CN104619407A

CN104619407A - Biomass conversion system having a single-vessel hydrothermal digestion unit and a catalytic reduction reactor unit for integrated stabilization of a hydrolysate and method for use thereof

Info

Publication number: CN104619407A
Application number: CN201380047441.0A
Authority: CN
Inventors: G·C·康普林; J·B·鲍威尔
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2012-09-27
Filing date: 2013-09-25
Publication date: 2015-05-13
Also published as: AU2013323745B2; AU2013323745A1; BR112015006256A2; EP2900359A1; IN2015DN00736A; US20140088330A1; WO2014052374A1; CA2885919A1

Abstract

Digestion of cellulosic biomass solids may be conducted in a pressure vessel that contains both a hydrothermal digestion unit and a catalytic reduction reactor unit. Biomass conversion systems incorporating such a feature may comprise: a pressure vessel that comprises a first section comprising a hydrothermal digestion unit and a second section comprising a first catalytic reduction reactor unit that contains a first catalyst capable of activating molecular hydrogen; wherein the hydrothermal digestion unit and the first catalytic reduction reactor unit are in fluid communication with one another; a biomass feed mechanism that is operatively connected to the pressure vessel, the biomass feed mechanism being capable of introducing cellulosic biomass solids to the pressure vessel and also capable of withdrawing a reaction product from the first catalytic reduction reactor unit; and a hydrogen feed line that is operatively connected to the first catalytic reduction reactor unit.

Description

For integrating the conversion systems for biomass with single container hydro-thermal slaking apparatus and catalytic reduction reactor device and the application process thereof of stabilised hydrolysate

Technical field

Present disclosure relates generally to the digestion of cellulose series biomass solid, with relate more specifically to conversion systems for biomass and application process thereof, its allows to use and comprises the hydrothermal digestion device of fluid coupling and the pressurizing vessel of catalytic reduction reactor device the hydrolysate containing soluble-carbohydrate is catalytically conveted to more stable product.

Background technology

The many kinds of substance with commercial significance can originate from natural resources, particularly living beings.Owing to having found various forms of multiple abundant carbohydrate wherein, cellulose series biomass in this respect may be advantageous particularly.As used herein, term " cellulose series biomass " refers to the biomaterial comprising cellulosic survival or survival recently.The ligno-cellulosic materials found in the cell membrane of high-grade plant is carbohydrate source the abundantest in the world.Usually the material produced by cellulose series biomass can comprise such as through the paper of partial digested generation and paper pulp and the bio-ethanol that produces through fermentation.

Plant cell wall is divided into two parts, i.e. primary cell wall and secondary cell wall.Primary cell wall is provided for the support structure of cell expansion and is made up of three kinds of main polysaccharide (cellulose, colloid and hemicellulose) and one group of glycoprotein.Secondary cell wall produces after cell completes growth, also comprises polysaccharide and by strengthening with the polymerism lignin of hemicellulose covalent cross-linking.Hemicellulose and the usual rich content of colloid, but cellulose is main polysaccharide and the abundantest carbohydrate source.As discussed below, it is more difficult that the complex mixture of each component co-existed in cellulose may make it deal with.

There is a large amount of notices to be placed on and developed on the fossil fuel substitute that obtained by renewable source.In this respect, cellulose series biomass enriches due to its storage and has found a large amount of different component (particularly cellulose and other carbohydrate) wherein and caused special attention.Although get a good chance of and cause the great interest of people, the exploitation of biologically based fuels technology and enforcement are still slowly.Until today, the fuel that prior art produces still has low energy density (such as bio-ethanol) and/or can not completely compatible with transport infrastructure with existing engine design (such as methyl alcohol, biodiesel, Fischer-Tropsch diesel oil, hydrogen and methane).Tackling aforementioned and other problem, will be special hope for cellulose series biomass being treated to energy and the cost effective method of the fuel mixture with similar fossil fuel composition.

When transform cellulose series biomass be fuel mixture and other material time, can extract the carbohydrate of cellulose and other complexity wherein existed, and be translated into simpler organic molecule, the latter can reform subsequently further.Fermentation is a kind of method that the complex carbohydrates from cellulose series biomass can be converted into more useful form.But fermentation process usually very slow, need the reactor of large volume, high diluting condition and generation to have initial reaction product (ethanol) compared with low energy densities.Digestion is the another kind of method that cellulose and other complex carbohydrates can be converted into more useful form.The carbohydrate breakdown of the cellulose in cellulose series biomass and other complexity can be simpler soluble-carbohydrate by digestion method, and the reforming reaction that the latter is adapted to pass through downstream transforms further.As used herein, term " soluble-carbohydrate " refers in digestion process, become soluble monose or polysaccharide.Although support digest cellulose and other complex carbohydrates and transform simple carbohydrates to be further and those similar organic compounds of existing in fossil fuel not yet develop that to be suitable for transforming cellulose series biomass be the high yield of fuel mixture and the digestion method of Energy Efficient according to understanding Essential Chemistry.In this respect, digest to application that to transform cellulose series biomass with other method be most primary demand that fuel mixture is relevant and be and realize transforming the energy needed and input and should not be greater than the obtainable Energy transmission of product fuel mixture.This primary demand causes multiple secondary issues, and these problems totally propose the great engineering challenge up till now for extremely also not solving.

Digest that cellulose series biomass to be converted into the relevant problem of fuel mixture not only complicated to applying with energy and the effective mode of expense, and they are different from those problems run in the digestion process of application usually in papermaking and pulp industry completely.Because the object of cellulose series biomass digestion retains solid matter (such as paper pulp) in papermaking and pulp industry, (be such as less than about 100 DEG C) usually at low temperatures and implement the incomplete digestion quite short time.In contrast, being applicable to transforming cellulose series biomass is that fuel mixture is configured to make maximize yields in high flux mode by dissolving the charging of initial fiber as much as possible element biolobic material with the digestion process of other material ideally.

Because multiple reason is by conventional adjustment papermaking and paper pulp digestion process, the soluble-carbohydrate produced for fuel mixture and other material is infeasible.It is undesirable for producing more soluble-carbohydrates from flux angle simply by the digestion process longer time running papermaking and pulp industry.Application digestive enhancers such as highly basic, alkali acid or sulphite make digestion rate accelerate and protection downstream components may to be needed not increase process costs and complexity by the infringement of these reagent due to the separating step of post processing.Digestion rate is made to accelerate to actually reduce yield due to the thermal degradation of soluble-carbohydrate may be there is at high digestion temperature by improving digestion temperature, particularly when the time of prolongation.Once be produced by digestion, soluble-carbohydrate very have activity and may fast degradation to produce caramelan and other heavy catabolite, particularly in hot conditions as at being greater than 150 DEG C.From energy efficiency angle, it is also undesirable for applying higher digestion temperature.Any one of these difficulties all can defeat the economic feasibility obtaining fuel mixture from cellulose series biomass.

A kind of method of soluble-carbohydrate not thermal degradation can be protected to be make them stand one or more catalytic reduction reactions, and described reaction can comprise hydrogenation and/or hydrogenolysis.Carry out stable meltable carbohydrate the digestion of cellulose series biomass can be allowed to implement at than possible higher temperature by implementing one or more catalytic reduction reactions, and can not excessive sacrifice yield.In addition, the product of catalytic reduction reaction process can be converted into fuel mixture and other material easily by the reforming reaction in downstream.Depend on reaction condition and the catalyst of use, the product formed owing to carrying out one or more catalytic reduction reactions to soluble-carbohydrate may comprise triol, glycol, monohydric alcohol or their any combination, and wherein some also may comprise remaining carbonyl functionality's (such as aldehydes or ketones).These product are than soluble-carbohydrate more thermal-stable and be easily converted into fuel mixture and other material by carrying out one or more downstream reforming reactions.In addition, the product of the above-mentioned type is the good solvent that wherein can carry out hydrothermal digestion, promotes that soluble-carbohydrate is if their product and cellulose series biomass component are as the dissolving of lignin thus.

