molecular hydrogen; an optional hydrogen feed line that is operatively connected to the hydrothermal digestion unit; and a fluid circulation loop comprising the hydrothermal digestion unit and a catalytic reduction reactor unit, the catalytic reduction reactor unit also containing the slurry catalyst.

Description

Use conversion systems for biomass and the using method thereof that integrated stable hydrolysate is provided of slurry catalyst

Quoting of related application

The rights and interests of the U.S. Patent application 61/665,641 that application claims was submitted on June 28th, 2012.

Summary of the invention

The disclosure relates generally to and uses digestion (digestion) to process cellulose biomass solid to produce hydrolysate, more specifically, the hydrolysate related to by using slurry catalyst to allow to comprise soluble carbohydrate is able to stable conversion systems for biomass and using method thereof during digestion.

Summary of the invention

The disclosure relates generally to and uses digestion process cellulose biomass solid to produce hydrolysate, more specifically, in digestion process, make to comprise the hydrolysates to stabilize of soluble carbohydrate by the use of slurry catalyst conversion systems for biomass and using method thereof is related to.

In some embodiments, the invention provides conversion systems for biomass, it comprises: comprising can the hydrothermal digestion unit of slurry catalyst (" molecular hydrogen actived slurry catalyst ") of anakmetomeres hydrogen; The optional hydrogen feeding line be operably connected with hydrothermal digestion unit; With the fluid circulation loop comprising hydrothermal digestion unit and catalytic reduction reactor unit, this catalytic reduction reactor unit also comprises slurry catalyst.

In some embodiments, the invention provides method, it comprises: in hydrothermal digestion unit, provide cellulose biomass solid, and described hydrothermal digestion unit comprises can the slurry catalyst (" molecular hydrogen actived slurry catalyst ") of anakmetomeres hydrogen; Under molecular hydrogen exists in hydrothermal digestion unit heating cellulose biomass solid, make slurry catalyst cycle through described hydrothermal digestion unit simultaneously, thus formed and comprise the hydrolysate of soluble carbohydrate in the liquid phase; At least partly soluble carbohydrate is converted into product when soluble carbohydrate is in hydrothermal digestion unit; With at least part of liquid phase is transferred to the catalytic reduction reactor unit also comprising slurry catalyst, further soluble carbohydrate is converted into product thus.

When the explanation of reading following preferred embodiment, feature and advantage of the present disclosure will be easily visible for those skilled in the art.

Background of invention

Many materials with commercial significance can from natural origin, especially living beings manufacture.Cellulose biomass especially has advantage in this respect, because the diversified rich in carbohydrate found wherein in a variety of forms.As used herein, term " cellulose biomass " refers to and comprises cellulosic lived or nearest lived biomaterial.The ligno-cellulosic materials found in higher plant cell wall is the source of carbohydrate the abundantest in the world.Usually comprise from the material that cellulose biomass is obtained, such as, the paper obtained via part digestion and paper pulp, and by the bio-ethanol obtained that ferments.

Plant cell wall is divided into two parts: primary cell wall and secondary cell wall.Primary cell wall provides structural support for expansion cell, and comprises three kinds of main polysaccharide (cellulose, pectin and hemicellulose) and one group of glycoprotein.Secondary cell wall produces after cell has terminated growth, and it also comprises polysaccharide, and is strengthened by the polymeric lignin covalently bound with hemicellulose.Hemicellulose and the usual rich content of pectin, but cellulose is main polysaccharide and the abundantest carbohydrate source.The complex mixture of the composition coexisted with cellulose can make it be difficult to process, as discussed hereinbelow.

Split the fossil fuel substitute aspect rising in renewable resource and pay obvious concern.Cellulose biomass has won special concern in this respect because of the diversity of the Multiple components that it is rich and wherein find (particularly cellulose and other carbohydrate).Although there is clear and definite and strong interest, exploitation and the enforcement of biologically based fuels technology are always slow.Prior art up to now produced there is low energy densities fuel (such as, bio-ethanol) and/or can not be completely compatible with transportation infrastructure with existing engine design fuel (such as, methyl alcohol, biodiesel, Fischer-Tropsch diesel oil, hydrogen and methane).Will be ideal for cellulose biomass being processed into the energy of the fuel mixture with the composition being similar to fossil fuel and cost effective method for solution aforementioned and other problem.

When cellulose biomass being converted into fuel mixture and other material, cellulose wherein and other complex carbohydrates can be extracted and be converted into better simply organic molecule, and the latter can reform subsequently further.Fermentation the complex carbohydrates of in the future authigenic material can be converted into a kind of method of more useful form.But fermentation method normally slowly, needs large volume reactor, and produce the initial reaction product (ethanol) of the energy density had.Digestion is the another kind of method that cellulose and other complex carbohydrates can be converted into more useful form.Cellulose in cellulose biomass and other complex carbohydrates can be decomposed into the better simply soluble carbohydrate being applicable to being transformed further by downstream reforming reaction by digestion method.As used herein, term " soluble carbohydrate " refers to the monose or polysaccharide that dissolve in digestion method.Recalling for being present in the organic compound in fossil fuel although potential chemistry is understood to that simple carbohydrates is also converted into by digestion cellulose and other complex carbohydrates further, not yet developing and being applicable to cellulose biomass to be converted into the high yield of fuel mixture and the digestion method of Energy Efficient.In this, be cause the energy needed for conversion to input should not to be greater than the utilisable energy of product fuel mixture to export to using digestion and other method cellulose biomass to be converted into fuel mixture the most basic relevant demand.This primary demand result in a lot of secondary problems, and its common designation is still unsolved great industry challenge so far.

Cellulose biomass being converted into the relevant problem of fuel mixture to using digestion with energy and cost effective mode is not only complicated, and they are different from those that run in digestion method usually used in paper and pulp industry completely.Object due to cellulose biomass digestion in paper and pulp industry retains solid material (such as, wood pulp), usually carries out the incomplete digestion of suitable short time at low temperature (such as, lower than 100 DEG C).On the contrary, the digestion method being applicable to cellulose biomass to be converted into fuel mixture and other material is placed through ideally dissolves pristine fibre cellulosic biomass as much as possible and makes maximize yield under high-throughput mode.

For a variety of reasons, not easily produce more substantial for the soluble carbohydrate in fuel mixture and other material via the routine change of paper and paper pulp digestion method.From the angle of production capacity, the digestion method of paper and pulp industry being run the longer time is simply undesirable to produce more soluble carbohydrate.Use the digestion promoter of such as highly basic, strong acid or sulphite can increase process costs and complexity to accelerate digestion speed, this is attributable to process rear separating step and the possible protection downstream component needs from these reagent (impact).In fact can reduce productive rate by improving digestion temperature quickening digestion speed, this is attributable to the thermal degradation of the soluble carbohydrate that can occur under higher digestion temperature.Once be produced by digestion, soluble carbohydrate is high response, and can degrade rapidly, especially under higher temperature conditions (such as, higher than 100 DEG C, especially higher than 150 DEG C).From energy efficiency angle, use higher digestion temperature also may be undesirable.Any economic feasibility can defeating the fuel mixture coming from cellulose biomass in these difficulties.

A kind of method path that the soluble carbohydrate in hydrolysate can be protected to avoid thermal degradation makes their experience catalytic reduction reaction processes, and this process can comprise hydrogenation and/or hydrogenolysis.By carry out one or more catalytic reduction reactions the soluble carbohydrate in hydrolysate is stablized can allow the digestion of cellulose biomass with other may compared with higher temperature and can not excessive sacrifice productive rate.In addition, the product of catalytic reduction reaction process can be converted into fuel mixture and other material easily through downstream reforming reaction.

To cellulose biomass is processed into the relevant other problem of fuel mixture because of become with cellulose biomass being feeded high conversion percentages soluble carbohydrate need produce.Specifically, when cellulose biomass solid is by digestion, their size is finally reduced to the degree that it becomes the smooth movement of energy.As used herein, can the cellulose biomass solid of smooth movement, be particularly of a size of the cellulose biomass solid of 3mm or less, will be called as " cellulose biomass particulate ".Cellulose biomass particulate can transport out from the digestion district of the system for transforming cellulose biomass and enter one or more wherein solid to be undesired and to can be harmful district.Such as, cellulose biomass particulate has the possibility of embolism catalyst bed, feed-line etc.In addition, although size is little, but cellulose biomass particulate can represent extraordinary (non-trivial) part of cellulose biomass charging, and if they are not converted further as soluble carbohydrate, may affect the ability obtaining being satisfied with conversion percentages.Because paper runs with relative low cellulose biomass conversion percentages with the digestion method of pulp industry, believe the cellulose biomass particulate that can generate small amount, and to those digestion methods, there is little effect.

Except required carbohydrate, other material also can be present in cellulose biomass, and they are to being especially debatable with energy and cost effective manner process.Sulfur-bearing and/or nitrogenous amino acid or other catalyst poison may be present in cellulose biomass.If be not removed, these catalyst poisons can affect and be used for the catalytic reduction reaction of stable meltable carbohydrate, thus cause the process shutdown phase in order to catalyst regeneration and/or replacing and reduce overall energy efficiency when restarting technique.On the other hand, the energy efficiency that also can affect biomass conversion process is removed in the process of these catalyst poisons, this is owing to generally carrying out lower than those temperature by digestion production soluble carbohydrate for the ion exchange process carried out needed for its removal, can introduce heat exchange operation thus, this heat exchange operation adds design complexity and may increase running cost.

As above confirm, cellulose biomass is the challenge representing extensive engineering challenge to effective conversion of fuel mixture.The disclosure solves these challenges and provides associated advantages.

Accompanying drawing explanation

The following drawings is involved so that some aspect of the present disclosure to be described, and should not be regarded as exclusiveness embodiment.Disclosed theme can have sizable amendment, change, combination and full scope of equivalents in form and functionally, such with benefit of the present disclosure as is known by those skilled in the art.

Fig. 1 shows the schematic diagram of the conversion systems for biomass with hydrothermal digestion unit and the catalytic reduction reactor unit be connected with each other in fluid circulation loop, and wherein hydrothermal digestion unit and catalytic reduction reactor unit all comprise slurry catalyst.

Detailed description of the invention

In embodiment described herein, the digestion speed of cellulose biomass solid can be accelerated under digestion solvent exists.In some cases, digestion solvent can keep at elevated pressures, and described elevated pressures makes digestion solvent still remain liquid state on its normal boiling point.Although under the condition of these types, cellulose biomass solid digestion speed may be desirable faster viewed from the angle of production capacity, as discussed above, soluble carbohydrate may easily be degraded at relatively high temperatures.

Degrade relevant problem with soluble carbohydrate for solving, present disclose provides the effective promotion simultaneously of digestion cellulose biomass solid by the heat-staple system and method for the soluble carbohydrate of its generation.Specifically, present disclose provides the system and method that hydrothermal digestion and one or more catalytic reduction reactions occur in same container.We have found if in like fashion, and the stable of soluble carbohydrate occurs most effectively.Foregoing can the slurry catalyst of anakmetomeres hydrogen realize by comprising at the hydrothermal digestion unit comprising cellulose biomass solid.As used herein, term " slurry catalyst " refer to can suspend at least partly via air-flow, liquid stream, mechanical agitation or their any combination in the liquid phase comprise can the catalyst of catalyst granules of smooth movement.In hydrothermal digestion unit, there is slurry catalyst can allow one or more original positions (integrated) catalytic reduction reaction occurs wherein, thus advantageously after soluble carbohydrate is formed, to intercept and transform soluble carbohydrate be as quickly as possible more stable product.As used herein, term " situ catalytic reduction reaction " refers to and the catalytic reduction reaction that digestion process occurs in same container.The formation of product can reduce the amount of the thermal degradation occurred in hydrothermal digestion process, thus makes the high yield conversion of cellulose biomass solid to required product can occur in time.

Except being except product by soluble carbohydrate immediate stability, from the angle of energy efficiency, it is also particularly favourable for carrying out one or more situ catalytic reduction reactions.Specifically, the hydrothermal digestion of cellulose biomass is endothermic process, and catalytic reduction reaction is heat release.Therefore, the excessive heat that situ catalytic reduction reaction produces can be used for driving hydrothermal digestion, thus reduces the amount of the extra heat energy input carried out needed for digestion.Because digestion and catalytic reduction occur in same container in embodiment described herein, there is the minimizing possibility of heat trnasfer loss, if catalytic reduction reaction carries out generation heat trnasfer to lose in independent position.In addition, in such structure, situ catalytic reduction reaction can provide the product increased gradually supply in hydrothermal digestion unit, and it can be used as and/or supplements digestion solvent.Because product and digestion solvent can be identical, be not separated before the further processing reaction product of downstream and the special needs of most of digestion solvent that circulates, from the angle of energy efficiency, this can be favourable further.

Although concerning stable meltable carbohydrate and realize heat integrated to carry out one or more situ catalytic reduction reactions can be ideal, the catalyst poison in cellulose biomass and other material may make to be difficult to carry out such process.When carrying out situ catalytic reduction reaction, have no chance to be removed before the slurry catalyst of catalyst poison contact distribution.A method that can solve this problem is the slurry catalyst using poisoning resistant, and wherein some are discussed hereinafter.Another kind of replacement scheme be use when be exposed to can easily in hydrothermal digestion unit or near the condition of foundation time reproducible slurry catalyst.Such as, in some embodiments, reproducible slurry catalyst is by being exposed to the water reuse (treatment of at least 300 DEG C of temperature.

Once soluble carbohydrate is converted into more stable product at least partly in hydrothermal digestion process, conversion from soluble carbohydrate to product can also use described slurry catalyst or can anakmetomeres hydrogen different catalysts independent catalytic reduction reactor unit in occur.The conversion occurred in catalytic reduction reactor unit can comprise the higher conversion to oxidation intermediates of the further reduction of initial reaction product degree of oxidation and/or soluble carbohydrate.As used herein, term " oxidation intermediates " refers to the alcohol, polyalcohol, ketone, aldehyde and composition thereof that produce from the catalytic reduction reaction of soluble carbohydrate.The feature of described conversion systems for biomass can allow the initially dissolved carbohydrate of significant quantity to be converted into the form that applicable following process is bio-fuel, simultaneously in hydrothermal digestion unit or near a small amount of as far as possible caramelan of formation and other catabolite.