To process cellulose series biomass be that another problem that fuel mixture is relevant with other material comes from the high conversion percentages needing cellulose series biomass charging to become soluble-carbohydrate.Particularly, when cellulose series biomass solid digests, their size is decreased to the point that they can become fluid flowing gradually.As what apply here, can will be called as " cellulose series biomass fine grained " by the cellulose series biomass solid, particularly size of the fluid flowing cellulose series biomass solid that is about 3mm or less.Cellulose series biomass fine grained can transport out from the digestion zone of the system for transforming cellulose series biomass, and enters one or more region not needing solid and solid to be harmful to.Such as, cellulose series biomass fine grained likely can blocking catalyst bed, feed-line etc.In addition, although size is little, but cellulose series biomass fine grained may represent the pith of cellulose series biomass charging, and if they can not be further converted to soluble-carbohydrate, the ability obtaining gratifying conversion percentages may will be affected.Because the digestion process of papermaking and pulp industry runs under quite low cellulose series biomass conversion percentages, believe that creating a small amount of cellulose series biomass fine grained has less impact with this to these digestion processes.

Except the carbohydrate wanted, may there is other material in cellulose series biomass, these materials may be a problem especially to processing with energy and the effective mode of expense.Sulfur-bearing and/or nitrogenous amino acid or other catalyst poison may exist in cellulose series biomass.If do not removed, these catalyst poisons may affect the catalytic reduction reaction for stable meltable carbohydrate, thus cause the process for catalyst regeneration and/or replacement to stop, and reduce total energy efficiency when restart procedure.On the other hand, remove the energy efficiency that these catalyst poisons also may affect biomass conversion process during the course, implement because implement to remove under the ion exchange process usually needed produces the temperature of soluble-carbohydrate through being everlasting lower than digestion, thus introducing heat exchange operation, this will increase the complexity of design and may increase running cost.Except catalyst poison beyond the region of objective existence, lignin (non-cellulose class biopolymer) may be supervened soluble-carbohydrate and be dissolved.If can not solve in some way, in biomass conversion process, lignin concentration may become enough high to such an extent as to finally sedimentation occur, and causes expensive system downtime thus.Alternatively, some lignin may keep not dissolving, and may finally need expensive system downtime it to be removed.

As aforementioned proved, effectively conversion cellulose series biomass is fuel mixture is the challenge with very big engineering challenge.The present invention tackles these challenges and provides associated advantages.

Summary of the invention

In some embodiments, the invention provides a kind of conversion systems for biomass, comprise: the pressure vessel comprising first paragraph and second segment, described first paragraph comprises hydrothermal digestion device and described second segment and comprises containing can the first catalytic reduction reactor device of the first catalyst of anakmetomeres hydrogen, wherein hydrothermal digestion device and the first catalytic reduction reactor device fluid communication with each other; Operate with pressure vessel the living beings feeding mechanism be connected, cellulose series biomass solid can be introduced pressure vessel and also can from the first catalytic reduction reactor device extraction product by described living beings feeding mechanism; And operate with the first catalytic reduction reactor device the hydrogen feeding line be connected.

In some embodiments, the invention provides a kind of conversion systems for biomass, comprising:

The pressure vessel comprising first paragraph and second segment is provided, described first paragraph comprises hydrothermal digestion device and second segment and comprises containing can the first catalytic reduction reactor device of the first catalyst of anakmetomeres hydrogen, wherein hydrothermal digestion device and the first catalytic reduction reactor device fluid communication with each other; Operate with pressure vessel the living beings feeding mechanism be connected, described living beings feeding mechanism can keep, during pressurization state, cellulose series biomass solid is introduced pressure vessel at pressure vessel; The hydrogen feeding line be connected is operated with the first catalytic reduction reactor device; With comprise pressure vessel and containing can the fluid circulation loop of the second catalytic reduction reactor device of the second catalyst of anakmetomeres hydrogen.

In some embodiments, the invention provides a kind of method, comprise: the pressure vessel comprising first paragraph and second segment is provided, described first paragraph comprises hydrothermal digestion device and second segment and comprises containing can the first catalytic reduction reactor device of the first catalyst (the first hydrogenation catalyst catalyst) of anakmetomeres hydrogen, wherein hydrothermal digestion device and the first catalytic reduction reactor device fluid communication with each other; Cellulose series biomass solid is added in pressure vessel; Cellulose series biomass solid in the hydrothermal digestion device of heated pressure container, is formed in liquid phase the hydrolysate comprising soluble-carbohydrate thus; Under molecular hydrogen exists, conveying liquid is mutually by the first catalytic reduction reactor device, thus described soluble-carbohydrate is converted into product at least partly; With at least part of described liquid phase is delivered to containing can the second catalytic reduction reactor device of the second catalyst (the second hydrogenation catalyst catalyst) of anakmetomeres hydrogen from pressure vessel, thus soluble-carbohydrate is further converted to product.

Read following to the description of preferred embodiment after, the features and advantages of the present invention will become more obvious to those skilled in the art.

Accompanying drawing explanation

Comprise following accompanying drawing to describe some aspect of the present invention, and should not regarded them as exclusiveness embodiment.Disclosed theme can carry out the adjustment of quite large degree, change, combination and equivalencing in form and function aspects, and this is clearly for those skilled in the art after benefiting from present disclosure.

Fig. 1 representatively illustrates descriptive cyclic pressure vessel, and described cyclic pressure vessel is included in the interior catalyst reduction reaction apparatus and outside hydrothermal digestion device that hold in external pressure shell.

Fig. 2 representatively illustrates in descriptive pressure vessel, and wherein hydrothermal digestion device and catalytic reduction reactor device are each other side by side in external pressure shell.

Fig. 3 representatively illustrates descriptive conversion systems for biomass, and described conversion systems for biomass has the hydrothermal digestion device and catalytic reduction reactor device that hold in pressure vessel.

Fig. 4 representatively illustrates descriptive conversion systems for biomass, described conversion systems for biomass has the hydrothermal digestion device and catalytic reduction reactor device that hold in pressure vessel, and wherein fluid circulation loop is set up direct flow and is communicated with between fluid intake and the fluid issuing of pressure vessel.

Detailed description of the invention

In embodiment described here, under digestion solvent exists, the digestion rate of cellulose series biomass can be accelerated at high temperature and pressure, and described high pressure makes digestion solvent be liquid state under higher than its normal boiling point.Although from the angle of flux, digestion rate may be wish faster, and soluble-carbohydrate may be easy to degraded under these conditions, as discussed in more detail below.In various embodiments, digestion solvent may comprise organic solvent, and the organic solvent of particularly original position generation, this organic solvent can provide some advantage, as described below.

This disclosure provides system and method, it allows cellulose series biomass solid effectively to digest to form soluble-carbohydrate, this carbohydrate is converted into the more stable product comprised containing oxygen intermediate by one or more catalytic reduction reactions (such as hydrogenolysis and/or hydrogenation) subsequently, and this product can be further processed as higher hydrocarbon.Higher hydrocarbon can be used for forming industrial chemical and transport fuel (i.e. bio-fuel), comprises as synthetic gasoline, diesel fuel, jet fuel etc.As herein apply, term " bio-fuel " refers to by the biogenic any transport fuel formed.Here this bio-fuel can be described as " fuel mixture ".Especially, constructing system and method described here makes cellulose series biomass solid can the digested hydrolysate produced containing soluble-carbohydrate, and at least part of soluble-carbohydrate wherein in hydrolysate can be rapidly converted into more stable product by catalytic reduction reaction after digestion before may degrading.In embodiment described here, complete together with hydrothermal digestion device being coupled at catalytic reduction reactor device fluid in pressure vessel.The hydrothermal digestion device of fluid coupling and the various structures of catalytic reduction reactor device are possible, as described below.Can the polytype catalyst (also referred to as " hydrogen activation catalyst " or " hydrogenation catalyst catalyst ") of anakmetomeres hydrogen may be used for regulating catalytic reduction reaction.Advantageously, cellulose series biomass solid may be used for promoting catalyst and is retained in pressure vessel, as described below.Soluble-carbohydrate is converted into the amount of the thermal decomposition occurred after more stable product can reduce hydrothermal digestion close to their starting point, which thereby enhances the yield of desired product and be conducive to high biomass conversion rate.By carrying out hydrothermal digestion and catalytic reduction also can realize other advantage in Pressure Vessel, as discussed below.

As herein apply, term " containing oxygen intermediate " refers to the alcohol, polyalcohol, ketone, aldehyde and their mixture that produce from the catalytic reduction reaction (such as hydrogenolysis and/or hydrogenation) of soluble-carbohydrate.As herein apply, the ratio that term " higher hydrocarbon " refers to oxygen and carbon is less than the hydrocarbon of at least one component of the biomass sources producing them.As used herein, term " hydrocarbon " refers to the organic compound mainly comprising hydrogen and carbon, although hetero atom such as oxygen, nitrogen, sulphur and/or phosphorus may be present in some embodiments.Therefore, term " hydrocarbon " also comprises the compound of the hybrid atom MCM-41 as carbon containing, hydrogen and oxygen.

When using digestion solvent in hydrothermal digestion at high temperature and pressure, digestion process may become suitable power consumption.If the energy input requirements of consumption process becomes too large, the economic feasibility of cellulose series biomass as raw material may be endangered.That is, if the energy input that digest cellulose biolobic material needs becomes too large, processing cost may higher than the real value producing product.In order to keep processing cost low, wish that the outside heat input quantity adding digestion process keeps low as far as possible, realize cellulose series biomass to the high as far as possible conversion ratio of soluble-carbohydrate, described soluble-carbohydrate can be converted into more stable product subsequently simultaneously.Hereinafter by the conversion of more detailed description soluble-carbohydrate to more stable product.

In embodiment described here, by there is at least part of stable meltable carbohydrate of catalytic reduction reaction occurred in the uniform pressure container of hydrothermal digestion wherein.Once soluble-carbohydrate is converted into more stable product at least partly, in the independent catalytic reduction reactor device not included in pressure vessel, the completely conversion of soluble-carbohydrate to product can occur, wherein said catalytic reduction reactor device also adopts can the slurry catalyst of anakmetomeres hydrogen or different catalyst.The feature of described conversion systems for biomass can allow a large amount of initially dissolved carbohydrate-modifying form for being appropriate to be treated to subsequently bio-fuel, forms the least possible caramelan and other catabolite in hydrothermal digestion device or near it simultaneously.

In embodiment as described here, by carrying out hydrothermal digestion and catalytic reduction can realize many advantages in identical pressure vessel.As discussed above, the important advantage of conversion systems for biomass as described herein is most of hydrolysate that tectonic system produces in hydrothermal digestion device with immediate stability.By completing the stable of hydrolysate the soluble-carbohydrate in hydrolysate being converted into product at least partly with the catalytic reduction reaction that occurs in the catalytic reduction reactor device of hydrothermal digestion device fluid coupling.Together with being coupled at catalytic reduction reactor device fluid by hydrothermal digestion device in Pressure Vessel, the conveying number of times of hydrolysate to catalytic reduction reactor device can be reduced, thus reduce the possibility of soluble-carbohydrate degraded.

Another important advantage of conversion systems for biomass described in the invention in Pressure Vessel, carries out hydrothermal digestion and catalytic reduction can allow to realize excellent heat integration and heat management.As described below, hydrothermal digestion is endothermic process, and catalytic reduction is exothermic process.Because these two processes occur in the uniform pressure container in conversion systems for biomass as described herein, the excessive heat produced by catalytic reduction reaction may be used for driving hydrothermal digestion process.This can need input with the total energy efficiency driving the amount of the external energy of hydrothermal digestion to improve biomass conversion process by restriction.

As discussed above, the initial reaction product produced in pressure vessel can be delivered to the second catalytic reduction reactor device and be used for being further converted to product, this product is easier to be converted into bio-fuel or other material.The the second catalytic reduction reactor device wherein occurring to transform further can separate with the pressure vessel that initial catalyst reduction reaction wherein occurs.The further conversion occurred can comprise reduce further initial reaction product degree of oxidation, increase soluble-carbohydrate to containing the conversion ratio of oxygen intermediate or both.The product obtained by the second catalytic reduction reactor device can be circulated in pressure vessel, and it can be used as digestion solvent wherein, and/or it can be extracted out for being converted into bio-fuel or other material subsequently from the second catalytic reduction reactor device.By at least partly soluble-carbohydrate being converted into product before hydrolysate arrives the second catalytic reduction reactor device, the requirement to the second catalytic reduction reactor device can be reduced, and also may realize the more high conversion of soluble-carbohydrate to product.In addition, likely application is than the second less catalytic reduction reactor device feasible in addition, because before arrival second catalytic reduction reactor device, at least part of soluble-carbohydrate is converted.Further, because by implementing hydrothermal digestion and initial catalyst reduction reaction can realize large heat integration efficiency in identical pressure vessel, may reduce to maintain Energy Efficient process from the second catalytic reduction reactor device circular response product to the demand of hydrothermal digestion device.Therefore, lower product recycle ratio can be applied, and the product can extracting greater part out is for being converted into bio-fuel subsequently.Preceding factors also can reduce the investment relevant to conversion systems for biomass and running cost.

Heat integration efficiency another in, conversion systems for biomass of the present invention also may be advantageous particularly, because the pressure vessel of system can maintain at high temperature and pressure continuously in some embodiments.Therefore, as long as fresh cellulose series biomass solid continuous or semicontinuous being supplied in pressure vessel pressure release can not occur, hydrothermal digestion just can recur.If not having ability to be that pressure vessel introduces fresh fiber element biolobic material solid when maintaining pressurization state, pressure release and cooling may be there is in living beings adding procedure, significantly reducing energy and the cost efficiency of conversion process.As used herein, term " adds " and grammer term of equal value refers in container, add the process of living beings when there is not complete pressure release in uninterrupted mode substantially continuously.As used herein, term " semicontinuous add " and grammer term of equal value thereof refer to discontinuous when there is not complete pressure release but in container, add living beings as required.The further describing of living beings feeding mechanism of living beings can be provided in pressurizing vessel to provide in more detail hereinafter.

In embodiment described here, can all kinds fluid flowing catalyst of anakmetomeres hydrogen all can be used for being present in the catalytic reduction reactor device in pressure vessel.As described below, at least some cellulose series biomass solid also may reside in the catalytic reduction reactor device of pressure vessel.Therefore, catalyst such as the fixed bde catalyst being easy to block under solid exists shall not be applied in this position usually.The descriptive catalyst type that can be used in the catalytic reduction reactor device of pressure vessel comprises as slurry catalyst, boiling-bed catalyst and fluid catalyst etc.Same catalyst or different catalysts can be present in the second catalytic reduction reactor device not being arranged in pressure vessel.

The FAQs relevant to the use of fluid flowing catalyst usually needs the holding mechanism (such as catalyst screen, filter etc.) be applicable to remain on desired position to make catalyst.But in embodiment described here, have been found that and can advantageously use cellulose series biomass solid to help fluid flowing catalyst to remain in pressure vessel and/or the mechanism of catalyst easily returning pressure container can be made in being provided in interpolation biomass process wherein.Particularly, have been found that the reunion of cellulose series biomass solid can effectively separate catalyst solid moving freely with limiting catalyst.Therefore, cellulose series biomass solid not only digests in pressure vessel, but also can at pressure vessel and/or for introducing in the living beings feeding mechanism of pressure vessel cellulose series biomass solid effectively as catalyst screen.In some embodiments, if wished, can be for the more effective size of screening catalyst by cellulose series biomass solids treatment before adding in pressure vessel.In addition, fluid flowing catalyst moves freely through the distribution that cellulose series biomass solid is conducive to promoting catalyst, causes more easily stable soluble-carbohydrate thus.