The product obtained from catalytic reduction reactor unit can be recycled to hydrothermal digestion unit, and here it can be used as digestion solvent, and/or discharges so that subsequent transformation is bio-fuel from catalytic reduction reactor unit.Before arriving catalytic reduction reactor unit at hydrolysate, soluble carbohydrate is converted into product at least partly, can be reduced the demand of catalytic reduction reactor unit, and likely realize the higher conversion of soluble carbohydrate to product.In addition, likely use catalytic reduction reactor unit less compared with related process, this is because soluble carbohydrate was converted before arrival catalytic reduction reactor unit at least partly.In addition, better hot integrated efficiency can be realized owing to carrying out catalytic reduction reaction in hydrothermal digestion unit, may less need product to be recycled to hydrothermal digestion unit to maintain the technique of Energy Efficient from catalytic reduction reactor unit.Therefore, lower product recycle ratio can be used, more product fraction can be discharged and be converted into bio-fuel or other material with follow-up.Preceding factors also can reduce the fund relevant with conversion systems for biomass and correlation technique and running cost.

In addition about heat integration efficiency, this conversion systems for biomass is also particularly favourable, this is because the hydrothermal digestion unit in some embodiments in system can continued operation at an elevated temperature and pressure.Continuous high temperature hydrothermal digestion realizes by constructing conversion systems for biomass as follows: fresh biomass can be supplied to hydrothermal digestion unit with semicontinuous continuously, and it operates with pressurized state simultaneously.When fresh biomass not being introduced the ability in the hydrothermal digestion unit of pressurization, decompression and the cooling of hydrothermal digestion unit may be there is in living beings adding procedure, significantly reducing energy and the cost efficiency of conversion process.As used herein, term " continuously add " and grammer equivalent components thereof refer to following process: wherein cellulose biomass adds hydrothermal digestion unit to and insufficient hydrothermal digestion unit that makes reduces pressure in an uninterrupted manner.As used herein, term " semi-continuous interpolation " and grammer equivalent components thereof refer to living beings to hydrothermal digestion unit discontinuous but as required add and insufficient hydrothermal digestion unit that makes reduces pressure.The further describing of solid introducing mechanism that living beings can be supplied to the hydrothermal digestion unit of pressurization describes hereinafter in more detail.

In embodiments more as herein described, slurry catalyst can simultaneously in hydrothermal digestion unit and catalytic reduction reactor unit to regulate soluble carbohydrate to the catalytic reduction reaction of product.Using slurry catalyst, especially in hydrothermal digestion unit, can be favourable, this is because fixed bde catalyst will be very easy to embolism under cellulose biomass solid exists.In addition, by using slurry catalyst in catalytic reduction reactor unit, because the embolism possibility such as such as caused by cellulose biomass particulate reduces.Still in addition, in some embodiments, by using slurry catalyst in hydrothermal digestion unit and catalytic reduction reactor unit simultaneously, without the need to isolating (sequester) catalyst in any position, it can freely circulate between.But, in some embodiments, in hydrothermal digestion unit, catalytic reduction reactor unit or the isolation that catalyst can be implemented in the two.Owing to there is cellulose biomass solid in hydrothermal digestion unit, slurry catalyst can part be stayed wherein advantageous by cellulose biomass charging, thus reduces the needs as carried out catalyst isolation in other slurry catalyst technique.The reservation of slurry catalyst in hydrothermal digestion unit also can be aided with the low recycle ratio that can use in conversion systems for biomass as herein described.In any case, slurry catalyst can provide good catalyst distribution through the circulation of cellulose biomass charging in hydrothermal digestion unit in living beings, thus allows soluble carbohydrate as far as possible promptly to be stablized via catalytic reduction reaction after the formation thereof.

Because slurry catalyst can be smooth mobile, hydrogen sprays, solvent circulates or their any combination can be used for slurry catalyst to be dispersed throughout cellulose biomass charging distribution in hydrothermal digestion unit.Catalyst distribution good in cellulose biomass is by tackling soluble carbohydrate before having mechanism of degradation meeting in soluble carbohydrate and improving productive rate.In addition, slurry catalyst is used can to allow more successfully to use fixed bed digestion unit, this is because without the need to mechanical agitation or similar mechanical agitation to affect catalyst distribution.This can utilize higher living beings/ratio of solvent by per unit volume digestion unit compared with able one in can allowing to construct with agitator tank or similar digestion unit.In addition, owing to stirring not necessarily, before digestion occurs, the special needs of biomass solid size are not changed.

Unless otherwise specified herein, should understand and use term " living beings " or " cellulose biomass " to refer to " cellulose biomass solid " in explanation herein.Solid can be any size, shape or form.Cellulose biomass solid can these solids size any, shape or the natural existence of form, or it can in the process that takes a step forward of hydrothermal digestion.In some embodiments, cellulose biomass solid can be shredded, is ground, smashed before hydrothermal digestion, pulverizing etc. to be to produce required size.In some or other embodiment, cellulose biomass solid can washing (such as, with water, acid, alkali and combination thereof etc.) before hydrothermal digestion occurs.

When implementing embodiments of the present invention, the suitable biological matter of any type can be used to originate.Suitable cellulose biomass source can comprise, such as, and forestry waste wood, agriculture waste wood, herbaceous material, Municipal solid rubbish, rubbish and recycled writing paper, paper pulp and papermaking waste wood and their any combination.Therefore, in some embodiments, suitable cellulose biomass can comprise, such as, and maize straw, straw, bagasse, Chinese silvergrass, Chinese sorghum slag, switchgrass, bamboo, water hyacinth, hardwood, hardwood chip, hardwood pulp, cork, cork sheet, softwood pulp and their any combination.Leaf, root, seed, stalk and shell can be used as cellulose biomass source.The general source of cellulose biomass can comprise, such as, agricultural waste wood (such as, maize straw, straw, seed hulls, bagasse, shuck etc.), timber (such as, timber or bark, sawdust, timber scrap (timber slash), plant wastes (mill scrap) etc.), municipal refuse (such as, waste paper, garden cutting thing (yard clippings) or remains etc.), and energy crop (such as, willow, willow, switchgrass (switch grass), clover, grassland bluegrass (prairie bluestream), corn, soybean etc.).Cellulose biomass can be selected based on following consideration: such as, such as, cellulose and/or hemicellulose level, content of lignin, growth time/season, growth position/cost of transportation, growth cost, harvesting cost etc.

The illustrative carbohydrate (carbohydrate) that can be present in cellulose biomass can comprise, such as, and carbohydrate (sugar), sugar alcohol, cellulose, lignocellulose, hemicellulose and their any combination.Once by soluble carbohydrate being removed from living beings matrix according to digestion method as herein described, this soluble carbohydrate can be converted into via catalytic reduction reaction the product comprising oxidation intermediates.In some embodiments, the product comprising oxidation intermediates can use any combination of further hydrogenolysis, hydrogenation, condensation reaction, isomerization reaction, oligomerization, hydrotreatment reaction, alkylated reaction etc. to be further converted to bio-fuel or other material.In some embodiments, at least part of oxidation intermediates can be recycled to hydrothermal digestion unit to be constituted to small part digestion solvent.At least part of oxidation intermediates is also particularly favourable to the recirculation of hydrothermal digestion unit in the integrated and process efficiency of heat.

In some embodiments, conversion systems for biomass as herein described can comprise: comprising can the hydrothermal digestion unit of slurry catalyst (" molecular hydrogen actived slurry catalyst ") of anakmetomeres hydrogen; The optional hydrogen feeding line be operably connected with hydrothermal digestion unit; With the fluid circulation loop comprising hydrothermal digestion unit and catalytic reduction reactor unit, this catalytic reduction reactor unit also comprises slurry catalyst.

In some embodiments, cellulose biomass solid can be continuously introduced into hydrothermal digestion unit.In other embodiment, cellulose biomass solid can by discontinuous introducing hydrothermal digestion unit.In multiple embodiment, hydrothermal digestion unit can at pressurized state (such as, pressure at least 30bar) under continued operation produce the hydrolysate comprising soluble carbohydrate, soluble carbohydrate is more stable product through catalytic reduction reaction converted in-situ.Keep pressurized state can promote the digestion of cellulose biomass solid by rapid pace ideally.In some embodiments, cellulose biomass solid can be added continuously to hydrothermal digestion unit, keeps pressurized state simultaneously.In some embodiments, cellulose biomass solid can semi-continuously add hydrothermal digestion unit to, keeps pressurized state simultaneously.

In multiple embodiment, fluid circulation loop can be configured to the fluid flowing of setting up in catalytic reduction reactor unit upwards.That is, in conversion systems for biomass as herein described, in such embodiment, catalytic reduction reactor unit can be used as the operation of bubble tower catalytic reduction reactor.In some embodiments, can there is slurry catalyst isolation (sequestration) mechanism, it can work to be remained in catalytic reduction reactor unit by least part of slurry catalyst.Such as, in some embodiments, catalyst screen or filter can use with catalytic reduction reactor unit associations.Such catalyst screen and filter be those skilled in the art be familiar with.Catalyst filter or screen cloth can comprise gauze or sintering metal or ceramic filter.Solid (such as, such as, sharp sand) bed or other solid-filling bed usually by volume with the porosity of 25% or lower also can be configured to catalytic filter with separating slurry catalyst and liquid much filtrate.The external filter of configurable such as cake filtration device (cake filter), wherein filter medium can be the grain bed of cloth, sintering metal, metallic sieve or fabric, porous ceramics, pressed felt or cotton-wool, supatex fabric, filter paper, polymer film or granular solids.Use the filter of these filter mediums can comprise cake filtration device, level or vertical leaf filter, plate and frame filter press, leaf filter, tubular filter, drum type filteration device, centrifugal discharge filter etc.Centrifuge, hydrocyclone and gravitation settler also can be used for separating slurry catalyst and liquid phase and circulation slurry catalyst.Pump, screw rod or conveyer belt, such as, can be used for the slurry catalyst of separation or enrichment to be transmitted back to catalytic reduction reactor unit.In other embodiment, catalytic reduction reactor unit can not comprise inner catalyst interrupter, and slurry catalyst can be looped back hydrothermal digestion unit simply when conversion systems for biomass works.

In some embodiments, hydrothermal digestion unit can be, such as, and the pressure vessel of carbon steel, stainless steel or similar alloy.In some embodiments, single hydrothermal digestion unit can be there is.In other embodiment, two or more hydrothermal digestion unit of parallel operation can be used.Suitable hydrothermal digestion unit can comprise, such as, " PANDIATM Digester " (Voest-AlpineIndustrienlagenbau GmbH, Linz, Austria), " DEFIBRATOR Digester " (Sunds Defibrator AB Corporation, Stockholm, Sweden), M & D (Messing & Durkee) digester (Bauer Brothers Company, Springfield, Ohio, and KAMYR Digester (Andritz Inc. USA), Glens Falls, New York, USA).The suitable constructions of hydrothermal digestion unit can comprise, and such as, trickle bed, heap formula (pile-type), fluid bed contact with stirring (stirred contact).In addition, concurrent flow or counter-current flow can be present in digestion unit.

In some embodiments, conversion systems for biomass also can comprise solid retraction mechanism, and it is operationally connected with hydrothermal digestion unit.Solid retraction mechanism can promote that cellulose biomass solid is to the introducing in digestion unit, and allows, when adding other cellulose biomass solid, digestion unit is remained on pressurized state.In multiple embodiment, solid retraction mechanism can comprise pressure transition district, and it circulates between lower pressure state and elevated pressures state.In some other embodiments, solid retraction mechanism also can comprise atmospheric pressure region.In some embodiments, solid retraction mechanism can comprise atmospheric pressure region and in atmospheric pressure and the pressure transition district of more circulating between high-pressure state.Position by solid retraction mechanism used is decided by the selection whether comprising atmospheric pressure region, as discussed in detail in institute below this paper.In some embodiments, solid retraction mechanism can be used for cellulose biomass solid to become the high pressure conditions being applicable to being introduced into pressurized thermal water digestion unit from low-pressure state.In some embodiments, solid retraction mechanism can be used for cellulose biomass solid to become the high pressure conditions being suitable for being introduced into hydrothermal digestion unit from atmospheric pressure.

When it is present, suitable atmospheric pressure region can comprise, such as, and ribbon conveyer, the tubular conveyor that shakes, screw feeder or transporter, collecting tank, buffer, box distributor etc.Can work and can to comprise with continuous or semi-continuous suitable pressure transition district cellulose biomass solid being added to pressurization digestion unit, such as, pressing screw feeder, pressures cycle room etc., as described in the U.S. Patent Application Publication 2013/0152457 and 2013/0152458 owned together.In some embodiments, even when the pressure of cellulose biomass solid is elevated to the pressure of rising from atmospheric pressure, atmospheric pressure region also can optionally be omitted.That is, in such embodiment, cellulose biomass solid can be added directly to pressure transition district and carry out pressures cycle to be introduced into pressurization digestion unit.

In some embodiments, solid retraction mechanism can allow cellulose biomass solid be introduced into hydrothermal digestion unit and digestion unit can not be made to reduce pressure completely.Digestion unit can be allowed to keep pressurization and continued operation the pressurization of cellulose biomass solid before introducing digestion unit.This can contribute to keeping the integrated and energy efficiency of the heat in living beings digestion process as described above.Before digestion, other benefit that cellulose biomass solid pressurizes also is discussed hereinafter.

In some embodiments, the pressurization in the pressure transition district of solid retraction mechanism can be undertaken by least part of liquid phase in digestion unit is introduced pressure transition district at least partly.In some or other embodiment, the pressurization in pressure transition district can be undertaken by being introduced in pressure transition district by gas at least partly.

In some embodiments, liquid phase can comprise organic solvent, and its product as catalytic reduction reaction produces.In other embodiment, external solvent can be used for pressure transition district to pressurize.

Use the liquid phase from digestion unit that the pressurization of cellulose biomass solid can be realized at least two benefits.First, digestion solvent can be made to immerse living beings biomass solid pressurization in the presence of a liquid phase, this can make living beings just be immersed in digestion solvent once introducing digestion unit.In addition, by adding hydro-thermal phase to the biomass solid in pressure transition district, needing to input less energy and making living beings reach temperature when it has just entered digestion unit.These features all can improve the efficiency of digestion process.