As described above, to be similar to mode catalyst occurring and separates, conversion systems for biomass as described herein can contribute to reducing the fine grain amount of cellulose series biomass being delivered to the second catalytic reduction reactor device by pressure vessel.Cellulose series biomass fine grained can naturally be present in introduce pressure vessel living beings in or living beings experience hydrothermal digestion process in produce.Therefore, in some embodiments, fluid flowing catalyst may be used for the second catalytic reduction reactor device, or in other embodiments, fixed bde catalyst may be used for the second catalytic reduction reactor device.Optionally, solid separating mechanism also may be used for separating any catalyst in the liquid phase being delivered to the second catalytic reduction reactor device and/or cellulose series biomass fine grained thus provides extra protection to it.

Conversion systems for biomass as described herein and correlation technique be different from papermaking and pulp industry further those, the object of the latter gathers in the crops partial digested wood pulp, instead of obtaining soluble-carbohydrates a large amount of as far as possible, this carbohydrate can be subsequently converted to the product comprised containing oxygen intermediate.Because the object of papermaking and pulp processing obtains thick wood pulp, this digestion process can be carried out at relatively low temperatures and pressures to remove the soluble-carbohydrate that can remove at a lower temperature and the non-cellulose class component of small amount from living beings.In some described here embodiments, by butt, can by the cellulose series biomass of at least 60% digestion to produce the hydrolysate comprising soluble-carbohydrate.In other described here embodiment, by butt, can by the cellulose series biomass of at least 90% digestion to produce the hydrolysate comprising soluble-carbohydrate.Consider the object of papermaking and pulp processing, expect the soluble-carbohydrate producing much less in these processes.The time of staying that the design of conversion systems for biomass of the present invention can keep long by minimizing catabolite formation in the process of process cellulose series biomass simultaneously in hydrothermal digestion process realizes this high conversion.

Although from stable meltable carbohydrate and the angle realizing excellent heat integration, the catalytic reduction reaction of the hydrothermal digestion and soluble-carbohydrate that carry out the cellulose series biomass solid combined in Pressure Vessel may be favourable, but may there is some challenges in the conversion systems for biomass carrying out this structure, as discussed above.Catalyst poisoning also may be the problem of some catalyst, because when carrying out catalytic reduction in the pressure vessel identical with hydrothermal digestion, and Removal of catalyst poisonous substance from hydrolysate of almost having no chance.A kind of method of this problem can be avoided to be use resistance to malicious catalyst, and wherein some are discussed below.Another replacement scheme uses the catalyst regenerated under being exposed to the condition can set up in pressure vessel.Such as, in some embodiments, slurry catalyst can by being exposed to the water reuse (treatment of at least 300 DEG C of temperature.

Another replacement scheme solving catalyst poisoning problem uses independently slaking apparatus to carry out the digestion of cellulose series biomass solid by stages.Many poisonous substances of catalyst failure can be made to be derived from sulfur-containing compound in crude fibre biolobic material solid and nitrogen-containing compound.At the digestion temperature that the temperature producing soluble-carbohydrate than cellulose is lower, these compounds can remove at least partly together with lignin with at least some hemicellulose from cellulose series biomass solid.By controlling digestion temperature, can produce and be rich in cellulose but the poor biomass slurry containing catalyst poison, hemicellulose and/or lignin, described catalyst poison, hemicellulose and/or lignin all do not wish to be present in for generation of in soluble-carbohydrate or the process of product that derived by soluble-carbohydrate.Advantageously, adding pressure vessel and process with before producing product, can from biomass slurry at least part of Removal of catalyst poisonous substance, hemicellulose and/or lignin, in embodiment as described here.That is, in some embodiments, the poor biomass slurry containing catalyst poison, hemicellulose and/or lignin at least partly can be introduced in pressure vessel as described herein.

Use multiple slaking apparatus not only can reduce the possibility of catalyst poisoning, and this use can also advantageously reduce lignin from liquid phase sedimentation and in conversion systems for biomass (such as in feed-line etc.) form the possibility of undesirable blocking.In some embodiments, conversion systems for biomass as described herein may further include lignin separation mechanism.By removing at least some lignin before generation hydrothermal digestion from cellulose series biomass solid, from liquid phase, separating lignin more infrequently can carry out than separation possible in addition.

If here do not pointed out in addition, be understood that in description here and apply term " living beings " or " cellulose series biomass " refers to " cellulose series biomass solid ".Described solid can be any size, shape or form.Cellulose series biomass solid can exist naturally with any one of these solids size, shape or form, or they here can process further in described embodiment before digestion.In embodiment described here, cellulose series biomass solid also can exist as a slurry.

In enforcement embodiment of the present invention, the suitable biological matter source of any type can be applied.Suitable cellulose series biomass source can comprise such as forestry residue, agricultural residue, draft material, municipal solid waste, paper, paper pulp and the paper mill residue discarding and reclaim and their any combination.Therefore, in some embodiments, suitable cellulose series biomass can comprise such as maize straw, straw, bagasse, Chinese silvergrass, chinese sorghum residue, switchgrass, bamboo, water hyacinth, hardwood, hardwood bits, cardboard slurry, cork, cork dust, tender pump and/or their any combination.Leaf, root, seed, stem, shell etc. can be used as the source of cellulose series biomass.The general source of cellulose series biomass can comprise such as agricultural wastes (as corn stalk, straw, seed hulls, bagasse, shuck etc.), timber (as wood or bark, sawdust, timber are cut and cut thing, logging headquarter disintegrating slag etc.), municipal waste (as waste paper, turf-mown thing or residue etc.) and energy crop (as white poplar, willow, switchgrass, clover, prairie bluestem, corn, soya bean etc.).Can based on considering that such as cellulose and/or hemicellulose level, content of lignin, growth time/season, growth place/cost of transportation, planting cost, harvesting cost etc. select cellulose series biomass as follows.

The exemplary carbohydrate that can exist in cellulose series biomass can comprise such as sugar, sugar alcohol, cellulose, lignocellulosic, hemicellulose and their any combination.Once be stripped of soluble-carbohydrate by digestion process by embodiment described herein from living beings matrix, soluble-carbohydrate can be converted into by catalytic reduction reaction the product comprised containing oxygen intermediate.In some embodiments, the combination that the product comprised containing oxygen intermediate can apply further hydrogenolysis, hydrogenation reaction, condensation reaction, isomerization reaction, oligomerization, hydrotreatment reaction, alkylated reaction etc. is further converted to bio-fuel.In some embodiments, solvent can be digested by being recycled to hydrothermal digestion device containing oxygen intermediate at least partially at least partially to comprise.From heat integration and process efficiency angle, it also may be particularly advantageous that recirculation contains oxygen intermediate to hydrothermal digestion device at least partially.

In some embodiments, conversion systems for biomass as described herein can comprise: the pressure vessel comprising first paragraph and second segment, described first paragraph comprises hydrothermal digestion device and described second segment and comprises containing can the first catalytic reduction reactor device of the first catalyst of anakmetomeres hydrogen, wherein hydrothermal digestion device and the first catalytic reduction reactor device fluid communication with each other; Operate with pressure vessel the living beings feeding mechanism be connected, cellulose series biomass solid can be introduced pressure vessel and also can from the first catalytic reduction reactor device extraction product by described living beings feeding mechanism; And operate with the first catalytic reduction reactor device the hydrogen feeding line be connected.

In some embodiments, conversion systems for biomass may further include the fluid circulation loop set up fluid and be communicated with between the fluid intake of pressure vessel and the fluid issuing of living beings feeding mechanism.That is, in such an implementation, conversion systems for biomass can be constructed and make liquid phase can be conducted through living beings feeding mechanism and returning pressure container subsequently.In other embodiments, fluid circulation loop directly can set up fluid communication between the fluid intake of pressure vessel and fluid issuing.That is, in such an implementation, liquid phase need not pass living beings feeding mechanism.Once returning pressure container, the product in liquid phase can be used as digestion solvent in hydrothermal digestion device and/or wherein unreacted soluble-carbohydrate can experience further catalytic reduction to produce product.In addition, as described above, the liquid phase of returning pressure container can contribute to the heat distribution maintaining it.