In some embodiments, slurry catalyst can comprise poisoning resistant catalyst.Use poisoning resistant catalyst can be particularly desirable, this is because do not removed from cellulose biomass solid by catalyst poison before generation hydrothermal digestion and integrated catalytic reduction.As used herein, " poisoning resistant catalyst " be defined as can anakmetomeres hydrogen but the catalyst that need not need regeneration or change because of low catalytic activity for continued operation at least 12 hours.Use poisoning resistant catalyst can avoid and catalyst regeneration or the shortcoming changing the relevant process shutdown phase.Except the loss production time, considerable energy expenditure may be needed when restarting hydrothermal digestion process.

In some embodiments, suitable poisoning resistant catalyst can comprise, such as, and the catalyst of sulfuration.Be applicable to the catalyst of the sulfuration of anakmetomeres hydrogen as described in the U.S. Patent Application Publication 2012/0317872,2012/0317873 and 2013/0109896 owned together.Sulfuration is undertaken by such as under type: use hydrogen sulfide treatment catalyst, simultaneously optional by catalyst deposit on a solid support.In embodiment more specifically, poisoning resistant catalyst can comprise the cobalt-molybdenum phosphate catalyst of sulfuration.We find, and according to reaction condition, the cobalt-molybdenum phosphate catalyst of sulfuration can produce C ₂-C ₆monohydric alcohol, glycol (comprising glycol), triol and combination thereof, can not form the C of volume simultaneously ₂-C ₄alkane.As used herein, term " monohydric alcohol " refers to the organic molecule comprising single alcohol functional group.The monohydric alcohol formed easily can be separated with water via rapid evaporation or liquid-liquid phase separation, and in acid or base catalyst, experiences condensation-oligomerization in a separate step to produce the liquid biofuel in gasoline, aviation kerosine gasoline or diesel range.Slurry catalyst containing Pt or Pd can be for the particularly useful poisoning resistant catalyst in present embodiment.

In some embodiments, poisoning resistant catalyst in methods described herein is suitable for by such as under type sulfuration: be dispersed in fluid-phase by slurry catalyst, and add vulcanizing agent wherein.Suitable vulcanizing agent can comprise, such as, and organic sulfoxide (such as, methyl-sulfoxide), hydrogen sulfide, sulfhydrate salt (such as, NaSH) etc.In some embodiments, slurry catalyst can be enriched in after curing in fluid-phase and to be added to hydrothermal digestion unit subsequently.

In some embodiments, slurry catalyst can be reproducible.Such as, in some embodiments, slurry catalyst regenerates higher than the water of its normal boiling point by being exposed to temperature.As used herein, " Regenrable catalyzed dose " even still recovers its at least some catalytic activity by regeneration when being poisoned by nitrogen compound impurity, oxidation of sulfur compound impurities or their any combination.Ideally, this Regenrable catalyzed dose should regenerate with the minimum process shutdown phase.In some embodiments, slurry catalyst is by being exposed to the water reuse (treatment that temperature is at least 200 DEG C.In some embodiments, slurry catalyst is by being exposed to the water reuse (treatment that temperature is at least 250 DEG C.In some embodiments, slurry catalyst is the water reuse (treatment of at least 300 DEG C by temperature.In some embodiments, slurry catalyst is the water reuse (treatment of at least 350 DEG C by temperature.In some embodiments, slurry catalyst is the water reuse (treatment of at least 400 DEG C by temperature.Water for regeneration slurry catalyst can be subcritical state or supercriticality.The ruthenium arranged on a solid support by being exposed to temperature higher than the specially suitable slurry catalyst of the water reuse (treatment of its normal boiling point, such as, such as, ruthenium on the titanium dioxide or the ruthenium on carbon.Other suitable slurry catalyst can comprise layout platinum on a solid support or palladium compound.Also can regenerate by heat-treating with hydrogen at least partly for the most effective catalyst of mediation catalytic reduction reaction.The regeneration of slurry catalyst can betide hydrothermal digestion unit, catalytic reduction reactor unit or other position as required.

In some embodiments, slurry catalyst can work to produce molecular hydrogen.Such as, in some embodiments, the catalyst (that is, APR catalyst) being suitable for aqueous phase reforming can be used.Suitable APR catalyst can comprise, and such as, forms alloy or the catalyst with the platiniferous of their modifications, palladium, ruthenium, nickel, cobalt or other group VIII metal with ruthenium, molybdenum, tin or other metal.Therefore, in embodiments more as herein described, external hydrogen can not be needed to supply.But in other embodiment, the external hydrogen that the hydrogen optionally occurred with inside can be used to combine supplies.

In multiple embodiment, slurry catalyst can have 250 microns or less particle diameter.In some embodiments, slurry catalyst can have 100 microns or less particle diameter.In some embodiments, slurry catalyst 10 microns or less particle diameter.In some embodiments, the minimum grain size of slurry catalyst can be 1 micron.In some embodiments, the slurry catalyst in methods described herein can comprise catalyst fines.As used herein, term " catalyst fines " refers to that nominal particle size is 100 microns or less solid catalyst.Catalyst fines can be produced by Catalyst Production technique, such as, in solid catalyst extrusion.Catalyst fines is also by grinding larger catalyst solid or producing in catalyst solid regenerative process.Produce the appropriate method of catalyst fines at United States Patent (USP) 6,030,915 and 6,127, describe in 299.In some cases, catalyst fines can be removed from solid catalyst production run, this is because they are difficult to isolation in some catalytic processs.The technology removing catalyst fines from larger catalyst solid can comprise, such as, and screening or similar particle diameter separation method.Due in embodiment described herein without the need to catalyst is retained in fixed position, catalyst fines especially can be tolerated.Advantageously, because its size is little, catalyst fines can be easy to fluidisation and be dispersed throughout cellulose biomass solids distribution.

In some embodiments, the catalytic reduction reaction carried out in hydrothermal digestion unit and catalytic reduction reactor unit can be hydrogenolysis.Hydrogenolysis describes in detail and is included in hereinafter.

In some embodiments, fluid circulation loop can be configured to set up fluid flowing upwards in hydrothermal digestion unit.As used herein, also referred to as " counter-current flow ", term " fluid flowing upwards " refers to that the product relative to the direction of living beings introducing digestion unit enters the direction of hydrothermal digestion unit in this article.By making the fluid flows upward comprising slurry catalyst enter in cellulose biomass charging, slurry catalyst can become well distributed in entirety.Specifically, fluid flowing upwards can cause the compacting of ground cellulose biomass charging to antigravity, thus makes the distribution of slurry catalyst easier.Also other flowing can be used to arrange, such as, such as, concurrent flow.

In some embodiments, the hydrothermal digestion unit of conversion systems for biomass as herein described can comprise the reservation mechanism for being remained on by cellulose biomass wherein.In some embodiments, the reservation mechanism in hydrothermal digestion unit can work to retain the cellulose biomass solid that particle diameter is 3mm or larger.That is, when there is reservation mechanism, cellulose biomass particulate and slurry catalyst freely can circulate in whole conversion systems for biomass, but larger cellulosic biomass particles can be retained in hydrothermal digestion unit.Suitable reservation mechanism can comprise, such as, and screen cloth etc.

In some embodiments, can there is the product be communicated with fluid circulation loop fluid and take out pipeline, wherein this product takes out pipeline between hydrothermal digestion unit and catalytic reduction reactor unit export.In some embodiments, the solid separating mechanism taking out pipeline with product and be operably connected can be there is.Solid separating mechanism in this position be used in product before downstream is further converted to bio-fuel or other material by solid from wherein removing.In some embodiments, product taking-up pipeline can be operably connected with hydrothermal digestion unit.The product be operationally connected with hydrothermal digestion unit is taken out the pipeline product that can be used as between hydrothermal digestion unit and catalytic reduction reactor unit export and is taken out substituting of pipeline or supplement and exist.

Be applicable to being included in the solid separating mechanism that the product in conversion systems for biomass takes out in pipeline or other position and can relate to any isolation technics known in the art, comprise, such as, filter, centrifugal force-or separating mechanism (such as, hydrocyclone), subsider, centrifuge etc. based on centrifugal force.Suitable filter can comprise, such as, and surface filter and deep filter.Surface filter can comprise, such as, and filter paper, film, porosu solid medium etc.Deep filter can comprise, and such as, is designed at the post of the porous media of its cored structure IT solid or plug.In some embodiments, can use two or more filters, at least one in its middle filtrator can by backwash, and fluid flowing upwards simultaneously continues through at least some in residue filter.In some embodiments, one or more hydrocyclone can be used.

Although also solid separation can be carried out in fluid circulation loop as required, solid is not usually needed to be separated in this position, this is because hydrothermal digestion unit and catalytic reduction reactor unit all comprise particulate matter (such as, slurry catalyst).

Previously described conversion systems for biomass will be adopted now and examines accompanying drawing and further describe.Fig. 1 shows the schematic diagram of the illustrative conversion systems for biomass in fluid circulation loop with hydrothermal digestion unit and the catalytic reduction reactor unit be connected with each other, and wherein hydrothermal digestion unit and catalytic reduction reactor unit all comprise slurry catalyst.Conversion systems for biomass 1 comprises hydrothermal digestion unit 2, and the latter is communicated with via fluid circulation loop 10 fluid with catalytic reduction reactor unit 4.As shown in the figure, fluid circulation loop 10 is configured to set up fluid flowing upwards in hydrothermal digestion unit 2.Be communicated with the fluid of other type of hydrothermal digestion unit 2 and be also fine.The flow direction of the living beings direction of introducing hydrothermal digestion unit 2 and wherein most of living beings as the dotted line arrows.Optional hydrogen feeding line 8 is operationally connected with hydrothermal digestion unit 2.Optional hydrogen feeding line also can operationally be connected with catalytic reduction reactor unit 4, but does not for clarity sake draw.Catalyst granules 9 and 9' can be present in hydrothermal digestion unit 2 and catalytic reduction reactor unit 4 respectively.As in Fig. 1 paint, fluid circulation loop 10 is configured to make fluid flow through catalytic reduction reactor unit 4 in an upward manner.

Cellulose biomass solid introduces hydrothermal digestion unit 2 by solid retraction mechanism 14, and described solid retraction mechanism 14 comprises atmospheric pressure region 15 and pressure transition district 16.Atmospheric pressure region 15 can comprise the structure that such as hopper, case etc. can hold the cellulose biomass solid introducing hydrothermal digestion unit 2.Pressure transition district 16 can comprise any structure of the pressure that can improve the solid be introduced in hydrothermal digestion unit 2.Also can circulate in pressure transition district 16 between atmospheric pressure and the pressure state of rising.Optionally, solid retraction mechanism 14 can be omitted, and cellulose biomass solid directly can add pressure transition district 16 to introduce in hydrothermal digestion unit 2.

Conversion systems for biomass 1 also comprises product and takes out pipeline 18, and it is communicated with fluid circulation loop 10 fluid after catalytic reduction reactor unit 4 exports.In conversion systems for biomass 1 operating process, product can be left catalytic reduction reactor unit 4 and flow through pipeline 20.Now, product can be taken out pipeline 18 by product subsequently and to be removed from fluid circulation loop 10 or to be recycled to hydrothermal digestion unit 2 by pipeline 22.Take out by product product that pipeline 18 removes can experience subsequently and be follow-uply further converted to bio-fuel.The product that product is taken out in pipeline 18 can have the solid be separated by it by optional solid separating mechanism 24.Suitable solid separating mechanism can comprise, and such as, one or more filters, one or more hydrocyclones, centrifuge, film, subsider etc., as discussed in detail further above.The product turning back to hydrothermal digestion unit 2 via pipeline 22 such as can be further converted to product as digestion solvent or experience.

Other optional member multiple can be present in conversion systems for biomass 1.A kind of optional member that can be included in conversion systems for biomass 1 is phase separation mechanism 26, and it is communicated with pipeline 20 fluid.As hereinafter further described, phase separation mechanism 26 can be used for the organic phase of product is at least part of and aqueous phase separation.Other position for phase separation mechanism 26 is also feasible.

Optional pipeline 30 can be used for shifting liquid phase from hydrothermal digestion unit 2.As in Fig. 1 paint, pipeline 30 can be used for shifting liquid phase with the pressure transition district 16 of solid retraction mechanism 14 of pressurizeing at least partly from hydrothermal digestion unit 2.Other structure for pipeline 30 is also feasible.Before pressurization and introducing Pressed bio matter to hydrothermal digestion unit 2, cellulose biomass solid can be supplied to pressure transition district 16 from atmospheric pressure region 15.By using pressure transition district 16, hydrothermal digestion unit 2 need not reduce pressure completely in cellulose biomass solid adding procedure, makes digestion process carry out in substantially unbroken mode thus.

In some embodiments, the method processing cellulose biomass solid can comprise: comprise can anakmetomeres hydrogen slurry catalyst hydrothermal digestion unit in cellulose biomass solid is provided; Under molecular hydrogen exists in hydrothermal digestion unit heating cellulose biomass solid, make slurry catalyst cycle through described hydrothermal digestion unit simultaneously, thus formed and comprise the hydrolysate of soluble carbohydrate in the liquid phase; When soluble carbohydrate is in hydrothermal digestion unit, soluble carbohydrate is converted into product at least partly; With at least part of liquid phase is transferred to the catalytic reduction reactor unit also comprising slurry catalyst so that further transforming soluble carbohydrate is product.

In some embodiments, the method of process cellulose biomass solid can comprise: provide conversion systems for biomass, it comprises: comprising can the hydrothermal digestion unit of slurry catalyst of anakmetomeres hydrogen, the optional hydrogen feeding line be operably connected with hydrothermal digestion unit, and comprise hydrothermal digestion unit and also comprise the fluid circulation loop of catalytic reduction reactor unit of slurry catalyst; Under molecular hydrogen exists in hydrothermal digestion unit heating cellulose biomass solid, make slurry catalyst cycle through described hydrothermal digestion unit simultaneously, thus formed and comprise the hydrolysate of soluble carbohydrate in the liquid phase; When soluble carbohydrate is in hydrothermal digestion unit, soluble carbohydrate is converted into product at least partly; Catalytic reduction reactor unit is transferred to, so that transforming soluble carbohydrate is further product with by least part of liquid phase.

In some embodiments, before digestion, cellulose biomass can be washed and/or be reduced size (such as, by chopping, fragmentation, peeling etc.) to reach ideal dimensions for digestion and amount.These operations can be removed the material of the further chemical conversion of interference soluble carbohydrate and/or be improved the infiltration of digestion solvent to living beings.In some embodiments, washing can betide in hydrothermal digestion unit before pressurization.In other embodiment, washing can occur before living beings are placed in hydrothermal digestion unit.

Usually, the digestion in hydrothermal digestion unit can occur in the liquid phase.In some embodiments, liquid phase can comprise the digestion solvent of water.In some embodiments, liquid phase also can comprise organic solvent.In some embodiments, organic solvent can comprise the oxidation intermediates produced by the catalytic reduction reaction of soluble carbohydrate.Such as, in some embodiments, digestion solvent can comprise the oxidation intermediates produced by the hydrogenolysis of soluble carbohydrate or other catalytic reduction reaction.In some embodiments, oxidation intermediates can comprise by situ catalytic reduction reaction and/or produced by catalytic reduction reactor unit those.In some embodiments, bio-ethanol can be added in water together with comprising the solvent of the oxidation intermediates produced subsequently as initial digestion solvent.Also can use as required can be miscible with water other organic solvent any as initial digestion solvent.Usually, the liquid phase that can there is q.s in digestion process keeps wetting to make biological surface.The amount of liquid phase can be chosen as further and keep the soluble carbohydrate of enough high concentrations to keep desirable high reaction speed in catalytic reduction process, but can not be too high so that be degraded into problem.In some embodiments, the concentration of soluble carbohydrate can keep below the 5wt% of liquid phase to make minimum degradation.But, should recognize and can use higher concentration in some embodiments.In some embodiments, organic acid such as acetic acid, oxalic acid, salicylic acid or acetylsalicylic acid can comprise in the liquid phase as the sour promoter of digestion process.

In some embodiments, digestion solvent can comprise the organic solvent of the oxidation intermediates comprising the catalytic reduction reaction deriving from soluble carbohydrate.Catalytic reduction reaction can occur in hydrothermal digestion unit and/or catalytic reduction reactor unit.In some embodiments, organic solvent can comprise at least one alcohol, ketone or polyalcohol.In substituting embodiment, digestion solvent can be supplied by external source at least partly.Such as, in some embodiments, bio-ethanol can be used for supplementary organic solvent.Other can also can use by the organic solvent miscible with water.In some embodiments, digestion solvent can separated, store or Selective implantation hydrothermal digestion unit in keep the soluble carbohydrate of ideal concentration or to provide temperature adjusting at hydrothermal digestion unit.

In multiple embodiment, digestion can occur within a period of time under the temperature and pressure raised.In some embodiments, digestion can carry out a period of time the temperature of 100 DEG C-240 DEG C.In some embodiments, time span can between 0.25 hour and 24 hours.In some embodiments, the digestion producing soluble carbohydrate can be carried out under the pressure between 1bar (absolute pressure)-100bar.Usually, temperature is higher, and the time quantum occurred needed for hydrothermal digestion step is shorter.As an example, hydrothermal digestion 180 DEG C-270 DEG C, the temperature that is more typically in 190 DEG C-250 DEG C can carry out 1 hour-10 hours.

In multiple embodiment, suitable living beings digestion technology can comprise, such as, and sour digestion, soda boiling solution, enzyme digestion and the digestion of use hot pressurized water.

In some embodiments, the method also can comprise at least part of product from conversion systems for biomass (such as, from the outlet of catalytic reduction reactor unit or from fluid circulation loop) discharge.In some embodiments, the method also can comprise and product is converted into bio-fuel, as hereinafter described in further detail.In some embodiments, the method also can be included in as described above by product from conversion systems for biomass discharge after from this product separating solids (such as, slurry catalyst, living beings particulate etc.).

In some embodiments, the method also can comprise at least part of liquid phase is recycled to hydrothermal digestion unit from catalytic reduction reactor unit.As mentioned above, conversion systems for biomass as herein described particularly advantageously promptly can transform soluble carbohydrate by carrying out situ catalytic reduction reaction in hydrothermal digestion unit is at least partly the product comprising oxidation intermediates.Similarly, as described above, the liquid phase comprising product can be recycled to hydrothermal digestion unit from catalytic reduction reactor unit, here liquid phase can, such as, contribute to regulating and controlling temperature wherein, as digestion solvent etc.Can different recycle ratio occur from catalytic reduction reactor unit to the recirculation of hydrothermal digestion unit.As used herein, term " recycle ratio " refers to and is recycled to hydrothermal digestion unit (such as, in fluid circulation loop) the amount of liquid phase relative to the amount of the liquid of discharging from conversion systems for biomass (such as, taking out pipeline by product).

The special benefit of carrying out situ catalytic reduction reaction in hydrothermal digestion unit can use lower recycle ratio when liquid phase being recycled to hydrothermal digestion, still keeps process efficiency and productive rate simultaneously.Specifically, can the digestion process heat supply that occurs to hydrothermal digestion unit from recirculation product of less needs, because there occurs the catalytic reduction reaction of heat release wherein.Therefore, the relatively a high proportion of liquid phase leaving catalytic reduction reactor unit can be discharged so that subsequent transformation is bio-fuel from conversion systems for biomass.Lower recycle ratio also can allow to use less reactor volume, because the total flow rate of liquid in hydrothermal digestion unit and catalytic reduction reactor reduces.High recycle ratio and high flow rate of liquid can cause too much pressure drop, high pump energy and size requirements and other unfavorable feature.Minimizing residence time can not be made can to cause comparatively low-yield before carrying out via catalytic reduction reaction stablizing.Due to benefit of the present disclosure, those skilled in the art can determine the recycle ratio of the suitable liquid phase recirculation realizing required hot integrated amount, balance the ideal velocity that downstream bio-fuel is produced simultaneously.In some embodiments, liquid phase is recycled to hydrothermal digestion unit with the recycle ratio of 0.2-10 from catalytic reduction reactor unit.In some embodiments, liquid phase can 1-10, or 1-5, or 0.2-2, or 0.5-2, or 1-2, or 0.2-1, or the recycle ratio of 0.5-1 is recycled to hydrothermal digestion unit from catalytic reduction reactor unit.In some embodiments, liquid phase can 2 or lower recycle ratio be recycled to hydrothermal digestion unit from catalytic reduction reactor unit.In some embodiments, liquid phase can 1 or lower recycle ratio be recycled to hydrothermal digestion unit from catalytic reduction reactor unit.In some embodiments, liquid phase can be recycled to hydrothermal digestion unit from catalytic reduction reactor unit, to make the fluid flowing of setting up in hydrothermal digestion unit upwards.In other embodiment, also can set up other type of flow in hydrothermal digestion unit, comprise such as concurrent flow.

In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can occur under the pressure of at least 30bar.Under remaining on the pressure of at least 30bar, digestion can guarantee that digestion is carried out with satisfactory rate.In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can carry out under the pressure of at least 60bar.In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can carry out under the pressure of at least 90bar.In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can carry out under the pressure of 30bar-430bar.In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can carry out under the pressure of 50bar-330bar.In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can carry out under the pressure of 70bar-130bar.In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can carry out under the pressure of 30bar-130bar.Pressure when aforementioned pressure refers to that digestion is carried out should be noted.That is, aforementioned pressure is the routine operating pressure of hydrothermal digestion unit.

Because conversion systems for biomass of the present invention provides the stable of soluble carbohydrate by carrying out situ catalytic reduction reaction in hydrothermal digestion unit, longer contact time is more feasible, this is because the degraded of soluble carbohydrate is less relevant.In some embodiments, can be 1 hour contact time or more.In some embodiments, can be 2 hours contact time or more, or 4 hours or more, or 6 hours or more, or 8 hours or more, or 10 hours or more, or 12 hours or more, or 24 hours or more.Especially, for batch processing, the time of 1 hour-24 hours can be used.

Usually, after the digestion in hydrothermal digestion unit occurs, only a small amount of initial fiber cellulosic biomass solid can keep not by digestion.In some embodiments, after being in hydrothermal digestion unit heating (such as, in the second temperature and the second time), the cellulose biomass solid being less than 40% based on dry weight can keep not by digestion.In some embodiments, after being in hydrothermal digestion unit heating, being less than 30% cellulose biomass solid and can keeping not by digestion based on dry weight.In some embodiments, after being in hydrothermal digestion unit heating, being less than 20% cellulose biomass solid and can keeping not by digestion based on dry weight.In some embodiments, after being in hydrothermal digestion unit heating, being less than 10% cellulose biomass solid and can keeping not by digestion based on dry weight.

In some embodiments, poisoning resistant slurry catalyst can be used for the method.Suitable poisoning resistant slurry catalyst describes above.In some embodiments, reproducible catalyst can be used for the method.In some embodiments, the method also can comprise regeneration slurry catalyst.In some embodiments, the method also can comprise and is at least 200 DEG C by being exposed to temperature, or at least 250 DEG C, or at least 300 DEG C, or at least 350 DEG C, or the water reuse (treatment slurry catalyst of at least 400 DEG C.

In some embodiments, method of the present invention also can comprise and carries out being separated of product.In some embodiments, be separated can be used in catalytic reduction reactor unit outlet after exist phase separation mechanism carry out.In multiple embodiment, the enforcement be separated can comprise bilayer (bilayer) and be separated, and implements solvent-stripping operation, implements extraction, implements to filter, implements distillation etc.In some embodiments, azeotropic distillation can be carried out.

In some embodiments, methods described herein also can comprise that to be converted into product be bio-fuel.In some embodiments, product can be converted into the product comprising oxidation intermediates from catalytic hydrogenolytic cleavage to the conversion of bio-fuel by the soluble carbohydrate produced from hydrothermal digestion, as mentioned above.As further described above, the liquid phase comprising product can be recycled to hydrothermal digestion unit with further auxiliary cooking solution preocess.In some embodiments, product transforms further by the further catalytic reforming reaction of any quantity, and described further catalytic reforming reaction comprises, such as, other catalytic reduction reaction (such as, hydrogenolysis, hydrogenation, hydrotreatment reaction etc.), condensation reaction, isomerization reaction, desulphurization reaction, dehydration, oligomerization, alkylated reaction etc.Initial hydrogenolysis and further catalytic reforming reaction describe hereinafter.

The multiple method of carbohydrate being carried out to hydrogenolysis is known.A kind of suitable method comprises and carbohydrate or stable hydroxy intermediate is comprised oxidation intermediates (such as with the hydrogen optionally mixed with diluent gas and hydrogenolysis catalyst effective formation, such as, comparatively Small molecular or polyalcohol) product condition under contact.As used herein, term " comparatively Small molecular or polyalcohol " comprises any molecule with lower molecular weight, and it can comprise carbon atom or the oxygen atom of lesser number compared with initial carbohydrate.In some embodiments, product can comprise the comparatively Small molecular of such as polyalcohol and alcohol.This one side of hydrogenolysis needs to destroy carbon-carbon bond.

In some embodiments, soluble carbohydrate can use hydrogenolysis can be converted into metastable oxidation intermediates under the catalyst existence of anakmetomeres hydrogen, such as, such as, and propylene glycol, ethylene glycol and glycerine.Suitable catalyst can comprise, such as, Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, Os separately or together with the promoter of such as Au, Ag, Cr, Zn, Mn, Sn, Bi, B, O and their alloy or any combination and their alloy or any combination.In some embodiments, catalyst and promoter can allow hydrogenation and hydrogenolysis simultaneously or recur, such as carbonyl hydrogenated to form alcohol.Catalyst also can comprise the carbonaceous pyropolymer catalyst comprising transition metal (such as, chromium, molybdenum, tungsten, rhenium, manganese, copper and cadmium) or group VIII metal (such as, iron, cobalt, nickel, platinum, palladium, rhodium, ruthenium, iridium and osmium).In some embodiments, catalyst can comprise any above-mentioned metal combining or adhere to catalytic activity carrier with alkaline earth oxide.In some embodiments, the catalyst described in hydrogenolysis can comprise catalyst carrier.

The condition of carrying out hydrogenolysis can change according to the type of such as living beings parent material and required product (such as gasoline or diesel oil).Those skilled in the art will appreciate that the appropraite condition for carrying out this reaction based on benefit of the present disclosure.Usually, hydrogenolysis can carry out the temperature of 110 DEG C-300 DEG C, preferably 170 DEG C-300 DEG C, most preferably 180 DEG C-290 DEG C.

In some embodiments, hydrogenolysis can carry out in the basic conditions, and preferred pH is 8-13, and even more preferably pH is 10-12.In some embodiments, hydrogenolysis can carry out under the pressure of 1bar (absolute pressure)-150bar, the pressure of preferred 15bar-140bar, the even more preferably pressure of 50bar-110bar.

Hydrogen used in hydrogenolysis can comprise external hydrogen, recycle hydrogen, generated in-situ hydrogen or their any combination.

In some embodiments, the product of hydrogenolysis can comprise more than 25mol%, or alternatively, more than the polyalcohol of 30mol%, this can cause being converted into bio-fuel more in subsequent treatment reaction.

In some embodiments, hydrogenolysis can be carried out, because also need facilitation of hydrolysis to react except hydrogenolysis under neutrality or acid condition.Such as, the hydrolysis of oligomeric carbohydrate can be combined with hydrogenation and be produced sugar alcohol, and the latter can experience hydrogenolysis.

The second aspect of hydrogenolysis needs to destroy-OH key, such as: RC (H) ₂-OH+H ₂→ RCH ₃+ H ₂o.This reaction is also called " hydrogenation deoxidation ", and the hydrogenolysis can destroyed with C-C key is parallel occurs.Glycol can be converted into single oxygenatedchemicals via this reaction.Due to reaction the order of severity with temperature raise or increase with catalyst contact time and increase, polyalcohol and glycol can reduce because of hydrogenation deoxidation relative to the concentration of single oxygenatedchemicals.Selective will the change with catalyst type and formula of C-C key hydrogenolysis contrast C-OH key hydrogenolysis.It is alkane that complete deoxidation also may occur, if but be intended that and produce single oxygenatedchemicals or can condensation or the oligomeric glycol for the more compound of high molecular and polyalcohol in subsequent processing steps, this is normally undesirable.Usually, higher polyol it is desirable to only single oxygenatedchemicals or glycol are sent to subsequent processing steps, because may cause too much coke to be formed in condensation or oligomerization process.On the contrary, alkane is nonreactive substantially, and easily can not combine the compound producing higher molecular weight.