In some embodiments, fluid circulation loop may further include containing can the second catalytic reduction reactor device of the second catalyst of anakmetomeres hydrogen.As described above, the second catalytic reduction reactor device may be used for making the soluble-carbohydrate in liquid phase be further converted to product.In some embodiments, the first catalyst and the second catalyst can be identical.In other embodiments, the first catalyst and the second catalyst can be different.Below further describe the applicable catalyst for catalytic reduction reactor device.

In some embodiments, conversion systems for biomass as described herein can comprise: the pressure vessel comprising first paragraph and second segment, described first paragraph comprises hydrothermal digestion device and described second segment and comprises containing can the first catalytic reduction reactor device of the first catalyst of anakmetomeres hydrogen, wherein hydrothermal digestion device and the first catalytic reduction reactor device fluid communication with each other; Operate with pressure vessel the living beings feeding mechanism be connected, living beings feeding mechanism can keep, during pressurization state, cellulose series biomass solid is introduced pressure vessel at pressure vessel; The hydrogen feeding line be connected is operated with the first catalytic reduction reactor device; And fluid circulation loop, described fluid circulation loop comprises pressure vessel and containing can the second catalytic reduction reactor device of the second catalyst of anakmetomeres hydrogen.

The various structures with the pressure vessel of independently hydrothermal digestion device and catalytic reduction reactor device are possible.In some embodiments, pressure vessel can comprise circulus, and described first paragraph forms the exterior section of circulus, and described second segment forms the interior section of circulus.That is, in such an implementation, conversion systems for biomass can comprise inner first catalytic reduction reactor device and outside hydrothermal digestion device, and the two all remains in external pressure shell.In other embodiments, described first paragraph and second segment can each other and come in pressure vessel.Other structure of pressure vessel is also possible, and usual fluid is connected but any pressure vessel with hydrothermal digestion device and catalytic reduction reactor device be separated from each other all can be used in the present embodiment.

Fig. 1 and 2 representatively illustrates descriptive pressure vessel, and described pressure vessel comprises hydrothermal digestion device and catalytic reduction reactor device, and the two fluid is connected but is separated from each other.Fig. 1 representatively illustrates descriptive cyclic pressure vessel 1, and described cyclic pressure vessel 1 comprises and is contained in interior catalyst reduction reaction apparatus 2 in external pressure shell 4 and outside hydrothermal digestion device 3.Fig. 2 representatively illustrates descriptive pressure vessel 5, and wherein hydrothermal digestion device 6 and catalytic reduction reactor device 7 are each other side by side in external pressure shell 8.Although Fig. 1 and 2 describes the pressure vessel of cylindric structure substantially, should be realized that and can use any shape.In Fig. 1 and 2 arrow representative in digestion process hydrolysate and main body living beings the flow direction and when in the process being converted into product by the flow direction of liquid phase during catalytic reduction reactor device.As described in figures 1 and 2, catalytic reduction reactor device 2 and 7 is as gas lift, slurries or fluidized bed reactor operation.But also can use other reactor structure.Above-mentioned pressure vessel can be combined with conversion systems for biomass as described herein.Fig. 3 and 4, hereafter will discuss in more detail, there is shown descriptive conversion systems for biomass, and described conversion systems for biomass has and is contained in hydrothermal digestion device in pressure vessel and catalytic reduction reactor device.

In some embodiments, conversion systems for biomass can comprise the living beings feeding mechanism operating with pressure vessel and be connected.In some embodiments, living beings feeding mechanism can keep, during pressurization state, cellulose series biomass solid is introduced pressure vessel at pressure vessel.In some embodiments, living beings feeding mechanism also can from pressure vessel extraction product.In various embodiments, living beings feeding mechanism can be included in the pressure transition district changed between low pressure state (such as normal pressure) and high voltage state.In some other embodiments, living beings feeding mechanism may further include atmospheric area.Cellulose series biomass solid can be introduced in pressure transition district, and their pressure can be increased to the level being suitable for introducing pressure vessel.

When it is present, the atmospheric area be applicable to of living beings feeding mechanism can comprise as conveyer belt, vibrating tube conveyer, screw feeder or conveyer, storage tank, surge tank and storehouse formula distributor etc.Can be used to or the semicontinuous pressure transition district that be applicable to that add cellulose series biomass solid continuous to pressure vessel and can comprise the pressurization screw feeder, pressure switch room etc. described in U.S. Patent Application Publication US2013/0152457 as owned together and US 2013/0152458.

In some embodiments, living beings feeding mechanism can allow cellulose series biomass solid to be introduced into pressure vessel when the incomplete pressure release of pressure vessel.Before introducing pressure vessel, cellulose series biomass solid being pressurizeed can allow hydrothermal digestion device to keep pressurized state and continued operation.As described above, pressurization can contribute to the heat integration and the energy efficiency that maintain living beings digestion process.More benefits that cellulose series biomass solid is pressurizeed also are discussed hereinafter.

In some embodiments, the cellulose series biomass solid in living beings feeding mechanism can be made at least partly to pressurize by least part of liquid phase in pressure vessel is introduced pressure transition district.In some or other embodiment, pressure transition district can be made at least partly to pressurize by introducing gas to pressure transition district.In some embodiments, described liquid phase can comprise the organic solvent that the product as catalytic reduction reaction produces.In other embodiments, can apply external solvent makes pressure transition district pressurize.

Use the liquid phase from slaking apparatus that cellulose series biomass solid is pressurizeed and can realize at least two benefits.First, make biomass solid pressurize in the presence of a liquid phase and digestion solvent may be made to infiltrate biomass solid, once introduce in pressure vessel, this may make biomass solid be immersed in digestion solvent.In addition, by adding the liquid phase of heat in pressure transition district in biomass solid, once introduce in pressure vessel, may need less energy input that biomass solid is heated up.These features all can improve the efficiency of digestion process.

Fig. 3 representatively illustrates descriptive conversion systems for biomass, and described conversion systems for biomass has and is contained in hydrothermal digestion device in pressure vessel and catalytic reduction reactor device.For the sake of simplicity, Fig. 3 describes the cyclic pressure vessel structure described in Fig. 1.But should be realized that other pressure vessel construction also can be used in embodiment as described herein.In addition, the catalytic reduction reactor device be contained in pressure vessel provides in cut away view, thus cellulose series biomass solid wherein and catalyst granules can more clearly be described.

As shown in Figure 3, conversion systems for biomass 10 comprises pressure vessel 12, and it comprises hydrothermal digestion device 14 in external pressure shell 18 and the first catalytic reduction reactor device 16.Hydrothermal digestion device 14 and the first catalytic reduction reactor device 16 are by fluid conduit systems district 26 fluid coupling each other.Fluid conduit systems district 26 allows the hydrolysate produced in hydrothermal digestion device 14 to flow downward under gravity and is upwards carried in the first catalytic reduction reactor device 16 under molecular hydrogen exists afterwards.As described in Figure 3, the first catalytic reduction reactor device 16 is operated at least partly by gas lift.

By living beings retraction mechanism 20, cellulose series biomass solid is introduced pressure vessel 12, shown living beings retraction mechanism 20 comprises atmospheric area 22 and pressure transition district 24.Cellulose series biomass solid can be contained in atmospheric area 22 and neutralize and add pressure transition district 24 as required.The cellulose series biomass solid adding pressure transition district 24 can be converted to pressurization state from normal pressure and make them can introduce pressure vessel 12.Can have and be present in various valve between atmospheric area 22 and pressure transition district 24 and between pressure transition district 24 and pressure vessel 12 or other pressure isolation mechanism, object for the sake of simplicity is not described them.Those skilled in the art are familiar with pressure isolation mechanism be applicable to and uses thereof.The living beings feeding mechanism be applicable to that cellulose series biomass solid can be supplied to pressurizing vessel has been described in detail above.