Once after forming oxidation intermediates by hydrogenolysis, a part of product can be recycled to hydrothermal digestion unit to be used as the inner digestion solvent generated.Another part of product can be discharged and by further reforming reaction, process forms bio-fuel subsequently.After the further reforming reaction of experience, oxidation intermediates is optionally separated into different component.Suitable separation can comprise, and such as, is separated, solvent stripper, extractor, filter, distillation etc.In some embodiments, product can process or carry out before being recycled to hydrothermal digestion unit by lignin and oxidation intermediates be separated subsequently further.

Oxidation intermediates can carry out processing to produce fuel mixture in one or more processing reaction.In some embodiments, condensation reaction can use to generate fuel mixture together with other reacts, and by comprising acid, alkali or the catalyst of the two.Usually, be not limited to any concrete theory, believe that alkaline condensation reaction can relate to following series of steps: the dehydrogenation reaction that (1) is optional; (2) optional dehydration, it can be acid catalyzed; (3) aldol reaction; (4) optional ketonize reaction; (5) optional furan nucleus ring-opening reaction; (6) hydrogenation of gained condensation product forms >C4 hydrocarbon; (7) their any combination.Acid catalyzed condensation can limit optional hydrogenation or dehydrogenation reaction similarly, dehydration and oligomerization.Also extra refining reaction can be used to meet specific fuel standard to make product, and the reaction carried out under being included in hydrogen and hydrogenation catalyst existence is to remove functional group from final fuel Products.In some embodiments, base catalyst, there is bronsted lowry acids and bases bronsted lowry functional site catalyst (optionally comprising metal function) simultaneously and can be used for realizing condensation reaction.

In some embodiments, aldol reaction can be used for producing the fuel mixture meeting diesel fuel or aviation kerosine demanded fuel.Traditional diesel fuel is the petroleum distillate being rich in alkane.Their boiling point is wide reaches 187 DEG C-417 DEG C, and it is suitable for burning in compression ignition engine, such as diesel-engine road vehicle.U.S. material is learned (ASTM) with test and is established diesel fuel grades according to boiling spread and with the allowable range of other fuel performance (such as Cetane number, cloud point, flash-point, viscosity, aniline point, sulfur content, moisture, dust burdening, copper strip corrosion and carbon residue).Therefore, any fuel mixture meeting ASTM D975 can be defined as diesel fuel.

The disclosure additionally provides the method preparing aviation kerosine fuel.Aviation kerosine fuel is transparent in festucine.Modal fuel be classified as Aeroplane A-1 unleaded/paraffinic base oil fuel, its produce to meet standard ISO group.Aviation kerosine fuel is the mixture of a large amount of different hydrocarbons, may reach thousands of kinds or more.The scope of its size (molecular weight or carbon number) needs limit by product, such as, and freezing point or smoke point.Kerosene-type aircraft fuel (comprising Jet A and Jet A-1) has the carbon number distribution between C8-C16.Long distillate or naphtha-type aircraft fuel (comprising JetB) have the carbon number distribution between C5-C15 usually.The fuel mixture meeting ASTM D1655 may be defined as aviation kerosine fuel.

In some embodiments, two kinds of aircraft fuels (Jet A and Jet B) all comprise multiple additives.Available additive includes, but are not limited to, and antioxidant, antistatic additive, corrosion inhibitor and fuel system are frozen and suppressed (FSII) agent.Antioxidant prevents cementing, and usually based on alkylating phenol, such as, AO-30, AO-31 or AO-37.Antistatic additive static dissipation also prevents sparking.Having dinonylnaphthalene sulfonic acid (DINNSA) as the Stadis 450 of active component is an example.Corrosion inhibitor (such as, DCI-4A) is for civil and military fuel, and DC I-6A is used for military fuel.FSII agent comprises, such as, and Di-EGME.

In some embodiments, oxidation intermediates can comprise the carbonyl containing compound that can participate in base catalyzed condensation reaction.In some embodiments, optional dehydrogenation reaction can be used for the amount of the carbonyl containing compound improved in the oxidation intermediates logistics being used as condensation reaction charging.In these embodiments, oxidation intermediates and/or the logistics of part biological based raw material can dehydrogenations in the presence of a catalyst.

In some embodiments, dehydrogenation can be preferred for the oxidation intermediates logistics comprising alcohol, glycol and triol.Usually, alcohol can not participate in aldol condensation directly.The oh group existed or multiple oh group can be converted into carbonyl (such as, aldehyde, ketone etc.) to participate in aldol reaction.Dehydrogenation can be comprised to realize the dehydrogenation of the alcohol, glycol or the polyalcohol that exist to form ketone and aldehyde.Dehydration catalyst is formed by the same metal for hydrogenation, hydrogenolysis or aqueous phase reforming usually.These catalyst describe hereinbefore in more detail.Dehydrogenation productive rate is improved by removing when forming hydrogen in course of reaction or consuming.Dehydrogenation step can carry out as independent reactions steps before aldol reaction, or dehydrogenation reaction can be carried out with aldol reaction is collaborative mutually.For dehydrogenation collaborative mutually and aldol reaction, dehydrogenation and aldol condensation function can occur on the same catalyst.Such as, metal hydrogenation/dehydrogenation degree of functionality can be present in and comprises on the catalyst of basic functionality.

Dehydrogenation reaction can cause producing carbonyl containing compound.Suitable carbonyl containing compound can include, but not limited to any compound comprising carbonyl functional group that can form ionic species or can react with ionic species in the condensation reaction.In one embodiment, carbonyl containing compound can include, but not limited to ketone, aldehyde, furfural, hydroxycarboxylic acid and carboxylic acid.Ketone can comprise ad lib, hydroxy-ketone, cyclic ketones, diketone, acetone (acetone), acetone (propanone), 2-oxo-propanal, butanone, fourth-2,3-diketone, 3-hydroxyl fourth-2-ketone, pentanone, cyclopentanone, penta-2,3-diketone, penta-2,4-diketone, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecyl ketone, ten diketone, methyl-glyoxal, diacetyl, pentanedione, diketone hexane, dihydroxyacetone (DHA) and their isomers.Aldehyde can comprise ad lib, aldol, acetaldehyde, glyceraldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, octanal, aldehyde C-9, capraldehyde, the hendecanal, lauric aldehyde and their isomers.Carboxylic acid can comprise formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid and their isomers and derivative ad lib, comprises hydroxylation derivative, such as 2-hydroxybutyric acid and lactic acid.Furfural can comprise hydroxymethylfurfural, 5-methylol-2 (5H)-furanone, dihydro-5-(methylol)-2 (3H)-furanone, tetrahydrochysene-2-furancarboxylic acid, dihydro-5-(methylol)-2 (3H)-furanone, tetrahydrofurfuryl alcohol, 1-(2-furyl) ethanol, methylol tetrahydrofurfural and their isomers ad lib.In one embodiment, dehydrogenation reaction can cause producing carbonyl containing compound, and itself and oxidation intermediates are combined into a part for the oxidation intermediates being fed into condensation reaction.

In one embodiment, acid catalyst can be used for optionally by least part of oxidation intermediates logistics dehydration.Suitable acid catalyst for dehydration can include, but not limited to mineral acid (such as, HCl, H ₂sO ₄), solid acid (such as, zeolite, ion exchange resin) and hydrochlorate (such as, LaCl ₃).Other acid catalyst can comprise ad lib, zeolite, carbide, nitride, zirconia, aluminium oxide, silica, aluminosilicate, phosphate, titanium dioxide, zinc oxide, vanadium oxide, lanthana, yittrium oxide, scandium oxide, magnesia, ceria, barium monoxide, calcium oxide, hydroxide, heteropoly acid, inorganic acid, acid modified resin, base modified resin and their any combination.In some embodiments, dehydration catalyst also can comprise modifier.Suitable modifier can comprise, such as, and La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba and their any combination.The hydrogenation/dehydrogenation that modifier especially can be used for carrying out working in coordination with mutually with dehydration is reacted.In some embodiments, dehydration catalyst also can comprise metal.Suitable metal can comprise, such as, and Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os and their alloy or any combination.Dehydration catalyst can be self-supporting, and load is on inert carrier or resin, or its solubilized is in the solution.

In some embodiments, dehydration can occur in vapor phase.In other embodiment, dehydration can occur in the liquid phase.For liquid-phase dehydration reaction, the aqueous solution can be used for reacting.In one embodiment, other solvent in addition to water can be used for forming the aqueous solution.Such as, water-miscible organic solvent can be there is.Suitable solvent can include, but not limited to hydroxymethylfurfural (HMF), methyl-sulfoxide (DMSO), 1-methyl-n-pyrrolidones (NMP) and their any combination.Other suitable aprotic solvent also can combinationally use separately or with these solvents any.

In one embodiment, processing reaction can comprise optional ketonize reaction.Ketonize reacts the ketone number that can be increased in small part oxidation intermediates.Such as, alcohol can be converted into ketone in ketonize reaction.Ketonize can be carried out under base catalyst exists.Any base catalyst of the basic component as aldol reaction recited above can be used for carrying out ketonize reaction.Suitable reaction condition is well known by persons skilled in the art, and usually corresponds to the reaction condition about aldol reaction listed above.Ketonize reaction can be used as independent reactions steps and carries out, or it can carry out with aldol reaction is collaborative mutually.Aldol condensation catalyst comprises ketonize and aldol reaction that alkaline functional site can cause working in coordination with.

In some embodiments, processing reaction can comprise optional furan nucleus ring-opening reaction.Furan nucleus ring-opening reaction can cause anyly comprising being converted at least partially of the oxidation intermediates of furan nucleus have more reactive compound in aldol reaction.Furan nucleus ring-opening reaction can be carried out in the presence of acidic.Any acid catalyst being used as the acid constituents of aldol reaction recited above can be used for carrying out furan nucleus ring-opening reaction.Suitable reaction condition is well known by persons skilled in the art, and usually corresponds to the reaction condition about aldol reaction listed above.Furan nucleus ring-opening reaction can be used as independent reactions steps and carries out, or it can carry out with aldol reaction is collaborative.Aldol condensation catalyst comprises sour functional site and can cause furan nucleus ring-opening reaction collaborative mutually and aldol reaction.Such embodiment can be favourable, because any furan nucleus can open loop use basic functionality to react in aldol reaction under acid functionality exists.For the charging of appointment oxidation intermediates, so collaborative reaction scheme can allow to produce more substantial higher hydrocarbon to be formed.

In some embodiments, the generation of >C4 compound occurs by condensation, and described condensation can be included in the aldol condensation of the oxidation intermediates under condensation catalyst existence.Alcohol aldehyde-condensation is usually directed to carbon-to-carbon coupling between two kinds of compounds (wherein at least one can comprise carbonyl group) to form larger organic molecule.Such as, acetone can react with hydroxymethylfurfural and form C9 species, and the latter can form C15 species with another hydroxymethylfurfural molecular reaction subsequently.In multiple embodiment, reaction is carried out usually under condensation catalyst exists.Condensation reaction can be carried out in steam or liquid phase.In one embodiment, reaction can occur the temperature of 5 DEG C-375 DEG C, and this depends on the reactivity of carbonyl group.

Condensation catalyst is generally can by connecting two molecules to form the catalyst compared with long-chain compound with new carbon-carbon bond, such as base catalyst, there is the multifunctional catalyst of bronsted lowry acids and bases bronsted lowry degree of functionality simultaneously, or also comprise arbitrary type catalyst of optional metal functionality.In some embodiments, multifunctional catalyst can be the catalyst simultaneously with strong acid and highly basic degree of functionality.In some embodiments, alcohol aldehyde catalyst can comprise Li, Na, K, Cs, B, Rb, Mg, Ca, Sr, Si, Ba, Al, Zn, Ce, La, Y, Sc, Y, Zr, Ti, hydrotalcite, zinc-aluminate, phosphate, the aluminosilicate zeolites of alkali treatment, basic resin, basic nitrogen compound and their alloy or any combination.In some embodiments, base catalyst also can comprise the oxide of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Co, Ni, Si, Cu, Zn, Sn, Cd, Mg, P, Fe or their any combination.In some embodiments, condensation catalyst can comprise mixed oxide base catalyst.Suitable mixed oxide base catalyst can comprise the combination of magnesium, zirconium and oxygen, and it can comprise ad lib: Si-Mg-O, Mg-Ti-O, Y-Mg-O, Y-Zr-O, Ti-Zr-O, Ce-Zr-O, Ce-Mg-O, Ca-Zr-O, La-Zr-O, B-Zr-O, La-Ti-O, B-Ti-O and their any combination.Form can the scope of 0.01-50 using of the different atomic ratios of the Mg/Zr of mixed oxide catalyst or the combination of other element multiple.In some embodiments, condensation catalyst also can comprise metal or comprise the alloy of various metals, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Bi, Pb, Os, its alloy or combination.When dehydrogenation reaction and aldol reaction are collaborative carry out time, such metal can be preferred.In some embodiments, preferred IA race material can comprise Li, Na, K, Cs and Rb.In some embodiments, preferred IIA race material can comprise Mg, Ca, Sr and Ba.In some embodiments, IIB race material can comprise Zn and Cd.In some embodiments, IIIB race material can comprise Y and La.Basic resin can comprise the resin of display basic functionality.Base catalyst can be self-supporting, or stick on any one carrier that hereinafter further describes, comprise the carrier comprising carbon, silica, aluminium oxide, zirconia, titanium dioxide, vanadium oxide, ceria, nitride, boron nitride, heteropoly acid, its alloys and mixts.

In one embodiment, condensation catalyst can come from MgO and Al forming hydrotalcite material ₂o ₃combination.Another kind of preferred material comprises ZnO and Al of zinc aluminate spinel form ₂o ₃.Still another kind of preferred material is ZnO, Al ₂o ₃with the combination of CuO.Also can comprise in each in these materials by the another kind of metal functionality of group VIIIB metal carrying confession, such as Pd or Pt.When dehydrogenation reaction and aldol reaction are collaborative carry out time, such metal can be preferred.In some embodiments, base catalyst can be the metal oxide comprising Cu, Ni, Zn, V, Zr or their mixture.In other embodiment, base catalyst can be the zinc aluminate metal comprising Pt, Pd, Cu, Ni or their mixture.

In some embodiments, the condensation reaction of base catalysis can use the condensation catalyst simultaneously with acid and basic functionality to carry out.Acid-ol aldehyde condensation catalyst can comprise hydrotalcite, zinc-aluminate, phosphate, Li, Na, K, Cs, B, Rb, Mg, Si, Ca, Sr, Ba, Al, Ce, La, Sc, Y, Zr, Ti, Zn, Cr or their any combination.In further embodiment, Acid-bast-catalyst also can comprise the oxide that one or more are selected from Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P and combination thereof.In some embodiments, Acid-bast-catalyst can comprise the metal functionality provided by Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, its alloy or combination.In some embodiments, catalyst also can comprise Zn, Cd or phosphate.In some embodiments, condensation catalyst can be the metal oxide comprising Pd, Pt, Cu or Ni, even more preferably comprises Mg and Cu, the aluminate of Pt, Pd or Ni or zirconium metal oxide.Acid-bast-catalyst also can comprise the hydroxyapatite (HAP) with any one in above-mentioned metal or multiple combination.Acid-bast-catalyst can be self-supporting, or adhere on any one carrier that further describes hereinafter, comprise the carrier of carbon containing, silica, aluminium oxide, zirconia, titanium dioxide, vanadium oxide, ceria, nitride, boron nitride, heteropoly acid, its alloys and mixts.

In some embodiments, condensation catalyst also can comprise zeolite and comprise other many porous carrier of IA compounds of group (such as, Li, Na, K, Cs and Rb).Preferably, the amount during IA race material can be less than and needed for support acidity character exists.Also by adding group VIIIB metal or Cu, Ga, In, Zn or Sn to provide metal function.In one embodiment, condensation catalyst can come from MgO and the Al forming hydrotalcite material ₂o ₃combination.Another kind of preferred material can comprise MgO and ZrO ₂combination, or ZnO and Al ₂o ₃combination.Each in these materials also can comprise the another kind of metal function provided by copper or group VIIIB metal (such as, the combination of Ni, Pd, Pt or aforementioned substances).

Condensation catalyst can be (that is, catalyst is without the need to being used as the another kind of material of carrier) of self-supporting, or can need the applicable independent carrier be suspended in by catalyst in reactant stream.Exemplary carrier is a silica, and the high surface that has obtained especially by sol-gel synthesis, precipitation or pyrolysismethod (is greater than 100m ²/ g) silica.In other embodiment, particularly when condensation catalyst is powder, antigravity system can comprise adhesive to help shaped catalyst as desirable catalyst shape.The forming method be suitable for can comprise extrude, be granulated, oil dripping or other known method.Zinc oxide, aluminium oxide and gelatinizing agent also can be mixed together and extrude to be made into shaped material.After drying, this material can at the temperature lower calcination of applicable formation Catalytic active phase.Also other catalyst carrier well known by persons skilled in the art can be used.

In some embodiments, when reaction condition overlaps each other to a certain extent, dehydration catalyst, dehydrogenation and condensation catalyst can be present in same reactor.In these embodiments, dehydration and/or dehydrogenation reaction can occur with condensation reaction substantially simultaneously.In some embodiments, catalyst can comprise except for the avtive spot for dehydration and/or dehydrogenation reaction except condensation reaction.Such as, catalyst can comprise independent site on a catalyst or the active metal for dehydration and/or dehydrogenation reaction and condensation reaction as alloy.Suitable active element can comprise listed above about dehydration catalyst, any kind in those of dehydrogenation and condensation catalyst.Or, the physical mixture of dehydration, dehydrogenation and condensation catalyst can be used.Although do not wish to be limited to theory, believe and use the condensation catalyst comprising metal and/or acid functionality can contribute to promoting the aldol reaction of balance restriction towards completing development.Advantageously, this can be used for the multiple condensation reaction carried out with intermediate dehydration and/or dehydrogenation, to form the oligomer of (via condensation, dehydration and/or dehydrogenation) higher molecular weight, as producing desired by aviation kerosine or diesel fuel.

The concrete >C4 compound produced in condensation reaction can be depending on many factors, comprise, but be not limited to, the type of oxidation intermediates, condensation temp, condensation pressure, the reactivity of catalyst and the flow velocity of reactant stream in reactant stream.Usually, condensation reaction can be carried out at the thermodynamic (al) temperature being conducive to proposed reaction.For condensation phase liquid reactions, the pressure of reactor can be enough at least part of reactant to remain condensation liquid phase at reactor inlet place.For vapor-phase reaction, reaction can be carried out at following temperature: at such a temperature, and the vapour pressure of oxygenatedchemicals is at least 0.1bar, and this temperature is beneficial to the thermodynamics of reaction.Condensation temp will depend on concrete oxidation intermediates used and become, but for the reaction occurred in vapor phase, usually within the scope of 75 DEG C-500 DEG C, more preferably within the scope of 125 DEG C-450 DEG C.For liquid phase reactor, condensation temp can between 5 DEG C-475 DEG C, and condensation pressure can between 0.01bar-100bar.Preferably, condensation temp can between 15 DEG C-300 DEG C, or between 15 DEG C-250 DEG C.

Change with first-class factor usually by the change of the concrete composition and productive rate that cause >C4 compound.Such as, the temperature of altering reactor system and/or pressure or specific catalyst formulation, can cause producing >C4 alcohol and/or ketone instead of >C4 hydrocarbon.>C4 hydrocarbon products also can comprise alkene and the alkane (being generally branched paraffin) of multiple different size.Depend on used condensation catalyst, hydrocarbon products also can comprise aromatic hydrocarbons and cyclic hydrocarbon compound.>C4 hydrocarbon products also can comprise undesirable high-level alkene, and it may cause coking or deposition in internal combustion engine, or other undesirable hydrocarbon products.In this case, hydrocarbon be optionally hydrogenated with by ketone body powder for alcohol and hydrocarbon, simultaneously alcohol and alkene can be reduced to alkane, thus form the hydrocarbon products more preferably with lower alkene, aromatic hydrocarbons or alcohol level.

Condensation reaction can be carried out in the reactor of any suitable design, comprises continuously-flow-type, batch-type, semi-batch or multisystem reactor, for the not restriction such as design, size, geometry, flow velocity.Reactor assembly also can use fluid catalytic bed system, rocking bed system, fixed bed system, moving bed system or above-mentioned combination.In some embodiments, two-phase (such as, liquid-liquid) and three-phase (such as, liquid-liquid-solid) reactor can be used for carrying out condensation reaction.

In continuous flowing type system, reactor assembly can comprise optional dehydrogenation bed (being applicable to produce the oxidation intermediates of dehydrogenation), optional dehydration bed (being applicable to produce the oxidation intermediates of dehydration) and condensation bed (being applicable to produce >C4 compound from oxidation intermediates).Dehydrogenation bed can be configured to receive reactant stream and the oxidation intermediates needed for generation, and the latter can have the raising of carbonyl containing compound amount.Dehydration bed can be configured to receive reactant stream and the oxidation intermediates needed for generation.Condensation bed can be configured to receive oxidation intermediates to contact with condensation catalyst and >C4 compound needed for producing.For the system with one or more refining (finishing) step, can be comprised another for carrying out the reaction bed of purification step or multiple purification step after condensation bed.

In some embodiments, the reaction of optional dehydration, optional dehydrogenation reaction, optional ketonize, optional ring-opening reaction and condensation catalyst bed can be disposed in same reactor vessel or be arranged in the independent reactor vessel of fluid communication with each other.Each reactor vessel preferably can comprise the outlet being applicable to product stream to remove from reactor vessel.For the system with one or more purification step, refining reaction bed or multiple refining bed can together with condensation bed in same reactor vessels, or in the independent reactor vessel be communicated with the reactor vessel fluid with condensation bed.

In some embodiments, reactor assembly also can comprise other outlet with allows to remove part reactant stream with promote further or guide reaction to move towards required product and allow to collect also circular response accessory substance in the other parts of system.In some embodiments, reactor assembly also can comprise other entrance with allow introduce supplementary material with promote further or guide reaction towards required product move and allow circular response accessory substance for other reaction in.

In some embodiments, reactor assembly also can comprise the element allowing reactant stream to be separated into different component, and it can find purposes or simply for promoting required reaction in differential responses scheme.Such as, separator unit (such as phase separator, extractor, purifier or destilling tower) can be set before condensation step to remove water thus promote the generation that condensation reaction is beneficial to higher hydrocarbon from reactant stream.In some embodiments, separative element can arrange to remove specific intermediate and comprise in specific carbon number range needed for hydrocarbon product stream to allow to produce, or is used as end-product or for other system or method.It is C that condensation reaction can produce carbon number ₄-C ₃₀or more multiple compounds.Exemplary compounds can comprise, such as, >C4 alkane, >C4 alkene, >C5 cycloalkane, >C5 cycloolefin, aryl compound, thick aryl compound, >C4 alcohol, >C4 ketone and composition thereof.>C4 alkane and >C4 alkene can be (the i.e. C of 4-30 carbon atom ₄-C ₃₀alkane and C ₄-C ₃₀alkene), and can be alkane or the alkene of side chain or straight chain.>C4 alkane and >C4 alkene also can comprise C respectively ₇-C ₁₄, C ₁₂-C ₂₄alkane and hydrocarbon fraction, wherein C ₇-C ₁₄part refers to aviation kerosine fuel mixture, and C ₁₂-C ₂₄part relates to diesel fuel blends and other industrial use.The example of multiple >C4 alkane and >C4 alkene can comprise ad lib, butane, butylene, pentane, amylene, 2-methybutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2, 2-dimethylbutane, 2, 3-dimethylbutane, heptane, heptene, octane, octene, 2, 2, 4-trimethylpentane, 2, 3-dimethylhexane, 2, 3, 4-trimethylpentane, 2, 3-dimethyl pentane, nonane, nonene, decane, decene, hendecane, hendecene, dodecane, laurylene, tridecane, tridecylene, the tetradecane, tetradecene, pentadecane, ten pentaenes, hexadecane, hexadecylene, heptadecane, 17 alkene, octadecane, octadecylene, nonadecane, 19 alkene, eicosane, icosa alkene, heneicosane, two hendecenes, docosane, docosene, tricosane, tricosene, lignocerane, two tetradecenes and their isomers.

>C5 cycloalkane and >C5 cycloolefin can have 5-30 carbon atom, and can be do not replace, monosubstituted or polysubstituted.When monosubstituted and polysubstitution compound, substituted radical can comprise side chain >C3 alkyl, straight chain >C1 alkyl, side chain >C3 alkylidene, straight chain >C1 alkylidene, straight chain >C2 alkylidene, aromatic yl group or their combination.In one embodiment, at least one substituting group can comprise side chain C3-C12 alkyl, straight chain C 1-C12 alkyl, side chain C3-C12 alkylidene, straight chain C 1-C12 alkylidene, straight chain C 2-C12 alkylidene, aromatic yl group or their combination.In still other embodiment, at least one substituted radical can comprise side chain C3-C4 alkyl, straight chain C 1-C4 alkyl, side chain C3-C4 alkylidene, straight chain C 1-C4 alkylidene, straight chain C 2-C4 alkylidene, aromatic yl group or their any combination.Desirable >C5 cycloalkane and the example of >C5 cycloolefin can comprise ad lib, pentamethylene, cyclopentene, cyclohexane, cyclohexene, methyl cyclopentane, methyl cyclopentene, ethyl cyclopentane, ethylcyclopentene, ethyl cyclohexane, ethyl-cyclohexene and their isomers.

Aromatic yl group comprises the armaticity alkyl not replacing (as phenyl), monosubstituted or polysubstituted form.When monosubstituted and polysubstitution compound, substituting group can comprise side chain >C3 alkyl, straight chain >C1 alkyl, side chain >C3 alkylidene, straight chain >C2 alkylidene, phenyl group or their combination.In some embodiments, at least one substituted radical can comprise side chain C3-C12 alkyl, straight chain C 1-C12 alkyl, side chain C3-C12 alkylidene, straight chain C 2-C12 alkylidene, phenyl group or their any combination.In still other embodiment, at least one substituted radical can comprise side chain C3-C4 alkyl, straight chain C 1-C4 alkyl, side chain C3-C4 alkylidene, straight chain C 2-C4 alkylidene, phenyl group or their any combination.The example of various aryl compound can comprise ad lib, benzene,toluene,xylene (dimethyl benzene), ethylbenzene, p-dimethylbenzene, m-dimethylbenzene, ortho-xylene and C9 aromatic hydrocarbons.

Fused-aryl compound can comprise do not replace, two rings of monosubstituted or polysubstituted form and polycyclic aromatic hydrocarbons (PAH).When monosubstituted and polysubstitution compound, substituted radical can comprise side chain >C3 alkyl, straight chain >C1 alkyl, side chain >C3 alkylidene, straight chain >C2 alkylidene, phenyl group or their combination.In other embodiment, at least one substituted radical can comprise side chain C3-C4 alkyl, straight chain C 1-C4 alkyl, side chain C3-C4 alkylidene, straight chain C 2-C4 alkylidene, phenyl group or their any combination.The example of multiple fused-aryl compound can comprise ad lib, naphthalene, anthracene, tetrahydronaphthalene and decahydronaphthalenes, dihydroindene, indenes and their isomers.

The midbarrel (moderate fractions) of such as C7-C14 is separable for aviation kerosine fuel, and such as C12-C24's is separable compared with heavy distillat for diesel oil purposes.The heaviest cut can be used as lubricant or cracking to produce other gasoline and/or diesel oil distillate.>C4 compound also can find to be used as industrial chemical, no matter is as intermediate or as end-product.Such as, aryl compound toluene, dimethylbenzene, ethylbenzene, paraxylene, meta-xylene and ortho-xylene can find the chemical intermediate being used as production plastics and other product.Meanwhile, C9 phenolic compound and fused-aryl compound (such as naphthalene, anthracene, tetrahydronaphthalene and decahydronaphthalenes) can find to be used as the solvent in industrial process.