In the process of operation conversion systems for biomass 10, continuous or semicontinuous benchmark can add cellulose series biomass solid to pressure vessel 12.As described above, cellulose series biomass solid can be added living beings feeding mechanism 20 and be increased to pressurization state.Afterwards, cellulose series biomass solid can introduce pressure vessel 12.When after introducing pressure vessel 12, cellulose series biomass solid can enter hydrothermal digestion device 14 and be converted into soluble-carbohydrate at least partly.In some embodiments, at least part of cellulose series biomass solid also can enter the first catalytic reduction reactor device 16.As described below, cellulose series biomass solid being introduced the first catalytic reduction reactor device 16 may be advantageous particularly.

The hydrolysate produced in hydrothermal digestion device 14 can enter fluid conduit systems district 26, and it can enter the first catalytic reduction reactor device 16 and upwards flow through wherein in the process being converted into product subsequently.By hydrogen feeding line 28, molecular hydrogen is introduced the first catalytic reduction reactor device 16.First catalytic reduction reactor device 16 comprises catalyst granules 30 and optional cellulose series biomass solid 32.As described above, cellulose series biomass solid 32 can contribute to catalyst granules 30 to be retained in the first catalytic reduction reactor device 16.Some catalyst granules that first catalytic reduction reactor device 16 can not retain are by the living beings that flow downward in hydrothermal digestion device 14 and hydrolysate conveying.As described above, these catalyst granules can be flowed in process wherein at hydrolysate and return the first catalytic reduction reactor device 16.

As described in Figure 3, fluid circulation loop 40 is set up fluid and is communicated with between the fluid intake 42 of pressure vessel 12 and the fluid issuing 44 of living beings feeding mechanism 20.Optionally, fluid circulation loop can be set up direct flow and is communicated with between the fluid issuing of pressure vessel 12 with fluid intake.Such as, in some embodiments, fluid circulation loop 40 can be set up direct flow and is communicated with (see Fig. 4) between the fluid issuing 46 of pressure vessel 12 with fluid intake 42.As described in Figure 3, fluid circulation loop 40 also comprises the second catalytic reduction reactor device 50, and the further conversion of hydrolysate wherein can occur.Can Tectono-fluids closed circuit 40 thus set up counter-current flow when liquid phase is wherein recycled to pressure vessel 12 in hydrothermal digestion device 14.Other type of flow (comprising concurrent flow) is also possible.Do not have the product of returning pressure container 12 to extract pipeline 64 out by product to extract out for further process from fluid circulation loop 40.

In the process of operation conversion systems for biomass 10, the open fluid communication between pressure vessel 12 and living beings feeding mechanism 20 can be had, make liquid phase can flow through pressure transition district 24.The product produced in first catalytic reduction reactor device 16 is by living beings feeding mechanism 20 outflow pressure container 12 (namely by fluid circulation loop 40, the operation of this fluid circulation loop 40 is connected to pressure transition district 24).Not to be retained in the first catalytic reduction reactor device 16 or can be divided by main body living beings and the hydrolysate stream catalyst granules 30 returned wherein in the cellulose series biomass solid that is interposed between and is contained in pressure transition district 24.Once be introduced in pressure vessel 12 by these cellulose series biomass solids, catalyst granules also can return wherein.Therefore, by making liquid phase flow through cellulose series biomass solid pressure transition district 24 from pressure vessel 12, even more effectively catalyst can be retained.

In some embodiments, can wish to make liquid phase not flow through pressure transition district 24 at least temporarily.Such as, when fresh fiber element biolobic material solid is added pressure transition district 24, pressure transition district can at ambient pressure, and it separates by pressure isolation mechanism and pressure vessel 12 in this case, as discussed above.In this case, by making liquid phase maintain the flowing in fluid circulation loop 40 by bypass line 48, the direct flow that this bypass line 48 is established to pressure vessel 12 by fluid issuing 46 is communicated with.

In some embodiments, fluid circulation loop can be connected directly to pressure vessel 12, instead of is connected to the pressure transition district 24 of living beings feeding mechanism 20.Although make the benefit of cellulose series biomass solid in liquid phase stream excess pressure transition region 24 have lost in such an implementation, this structure represents the feasible alternative structure that the fluid for fluid circulation loop 40 circulates.Fig. 4 representatively illustrates descriptive conversion systems for biomass, described conversion systems for biomass has and is contained in hydrothermal digestion device in pressure vessel and catalytic reduction reactor device, and wherein fluid circulation loop establishes and is communicated with the direct flow between fluid issuing at the fluid intake of pressure vessel.Feature in Fig. 4 has with the identical Reference numeral described in Fig. 3 and is described above.For the sake of simplicity, these features are no longer described in detail.

Although foregoing teachings has described the benefit using cellulose series biomass solid to separate catalyst granules, will be appreciated that and conventional catalyst screen cloth and filter can be used to be remained on by catalyst in the first catalytic reduction reactor device 14, in the second catalytic reduction reactor device 50 or in both.To those skilled in the art, these catalyst screen or filter are familiar.Catalyst filter or screen cloth can comprise woven wire or sintering metal or ceramic filter.Solid bed such as usual voidage is that the sharp sand of 25vol% or less or the packed bed of other solid also can be used as catalytic filter, to isolate slurry catalyst from liquid filtrate.Such as, external filter can be adopted as cake filtration device, wherein filter medium can be the particle layers etc. of filter cloth, sintering metal, metallic sieve or fabric, porous ceramics, overfelt or cotton-wool, non-woven fabrics, filter paper, polymer film, granular solids.The filter applying these filter mediums can comprise cake filtration device, level or vertical leaf filter, filter press, from open filter, tubular filter, drum type filteration device, centrifugal discharge formula filter etc.Also can apply centrifuge, hydrocyclone and gravitational settler and carry out separated slurry catalyst from liquid phase and loop slurry catalyst.Such as, using pump, screw rod or conveyer belt etc. the slurry catalyst of separation or enrichment can be transmitted back to catalytic reduction reactor device.

Various optional member also may reside in conversion systems for biomass as described herein.In some embodiments, solid separating mechanism 60 can be had in fluid circulation loop 40.The use of solid separating mechanism can protect the second catalytic reduction reactor device 50 not by such as catalyst granules and cellulose series biomass fine grained block.Applicable solid separating mechanism will be described in more detail hereinafter.In some embodiments, phase separation mechanism 62 can be had in fluid circulation loop 40.Phase separation mechanism 62 may be used for organic phase and the aqueous phase of the product being separated outflow second catalytic reduction reactor device 50 at least partly.The phase separation mechanism be applicable to also is discussed hereinafter in more detail.

In various embodiments, the material be applicable to for pressure vessel can comprise as carbon steel, stainless steel or similar alloy.In some embodiments, pressure vessel can keep the pressure of at least 30bar.In some embodiments, pressure vessel can keep the pressure of at least 60bar.In some embodiments, pressure vessel can keep the pressure of at least 90bar.

Various catalyst can use in conjunction with catalytic reduction reactor device as described herein.In some embodiments, the first catalytic reduction reactor device can be identical with the catalyst in the second catalytic reduction reactor device.In other embodiments, they can be different.In some embodiments, the catalyst in the first catalytic reduction reactor device can comprise slurry catalyst, boiling-bed catalyst or fluid catalyst.In some embodiments, the catalyst in the second catalytic reduction reactor device can comprise fixed bde catalyst, slurry catalyst, boiling-bed catalyst or fluid catalyst.In some embodiments, the first catalyst, the second catalyst or both can comprise slurry catalyst.

In some embodiments, the first catalyst, the second catalyst or both can comprise resistance to malicious catalyst.When catalyst poison failed to remove from the liquid phase of hydrolysate before there is catalytic reduction, use resistance to malicious catalyst may be special hope.As what apply here, " resistance to malicious catalyst " is defined as can anakmetomeres hydrogen and do not need the catalyst that carries out regenerating or changing due to low catalytic activity at least 12 hours in continued operation.Apply resistance to malicious catalyst can avoid and catalyst regeneration and the shortcoming changing relevant process down time.Except the loss production time, when restarting hydrothermal digestion process, considerable energy ezpenditure may be needed.