In some embodiments, other process process fuel mixture can be used to remove some component or to make fuel mixture meet diesel oil or aviation kerosine fuel standard further.Suitable technology can comprise hydrotreatment to reduce the amount of any remaining oxygen, sulphur or nitrogen in fuel mixture or to be removed.The condition of hydrocarbon stream hydrotreatment is well known by persons skilled in the art.

In some embodiments, hydrogenation or can be carried out making at least some ethylene linkage saturated at alternative hydroprocessing processes after hydroprocessing processes.In some embodiments, hydrogenation carries out with aldol reaction is collaborative by comprising metal functional group on aldol condensation catalyst.Such hydrogenation can be carried out and meet specific fuel standard (such as, diesel fuel standard or aviation kerosine fuel standard) to make fuel mixture.The hydrogenation of fuel mixture logistics can be carried out according to known procedure, uses continuously or batch processes.Hydrogenation can be used for removing remaining carbonyl group and/or oh group.In this case, any hydrogenation catalyst as above can be used.Usually, purification step can be carried out at the extraction temperature of 80 DEG C-250 DEG C, and refining pressure can be between 5bar-150bar.In some embodiments, purification step can be carried out in vapor phase or liquid phase, and uses external hydrogen, recycle hydrogen or their combination where necessary.

In some embodiments, isomerization can be used for processing fuel mixture to introduce branching or other shape selective of required degree at least some component in fuel mixture.Useful removed any impurity in addition before being contacted with isomerization catalyst by hydrocarbon.Isomerization steps can comprise optional stripping step, wherein from the fuel mixture of oligomerization by purifying with steam or suitable gas (such as lighter hydrocarbons, nitrogen or hydrogen).Optional stripping step can carry out in a counter-current configuration in the unit (wherein gas and liquid contact with each other) of isomerization catalyst upstream, or carries out in the independent steam stripping unit utilizing countercurrent action before the isomerization reactor of reality.

After optional stripping step, fuel mixture can be made to pass into comprise the reactive isomerization unit of one or more catalyst bed.The catalyst bed of isomerization unit can also stream or reflux type operation.In isomerization unit, pressure can change between 20bar-150bar, preferred 20bar-100bar, and temperature, between 195 DEG C-500 DEG C, is preferably 300 DEG C-400 DEG C.In isomerization unit, any isomerization catalyst known in the art can be used.In some embodiments, suitable isomerization catalyst can comprise molecular sieve and/or from the metal of VII race and/or carrier.In some embodiments, isomerization catalyst can comprise SAPO-11 or SAPO41 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and A1 ₂o ₃or SiO ₂.Typical isomerization catalyst can comprise, such as, and Pt/SAPO-11/Al ₂o ₃, Pt/ZSM-22/Al ₂o ₃, Pt/ZSM-23/Al ₂o ₃and Pt/SAPO-11/SiO ₂.

Other factors, the such as concentration of water or unwanted oxidation intermediates, also may affect composition and the productive rate of >C4 compound, and the activity of condensation catalyst and stability.In this case, the method removes the dehydration of a part of water before can being included in condensation reaction and/or optional dehydration, or for removing the separative element of unwanted oxidation intermediates.Such as, separator unit, to remove a part of water from the reactant stream comprising oxidation intermediates before such as phase separator, extractor, purifier or destilling tower can be arranged on condensation reactor.Separative element also can be installed as to be removed specific oxidation intermediates and comprises within the scope of particular carbon needed for hydrocarbon product stream to allow to produce, or as end-product or for other system or method.

Therefore, in some embodiments, the fuel mixture produced by methods described herein can be the hydrocarbon mixture (such as, meeting ASTM D1655) meeting aviation kerosine demanded fuel.In other embodiment, the product of methods described herein can be comprise meet fuel mixture that diesel fuel requires hydrocarbon mixture (such as, meeting ASTM D975).

In other embodiment, the fuel mixture (that is, Fuel Petroleum) comprising gasoline hydrocarbon can be produced." gasoline hydrocarbon " refers to the hydro carbons mainly comprising C5-9 hydrocarbon, and such as, boiling spread is at the C6-8 hydrocarbon of 32 DEG C of (90 °F)-204 DEG C (400 °F).Gasoline hydrocarbon can include, but not limited to direct steaming gasoline, naphtha, the gasoline of fluidisation or thermocatalytic cracking, VB gasoline and coker gasoline.Gasoline hydrocarbon content is measured by ASTM method D2887.

In still other embodiment, >C2 alkene is prepared by oxidation intermediates is carried out catalytic reaction in the presence of a dehydration catalyst under dehydration temperaturre and dewatering pressure, to produce the reaction logistics comprising >C2 alkene.>C2 alkene can comprise the straight or branched hydrocarbon comprising one or more carbon-to-carbon double bond.Usually, >C2 alkene can comprise 2-8 carbon atom, more preferably 3-5 carbon atom.In some embodiments, alkene can comprise two or more mixture any in propylene, butylene, amylene, the isomers of aforementioned substances and aforementioned substances.In other embodiment, >C2 alkene can comprise the >C4 alkene produced by least part of >C2 alkene is carried out catalytic reaction through olefin isomerization catalyst.

Dehydration catalyst can comprise and is selected from two or more combination any in acidic alumina, aluminum phosphate, silica-aluminophosphates (alumina phosphate), amorphous silica-alumina, aluminosilicate, zirconia, sulfated zirconia, tungstated zirco, tungsten carbide, molybdenum carbide, titanium dioxide, sulphation carbon, phosphorylation carbon, phosphated silica, phosphated alumina, acidic resins, heteropoly acid, inorganic acid and aforementioned substances.In some embodiments, dehydration catalyst also can comprise and is selected from two or more modifier of combination any in Ce, Y, Sc, La, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi and aforementioned substances.In other embodiment, dehydration catalyst also can comprise element oxide, and described element is selected from two or more combination any in Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P and aforementioned substances.In still other embodiment, dehydration catalyst also can comprise be selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, aforementioned substances any two or more alloy and aforementioned substances in two or more metal of combination any.

In still other embodiment, dehydration catalyst can comprise aluminosilicate zeolites.In some embodiments, dehydration catalyst also can comprise and is selected from two or more modifier of combination any in Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned substances.In some embodiments, dehydration catalyst also can comprise be selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, aforementioned substances any two or more alloy and aforementioned substances in two or more metal of combination any.

In other embodiment, dehydration catalyst can comprise the aluminosilicate zeolites comprising difunctional five yuan of silica-rich zeolite rings.In some embodiments, dehydration catalyst also can comprise and is selected from two or more modifier of combination any in Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned substances.In some embodiments, dehydration catalyst also can comprise be selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, aforementioned substances any two or more alloy and aforementioned substances in two or more metal of combination any.

Dehydration can be carried out being beneficial under thermodynamic (al) temperature and pressure.Usually, reaction can be carried out in vapor phase, liquid phase or the combination of the two.In some embodiments, dehydration temperaturre can between 100 DEG C-500 DEG C, and dewatering pressure can between 1bar (absolute pressure)-60bar.In some embodiments, dehydration temperaturre can between 125 DEG C-450 DEG C.In some embodiments, dehydration temperaturre can between 150 DEG C-350 DEG C, and dewatering pressure can between 5bar-50bar.In some embodiments, dehydration temperaturre can between 175 DEG C-325 DEG C.

>C6 alkane produces by such as under type: by >C2 alkene and the logistics of >C4 isoparaffin under alkylation catalyst exists under alkylation temperature and alkylation pressures catalytic reaction to produce the product stream comprising >C6 alkane.>C4 isoparaffin can comprise the alkane and cycloalkane with 4-7 carbon atom, such as iso-butane, isopentane, cycloalkane and there is tertiary carbon atom higher homologue (such as, 2-methybutane and 2,4-dimethyl pentane), two or more mixture any in the isomers of aforementioned substances and aforementioned substances.In some embodiments, the logistics of >C4 isoparaffin can comprise two or more combination any in inner the >C4 isoparaffin, outside >C4 isoparaffin, circulation >C4 isoparaffin or the aforementioned substances that generate.

>C6 alkane can be branched-chain alkane, but also can comprise normal paraffin hydrocarbons.In one aspect, >C6 alkane can comprise and is selected from two or more member of mixture any in side chain C6-10 alkane, side chain C6 alkane, side chain C7 alkane, side chain C8 alkane, side chain C9 alkane, side chain C10 alkane or aforementioned substances.In one aspect, >C6 alkane can comprise, such as, dimethylbutane, 2,2-dimethylbutane, 2,3-dimethylbutanes, methylpentane, 2-methylpentane, 3-methylpentane, dimethyl pentane, 2,3-dimethyl pentanes, 2,4-dimethyl pentane, methyl hexane, 2,3-dimethylhexane, 2,3,4-trimethylpentanes, 2,2,4-trimethylpentane, 2,2,3-trimethylpentanes, 2, two or more mixture any in 3,3-trimethylpentane, dimethylhexane or aforementioned substances.

Alkylation catalyst can comprise and is selected from sulfuric acid, hydrofluoric acid, aluminium chloride, boron trifluoride, solid phosphoric acid, chloride-oxidation aluminium, acidic alumina, aluminum phosphate, silica-aluminophosphates, amorphous silica-alumina, aluminosilicate, aluminosilicate zeolites, zirconia, sulfated zirconia, tungstated zirco, tungsten carbide, molybdenum carbide, titanium dioxide, sulphation carbon, phosphorylation carbon, phosphated silica, phosphated alumina, acidic resins, heteropoly acid, two or more member of combination any in inorganic acid and aforementioned substances.Alkylation catalyst also can comprise the mixture of mineral acid and Friedel-Crafts metal chloride (such as aluminium bromide) and other proton donor.

In some embodiments, alkylation catalyst can comprise aluminosilicate zeolites.In some embodiments, alkylation catalyst also can comprise and is selected from two or more modifier of combination any in Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned substances.In some embodiments, alkylation catalyst also can comprise be selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, aforementioned substances any two or more alloy and aforementioned substances in two or more metal of combination any.

In some embodiments, alkylation catalyst can comprise the aluminosilicate zeolites comprising difunctional five yuan of silica-rich zeolite rings.In some embodiments, alkylation catalyst also can comprise the modifier be selected from Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned substances in two or more combination any.In some embodiments, alkylation catalyst also can comprise be selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, aforementioned substances any two or more alloy and aforementioned substances in two or more metal of combination any.In one aspect, to can be atom identical for dehydration catalyst and alkylation catalyst.

Alkylated reaction can carry out being beneficial to thermodynamic (al) temperature.Usually, alkylation temperature can between-20 DEG C to 300 DEG C, and alkylation pressures can be between 1bar (absolute pressure)-80bar.In some embodiments, alkylation temperature can between 100 DEG C-300 DEG C.On the other hand, alkylation temperature can between 0 DEG C-100 DEG C.In still other embodiment, alkylation temperature can between 0 DEG C-50 DEG C.In still other embodiment, alkylation temperature can between 70 DEG C-250 DEG C, and alkylation pressures can between 5bar-80bar.In some embodiments, alkylation catalyst can comprise mineral acid or strong acid.In other embodiment, alkylation catalyst can comprise zeolite, and alkylation temperature can higher than 100 DEG C.

In some embodiments, olefin oligomerization can be carried out.Oligomerization can carry out in any suitable reactor structure.Suitable structure can include, but not limited to the design of batch-type reactor, semi-batch reactor or flow reactor, such as, such as, has the fluidized-bed reactor of external regeneration vessels.Reactor design can include, but are not limited to tubular reactor, fixed bed reactors or be applicable to carrying out other type of reactor any of oligomerization.In some embodiments, continuous oligomerization method for the production of the hydrocarbon of diesel oil and aviation kerosine fuel boiling range can use oligomerization reactor to carry out, and is wherein contacted at an elevated temperature and pressure with zeolite catalyst with the fuel mixture be converted into by this short-chain olefin in diesel boiling range by the olefin feed stream comprising the short-chain olefin with 2-8 carbon atom chain length.Oligomerization reactor can operate under the relatively high pressure of 20bar-100bar, temperature between 150 DEG C-300 DEG C, preferably between 200 DEG C-250 DEG C.

The oligomer conductance of gained causes the fuel mixture being formed and can have multi-products, and described product comprises C5-C24 hydrocarbon.Process in addition can be used for obtaining the fuel mixture meeting required standard.Initial process step can be used for producing the fuel mixture with narrower carbon number range.In some embodiments, the separation method such as way of distillation can be used for producing the fuel mixture comprising C12-C24 hydrocarbon for processing further.Remaining hydrocarbon can be used for producing for being recycled to oligomerization reactor or the fuel mixture for the gasoline in other method.Such as, kerosene distillate can produce together with diesel oil distillate, and can be used as illumination (illuminating) alkane, rough as routine or synthesize in derivative aviation kerosine fuel aviation kerosine fuel mix composition, or as the reactant (especially C10-C13 cut) produced in the method for LAB (linear alkylbenzene (LAB)).Naphtha cut can be sent to heat cracker to produce ethene and propylene after hydrotreatment, or is sent to cat cracker to produce ethene, propylene and gasoline.

Other method can be used for process fuel mixture to remove some component or to make fuel mixture meet diesel oil or aviation kerosine fuel standard further.Suitable technology can comprise hydrotreatment to remove any remaining oxygen, sulphur or nitrogen in fuel mixture.Hydrogenation can be carried out to make at least some ethylene linkage saturated after hydrotreatment.Such hydrogenation can be carried out making fuel mixture meet specific fuel standard (such as, diesel fuel standard or aviation kerosine fuel standard).The step of hydrogenation of fuel mixture logistics can be carried out with continuous or batch mode according to program known in the art.

For contributing to understanding the present invention better, provide the example of following preferred embodiment.Following examples should not read as restriction by any way or be defined scope of the present invention.

Embodiment

Unless shown in addition hereinafter, react and carry out in Parr 5000HASTELLOY multiple reactor unit, it comprises 6x75mL reactor, 135bar at the most pressure and be operated in parallel at the temperature of 275 DEG C at the most, stir with magnetic stirring bar.Research is in addition carried out in 100mLParr 4590 reactor, and with the mixing of drive-type shaft impeller, it also can reach the pressure of 135bar and the temperature of 275 DEG C.Liquid-phase chromatographic analysis is undertaken by HPLC, and use Bio-RadAminex HPX-87H post (300mmx7.8mm), flow velocity is 0.6mL/min, uses 5mM sulfuric acid/water, case temperature 30 DEG C.Running time is 70 minutes.