In some embodiments, suitable resistance to malicious catalyst can comprise such as sulphurized catalyst.The sulphurized catalyst being suitable for anakmetomeres hydrogen is stated in the U.S. Patent Application Publication US2012/0317872 owned together and US 2013/0109896.Sulfuration can by implementing with hydrogen sulfide or other sulfiding reagent process catalyst, and optional catalyst deposit simultaneously on a solid support.In a more specific embodiment, resistance to malicious catalyst can comprise the cobalt-molybdenum phosphate catalyst of sulfuration.We find that the cobalt-molybdenum phosphate catalyst of sulfuration can obtain high containing oxygen intermediate yield and can not form excessive C ₂-C ₄alkane.Easily formed can be separated with water containing oxygen intermediate by flash distillation or liquid-liquid phase separation, under acid or base catalyst effect, experience polycondensation reaction in a separate step, thus produce the liquid biofuel in gasoline, aviation fuel or diesel range.Use resistance to malicious catalyst to reduce occurring before catalytic reduction reaction progressively digesting or the needs of hydrolysate purifying (such as passing through ion-exchange).Even if when catalyst poison removes from hydrolysate, resistance to malicious catalyst still can be used for minimizing process downtime.

In some embodiments, catalyst can be reproducible.In some embodiments, catalyst can be reproducible slurry catalyst.Such as, in some embodiments, slurry catalyst can be made by being exposed to temperature to regenerate higher than the water of its normal boiling point.As what apply here, " reproducible catalyst " can recover its catalytic activity at least partially by regeneration, though when by nitrogen compound impurity, oxidation of sulfur compound impurities or its any combination poisoning be also like this.Ideally, these Regenrable catalyzed dose should regenerate by minimum process down time.In some embodiments, can be that the water of at least 200 DEG C makes it regenerate by slurry catalyst being exposed to temperature.In some embodiments, can be that the water of at least 250 DEG C makes it regenerate by slurry catalyst being exposed to temperature.In some embodiments, can be that the water of at least 300 DEG C makes it regenerate by slurry catalyst being exposed to temperature.In some embodiments, can be that the water of at least 350 DEG C makes it regenerate by slurry catalyst being exposed to temperature.In some embodiments, can be that the water of at least 400 DEG C makes it regenerate by slurry catalyst being exposed to temperature.Be exposed to the water being in subcritical state or supercriticality and can be used for regenerated catalyst.The regeneration of slurry catalyst can occur in any position in conversion systems for biomass, but more generally, regeneration occurs in hydrolysate and do not carry out wherein in one of catalytic reduction reactor device processed.Effectively facilitate most of catalyst of catalytic reduction reaction can regenerate at least partly by heat-treating with hydrogen.Can such as, by being exposed to ruthenium, the ruthenium on titanium dioxide or the ruthenium on carbon that temperature is load on a solid support higher than the specially suitable slurry catalyst of the water reuse (treatment of its normal boiling point.Other suitable slurry catalyst can be platinum or the palladium compound of load on a solid support.

In some embodiments, the catalytic reduction reaction implemented in hydrothermal digestion device and catalytic reduction reactor device can be hydrogenolysis.There is the detailed description of hydrogenolysis hereinafter.

In some embodiments, can Tectono-fluids closed circuit, thus counter-current flow is set up in the hydrothermal digestion device of pressure vessel.As used herein, term " counter-current flow " refers to that product enters the direction of hydrothermal digestion device relative to the flow direction of main body living beings in hydrothermal digestion device.If need, also can apply other flow pattern as and flow.

In some embodiments, the solid separating mechanism be positioned between the fluid issuing of the inherent living beings feeding mechanism of fluid circulation loop and the fluid intake of the second catalytic reduction reactor device may be had.In some embodiments, the solid separating mechanism between the fluid intake that may have the fluid issuing being positioned at fluid circulation loop intrinsic pressure container and a second catalytic reduction reactor device.May be used for protection second catalytic reduction reactor device at the solid separating mechanism of this position and reduce the possibility of blocking.Solid separating mechanism can comprise any isolation technics known in the art, comprises such as filter, centrifugal force or centrifugal force base separating mechanism (as hydrocyclone), settling tank, centrifuge etc.Suitable filter can comprise such as surface-type filters and depth filter.Surface-type filters can comprise such as filter paper, film, porosu solid medium etc.Depth filter can comprise the pillar or slug that are such as designed for the porous media of catching solid in its cored structure.In some embodiments, two or more filters can be used in fluid circulation loop, wherein at least one filter can recoil to hydrothermal digestion device, and simultaneously forward fluid stream flows continuously through the remaining filter of at least some and forward to catalytic reduction reactor device.Namely two or more filters can be operated in complex way.In some embodiments, one or more hydrocyclone can be used in fluid circulation loop.In fluid circulation loop, use filter and hydrocyclone to be described in the U.S. Patent Application Publication US 2013/0152456 owned together and US2013/0158308.

In some embodiments, in fluid circulation loop, phase separation mechanism may be had between the fluid issuing of the second catalytic reduction reactor device and the fluid intake of pressure vessel.The phase separation mechanism be applicable to and technology will be discussed below in more detail.

In some embodiments, may have the product be communicated with fluid circulation loop fluid and extract pipeline out, wherein said product extracts pipeline out between the fluid intake and the fluid issuing of the second catalytic reduction reactor device of pressure vessel.In some embodiments, the solid separating mechanism extracted pipeline operation with product out and be connected may be had.In product before downstream is converted further as bio-fuel or other material, the solid separating mechanism can applying this position removes solid from product.Be applicable to solid separating mechanism can comprise before describe those.

In some embodiments, there has been described the method for the treatment of cellulose series biomass solid.In some embodiments, method for the treatment of cellulose series biomass solid can comprise: provide the pressure vessel comprising first paragraph and second segment, described first paragraph comprises hydrothermal digestion device and second segment and comprises containing can the first catalytic reduction reactor device of the first catalyst of anakmetomeres hydrogen, wherein hydrothermal digestion device and the first catalytic reduction reactor device fluid communication with each other; Cellulose series biomass solid is added in pressure vessel; Cellulose series biomass solid in the hydrothermal digestion device of heated pressure container, is formed in liquid phase the hydrolysate comprising soluble-carbohydrate thus; Under molecular hydrogen exists, conveying liquid is mutually by the first catalytic reduction reactor device, thus described soluble-carbohydrate is converted into product at least partly; With at least part of described liquid phase is delivered to containing can the second catalytic reduction reactor device of the second catalyst of anakmetomeres hydrogen from pressure vessel, thus soluble-carbohydrate is further converted to product.

In some embodiments, can keep during pressurization state, cellulose series biomass solid being added in pressure vessel at pressure vessel.In some embodiments, under pressure vessel can remain on the pressure of at least 30bar when adding cellulose series biomass solid.In some embodiments, can add pressure vessel from living beings feeding mechanism by cellulose series biomass solid, wherein living beings feeding mechanism can keep, during pressurization state, cellulose series biomass solid is introduced pressure vessel at pressure vessel.The pressure vessel being suitable for above-mentioned purpose is described above.In some embodiments, at least some fibre element biolobic material solid can add in the hydrothermal digestion device of pressure vessel by living beings feeding mechanism.In some or other embodiment, at least some fibre element biolobic material solid can add in the first catalytic reduction reactor device of pressure vessel by living beings feeding mechanism.

In some embodiments, described method may further include, by living beings feeding mechanism, liquid phase is delivered to the second catalytic reduction reactor device.In some embodiments, when conveying liquid phase time living beings feeding mechanism may be empty.In other embodiments, when conveying liquid can comprise cellulose series biomass solid by living beings feeding mechanism time wherein mutually.As described above, the cellulose series biomass solid in living beings feeding mechanism may be used for separating the catalyst solid on it and limits them and is delivered to the second catalytic reduction reactor device.Point being interposed between catalyst solid on living beings feeding mechanism inner cellulose biolobic material solid can returning pressure container in subsequently to the process wherein adding cellulose series biomass solid.