Gas chromatographic analysis uses the 60mx0.32mm ID DB-5 post of 1 μm of thickness to carry out, and split ratio is 50:1, and helium flow speed is 2ml/min, and post case temperature 40 DEG C runs 8 minutes, and then rise to 285 DEG C gradually with 10 DEG C/min, retention time is 53.5 minutes.Injector temperature is set to 250 DEG C, and detector temperature is set to 300 DEG C.

Embodiment 1: the paste of high-cellulose biomass solid carrying capacity is formed.In cylinder with a scale, pine sawdust levigate for the 2.08g comprising 11.3% moisture is added in 25.5g deionized water.After mixing and allowing wood chip balance, shift out 10.4g water with syringe from wood chip bed top.Subsequently cylinder is tilted to go out extra water with decant, but only shift out the extra water of 1g, obtain final water: solid body is than being 8.3:1.Add the slurry catalyst that 0.1g particle diameter is 1-25 micron, and for several times cylinder is mixed by reversing.Because levigate wood chip defines paste, in fact do not observe mixing of slurry catalyst and wood chip.

Embodiment 2: living beings particle diameter is to the effect of digestion speed.Multiple Parr 5000 reactor of parallel connection is loaded into 20.0g 2-propyl alcohol/deionized water (50%), wherein comprises 0.05g sodium carbonate.Cork pine sheet 2.70g being contained 39% moisture adds in each reactor.In first reactor, add the wood chip of single 1 inch of x1 inch x3mm.In a second reactor, pine is become the small pieces of several 1/4 inch of x1/4 inch x3mm with hand strip off.In the 3rd reactor, pine is ground in coffee grinder full-size and is nominally 3mm.

All three reactors all use H ₂be pressurized to 51bar, be heated to 190 DEG C and keep 1 hour, be elevated to 240 DEG C subsequently gradually to complete 5 hours periods.Reactor content by WhatmanGF/F Filter paper filtering, with the paper of solid in 90 DEG C of dried overnight in vacuum drying oven.On anhydrous basis, the wood in first reactor has dissolved 78wt%, the dissolving obtaining 72wt% compared with spile in two other reactor.Believe that the test error of these results is substantially identical, digestion speed does not affect by wood plate size substantially.

Embodiment 3: digestion cellulose biomass under bottom loaded slurry catalyst exists.The 2.25-inch district, bottom of the digestion pipe of 12.5 inches of x0.5-inch external diameters (0.402 inch of internal diameter) fills by 1/8-inch Ceramic Balls (Denstone), is then the 14x40 order filter sand of 0.7-inch.Sand is placed the cobalt molybdate catalyst (DC2534 of 0.604g sulfuration, Criterion Catalyst & Technologies L.P), it is included in the cobalt oxide and the molybdenum trioxide (at the most 30wt%) that are crushed to particle diameter and are less than the 1-10% on the aluminium oxide of 100 μm.The sulfuration of catalyst in advance as described in U.S. Patent Application Publication 20100236988.Be the Southern Pine wood chip filling of 3mmx5mmx5mm subsequently by effective 4.00g nominal size, thus form 8.7 inches of wood chip beds.

Digestion unit is full of from bottom with the 2-propyl alcohol/deionized water of 50%, cushions with 0.3wt% sodium carbonate.Continue to add digestion solvent, until the hole of wood chip bed is filled and just obtains the liquid level higher than 0.5 inch in bed.In packed bed, solvent is less than 5.8:1 with the ratio of dry timber.Stop liquid flow subsequently.Subsequently by digestion unit H ₂be pressurized to 70bar, under normal room temperature and atmospheric pressure (STP), add continuous hydrogen stream with the flow velocity of 95ml/min from digestion unit bottom and discharge from top.This flow velocity is equivalent to hydrogen stream with the apparent linear speed of 0.05cm/ second by digestion unit.Bottom inlet is the pipe of nominal size 3mm external diameter (2mm internal diameter), is therefore used as the nozzle that bubble is formed.

Subsequently digestion unit be heated to 190 DEG C and keep 1.5 hours, be heated to 240 DEG C subsequently and keep 3.5 hours.When off-test, discharge 9.24g product liquid from digestion unit.Also from spraying the overflow collection that the causes product liquid of 7.8g condensation with hydrogen.Liquid product analyses shows the carbohydrate amount based on existing in initial timber charging, obtains oxidation product mixture (comprising monohydric alcohol and glycol) with 82% of expectancy theory productive rate.Timber solid is not remained at the end of the digestion phase.

Embodiment 4: digestion cellulose biomass under top loading slurry catalyst exists.Repeat the test of embodiment 3, difference is 0.600g catalyst to be placed under wood chip bed top instead of wood chip bed.The initial ratio of solvent and dry timber is lower than 5.5:1.After digestion, discharge 10.1g product liquid from digestion unit, and from the product liquid of overflow collection 7.28g condensation.Equally, at the end of the digestion phase, observable timber solid residue is not had.Under wood chip bed, (it produces relatively high productive rate) is different from catalyst loading, and catalyst loading only creates 28% of theoretical yield at wood chip bed top.The LC/MS of product liquid analyzes the oligomeric side-products showing and may there is molecular weight and be greater than 300, and its molecular weight is too high so that cannot pass through gas chromatographic detection.

Embodiment 5: digestion cellulose biomass under bottom loaded formula slurry catalyst exists at low pressures.Use 6.05g Southern Pine wood chip and 15.4mL digestion solvent to repeat the test of embodiment 3, add from bottom, until do not have wood chip bed completely.In this case, relative to being 32bar with the solvent vapour pressure estimated, digestion unit is only pressurized to 37bar.Discharging hydrogen flow velocity is 97mL/min, the digestion solvent of the 2-propyl alcohol/deionized water of 50% from digestion unit bottom with the common charging of the flow velocity of 0.05mL/min.Digestion unit is heated to 190 DEG C and keeps 1.5 hours, is heated to 240 DEG C subsequently and keeps 5 hours, and hydrogen and digestion solvent flow rate remain on same level.When end of run, 18.53g product liquid is discharged from overflow, and 8.17g discharges from digestion unit.Need 5.167g wood chip that digestion unit is recharged its previous level.This result is minimum under being presented at digestion condition there occurs 85% digestion.Gas chromatographic analysis display only 31% is converted into required product.This result and embodiment 3 relatively show the hydrogen pressure that improves and facilitate the stable of soluble carbohydrate in the mode of more high yield.

Embodiment 6: do not use hydrogen stream digestion cellulose biomass under bottom loaded formula slurry catalyst exists.Repeat the test of embodiment 5 with the initial press of 70bar hydrogen, but be only maintained by the digestion solvent streams of cellulose biomass and do not use hydrogen stream.When end of run, discharge 17.45g product liquid from overflow, and discharge 7.4g product liquid from digestion unit.After running, also have collected the timber of the non-digestion of 8ml, show 50% conversion ratio.Gas chromatographic analysis is presented in product liquid the required product having 27% productive rate.Meanwhile, when by stopping hydrogen flowing minimizing available hydrogen amount, there occurs poor stablizing.

Embodiment 7: the digestion cellulose biomass when there is not slurry catalyst.After adding 6.76g pine sheet, repeat the test of embodiment 3, but do not comprise slurry catalyst.Although all timber chargings digestion in 6.5 hours, GC analyzes the required product that display only defines 3%.

Embodiment 8: use air-flow and liquid stream digestion cellulose biomass in room temperature under bottom loaded formula slurry catalyst exists.Add 5.29g Southern Pine wood chip, repeat the test of embodiment 3, but digestion unit remains on 23.5 DEG C between exposure period.7.597g product liquid has been discharged from digestion unit when end of run.The wood chip bed analysis display catalyst carried out after removing product liquid is dispersed throughout the whole high uniformity dispersion of cellulose biomass bed, thus slurry catalyst can be distributed in cellulose biomass solid by display air-flow and liquid stream effectively.

Embodiment 9: only use liquid stream digestion cellulose biomass in room temperature under bottom loaded formula slurry catalyst exists.After again filling with 7.13g pine sheet, repeat the test of embodiment 8, difference is the upwards flowing not using hydrogen, only there is the upwards flowing of the digestion solvent of 0.05mL/min.Discharge 1.36g product liquid from overflow, and obtain 10.67g product liquid from digestion unit.The analysis display catalyst of the wood chip bed carried out after removing product liquid is only distributed in the bottom about 20% of wood chip bed, does not find the catalyst distributed on wood chip charging top.

Embodiment 10: measure the minimum gas velocity making slurry catalyst fluidisation.NiMo/ alumina slurry catalyst and the 50g deionized water of 1g nominal 1-25 μm will be loaded in cylinder with a scale for 100mL.To sinter bubbling stone (fritted sparging stone) (ACE Glass) be placed in bottom of cylinder with a scale and with the N using 1/8-inch Teflon pipe ₂supply connects.Change N ₂flow velocity makes the complete fluidisation of slurry catalyst reach lowest speed needed for liquid column top to measure.The gas linear speed corresponding to complete fluidisation using the method to measure is 0.037cm/ second.When using in the embodiment above, hydrogen flow rate has exceeded the minimum speed that this makes catalyst fluidization and suspension.

Therefore, the present invention is suitable for that realization is mentioned and wherein intrinsic target and advantage very much.Disclosed particular implementation is only illustrative above, and the present invention can modify concerning different but equivalent mode the those skilled in the art with the interests of instructing herein and implement.In addition, except described in claims which follow, to the details of construction or design shown in herein without any restriction.Therefore, provable disclosed specific illustrated embodiment above can change, combines or revise, and all variations like this can be regarded as in scope and spirit of the present invention.Herein illustrative invention disclosed can when do not exist any not in this article concrete disclosed element and or any optional member disclosed herein implement.Although composition and method are described to " comprising ", " comprising " or " containing " multiple different component or step, composition and method also can substantially be formed by these components and step or are made up of them.Disclosed all numerals and scope can have a certain amount of change above.No matter suitablely disclose the number range with lower limit and the upper limit, also clearly openly fall into any numeral within the scope of this and anyly comprise scope.Particularly, each number range disclosed herein (comprises following form: " from a to b (a-b) ", or equally, " from roughly a to b ", or equally, " from roughly a-b ") be interpreted as having set forth each numeral and scope of comprising in broader numerical.Meanwhile, unless clearly known definition by patentee in addition, the term in claim has its generally general implication.And when using in the claims, indefinite article " a or an (//a kind of /) " is defined as in this article and represents one or more/one or more instead of one/a kind of key element that it is introduced.If the use of the word in description or term has any conflict with the one or more patent quoted or other file herein, the definition consistent with this description should be adopted.

Claims

1. a conversion systems for biomass, comprising:

Hydrothermal digestion unit, it comprises molecular hydrogen actived slurry catalyst;

Optional hydrogen feeding line, it is operably connected with hydrothermal digestion unit; With

Fluid circulation loop, this fluid circulation loop comprises hydrothermal digestion unit and catalytic reduction reactor unit, and this catalytic reduction reactor unit also comprises described slurry catalyst.

2. according to claim mistake! Do not find the conversion systems for biomass quoted described in source, wherein said fluid circulation loop is configured to the fluid flowing of setting up in described hydrothermal digestion unit upwards.

3., according to conversion systems for biomass according to claim 1 or claim 2, also comprise:

Reservation mechanism in described hydrothermal digestion unit, it can operate to retain the cellulose biomass solid that particle diameter is about 3mm or more.

4., according to conversion systems for biomass in any one of the preceding claims wherein, also comprise:

The product be communicated with described fluid circulation loop fluid takes out pipeline, and described product takes out pipeline between described hydrothermal digestion unit and the outlet of described catalytic reduction reactor unit.

5., according to conversion systems for biomass in any one of the preceding claims wherein, also comprise:

The solid separating mechanism that pipeline is operably connected is taken out with described product.

6., according to conversion systems for biomass in any one of the preceding claims wherein, wherein said slurry catalyst comprises poisoning resistant catalyst.

7., according to conversion systems for biomass in any one of the preceding claims wherein, wherein said slurry catalyst is at least about the water of 200 DEG C by being exposed to temperature and regenerating.

8., according to conversion systems for biomass in any one of the preceding claims wherein, wherein said slurry catalyst can work to produce molecular hydrogen.

9., according to conversion systems for biomass in any one of the preceding claims wherein, also comprise:

The solid retraction mechanism be operably connected with described hydrothermal digestion unit, described solid retraction mechanism comprises atmospheric pressure region and in atmospheric pressure and the pressure transition district of more circulating between high-pressure state.

10., according to conversion systems for biomass in any one of the preceding claims wherein, wherein said fluid circulation loop is configured to the fluid flowing of setting up in described catalytic reduction reactor unit upwards.

11. 1 kinds of methods, comprising:

Cellulose biomass solid is provided in the hydrothermal digestion unit comprising molecular hydrogen actived slurry catalyst;

Under molecular hydrogen exists, in described hydrothermal digestion unit, heat described cellulose biomass solid, make described slurry catalyst cycle through described hydrothermal digestion unit simultaneously, thus form the hydrolysate comprising soluble carbohydrate in the liquid phase;

When soluble carbohydrate is in described hydrothermal digestion unit, described soluble carbohydrate is converted into product at least partly; With

At least part of described liquid phase being transferred to also comprises in the catalytic reduction reactor unit of described slurry catalyst, is described product to transform described soluble carbohydrate further.

12. methods according to claim 11, also comprise:

At least part of described liquid phase is recycled to described hydrothermal digestion unit from described catalytic reduction reactor unit.

13., according to claim 11 or method according to claim 12, also comprise:

After transforming described soluble carbohydrate further and being described product, described for part product is discharged from described catalytic reduction reactor unit; With

Described product is converted into bio-fuel.

14. methods according to any one of claim 11-13, also comprise:

Separating solids from described product after discharge.

15. methods according to any one of claim 11-14, also comprise:

Described product is formed further in described catalytic reduction reactor unit.