In some embodiments, described method may further include and liquid phase is delivered to the second catalytic reduction reactor device and do not make liquid phase by living beings feeding mechanism.Such as, liquid phase directly can lead to the fluid intake of the second catalytic reduction reactor device from the fluid issuing of pressure vessel.In some embodiments, when living beings feeding mechanism directly can carry liquid phase at ambient pressure with when loading extra cellulose series biomass solid.In other embodiments, can bypass living beings feeding mechanism completely.Such as, if catalyst solid is retained in pressure vessel effectively, can bypass living beings feeding mechanism when liquid phase being delivered to the second catalytic reduction reactor device.

In some embodiments, before digestion, cellulose series biomass can wash and/or reduce size (such as by mincing, pulverizing, peeling etc.), to reach size needed for digestion and quality.Described operation can remove the material of the further chemical conversion of interference soluble-carbohydrate and/or improve digestion solvent to the infiltration in living beings.In some embodiments, can wash in the hydrothermal digestion device of pressure vessel before pressurization.In other embodiments, can wash before living beings are put into pressure vessel.Such as, in some embodiments, can washing biomass in biomass feeding unit capable before the pressing.

Digestion in hydrothermal digestion device can be implemented usually in the liquid phase.In some embodiments, liquid phase can comprise the digestion solvent of water.In some embodiments, liquid phase may further include organic solvent.In some embodiments, organic solvent can comprise by soluble-carbohydrate catalytic reduction reaction produce containing oxygen intermediate.Such as, in some embodiments, digest solvent can comprise by soluble-carbohydrate hydrogenolysis or other catalytic reduction reaction produce containing oxygen intermediate.In some embodiments, bio-ethanol can be added to the water as initial digestion solvent, produce the solvent comprised containing oxygen intermediate subsequently.If needed, also initial digestion solvent can be used as with mixable other organic solvent any of water.Usually, the liquid phase of q.s can be there is in digestion process, thus make biological surface keep wetting.The amount of liquid phase can be selected further to keep the concentration of soluble-carbohydrate enough high, thus in catalytic reduction process, reach required high reaction speed, but too highly can not cause the problem of being degraded into.In some embodiments, the concentration of soluble-carbohydrate can keep below the 5wt% of liquid phase to make degraded the least possible.But will be appreciated that and can apply higher concentration in some embodiments.In some embodiments, organic acids 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, digest solvent and can comprise the organic solvent containing oxygen intermediate containing and produced by the catalytic reduction reaction of soluble-carbohydrate.Catalytic reduction reaction can occur in catalytic reduction reactor device.In some embodiments, organic solvent can comprise at least one alcohol, ketone or polyalcohol.In an alternative embodiment, digest solvent can be provided by external source at least partly.Such as, in some embodiments, supplementary organic solvent can be carried out by applying biological ethanol.Also the organic solvent that other and water are miscible can be applied.In some embodiments, by digestion separated from solvent, storage or optionally can inject hydrothermal digestion device, thus in hydrothermal digestion device, keep required soluble-carbohydrate concentration or provide temperature to regulate.

In various embodiments, digestion can implement a period of time at high temperature and pressure.In some embodiments, digestion can implement a period of time at the temperature of 100-250 DEG C.In some embodiments, the described time period can be 0.25-24 hour.In some embodiments, the digestion producing soluble-carbohydrate can be implemented under the pressure of 1-100bar (absolute pressure).In some embodiments, digestion process can be implemented: wherein the first stage implements under 160 DEG C or lower temperature in multiple stage, for hemicellulose being dissolved and being converted into product, implement under 160 DEG C or higher temperature with second stage, for by cellulose dissolution and be converted into product.Lower temperature digestion also can from cellulose series biomass solids removal at least some catalyst poison and lignin.

In various embodiments, suitable living beings digestion techniques can comprise the digestion of such as acid digestion, alkali digestion, enzymic digestion and application hot pressurized water.

In some embodiments, described method may further include and be drawn to small part product from conversion systems for biomass.Such as, in some embodiments, described method may further include after soluble-carbohydrate is further converted to product, from the fluid issuing extraction section product of the second catalytic reduction reactor device.In some embodiments, it is bio-fuel that described method may further include conversion reaction product, as hereafter specifically described.In some embodiments, described method may further include as mentioned above when carrying liquid phase to the second catalytic reduction reactor device from liquid phase separating solids.

In some embodiments, described method may further include and at least part of liquid phase is circulated to pressure vessel from the second catalytic reduction reactor device.Liquid phase is circulated to pressure vessel from the second catalytic reduction reactor device such as may contribute to regulating the temperature of its inside, supplement the digestion solvent etc. of digestion process.Can implement with various recycle ratio from the second catalytic reduction reactor device to the circulation of pressure vessel.As used herein, term " recycle ratio " refers to the amount of liquid phase being circulated to pressure vessel (such as in fluid circulation loop) relative to the amount of liquid phase of extracting (such as extracting pipeline out by product) from conversion systems for biomass out.

The special benefit implementing hydrothermal digestion and catalytic reduction in uniform pressure container be when by liquid phase circulation to hydrothermal digestion time, lower recycle ratio can be applied, simultaneously can maintenance process efficiency and yield.Particularly, assuming that there is the catalytic reduction reaction of heat release in hydrothermal digestion device, the product circulated may have not too been needed to provide heat for the digestion process occurred in pressure vessel.Therefore, the liquid phase of relatively a high proportion of outflow second catalytic reduction reactor device can be extracted out from conversion systems for biomass, be converted into bio-fuel subsequently.Lower recycle ratio also can allow to apply less reactor volume, because the total flow rate of liquid in hydrothermal digestion device and catalytic reduction reactor can reduce.High recycle ratio and high flow rate of liquid can produce too much pressure drop, the energy of high pump and size requirements and other negative characteristics.Before stable by catalytic reduction reaction, the energy minimization time of staying may also can not cause yield lower.In addition, lower recycle ratio may help lend some impetus to catalyst and be retained in pressure vessel the demand be retained in by catalyst with minimizing cellulose series biomass solid wherein.Based on benefit of the present invention, the suitable recycle ratio of liquid phase circulation when those of ordinary skill in the art can determine to reach required heat integration amount, balances the hope speed that downstream bio-fuel is produced simultaneously.In some embodiments, under the recycle ratio of 0.2-10, liquid phase can be circulated to pressure vessel from the second catalytic reduction reactor device.In some embodiments, under the recycle ratio of 1-10 or 1-5 or 0.2-2 or 0.5-2 or 1-2 or 0.2-1 or 0.5-1, liquid phase can be circulated to pressure vessel from the second catalytic reduction reactor device.In some embodiments, under the recycle ratio of 2 or less, liquid phase can be circulated to pressure vessel from the second catalytic reduction reactor device.In some embodiments, under the recycle ratio of 1 or less, liquid phase can be circulated to pressure vessel from the second catalytic reduction reactor device.In some embodiments, liquid phase can be circulated to pressure vessel from the second catalytic reduction reactor device, thus set up counter-current flow in hydrothermal digestion device.In other embodiments, other flow pattern can be set up in hydrothermal digestion device, comprise such as and flow.

In some embodiments, in pressure vessel, heating cellulose biolobic material solid can be implemented under the pressure of at least 30bar.Maintain digestion can guarantee to digest with gratifying speed under the pressure of at least 30bar.In some embodiments, in pressure vessel, heating cellulose biolobic material solid can be implemented under the pressure of at least 60bar.In some embodiments, in pressure vessel, heating cellulose biolobic material solid can be implemented under the pressure of at least 90bar.In some embodiments, in pressure vessel, heating cellulose biolobic material solid can be implemented under the pressure of 30-430bar.In some embodiments, in pressure vessel, heating cellulose biolobic material solid can be implemented under the pressure of 50-330bar.In some embodiments, in pressure vessel, heating cellulose biolobic material solid can be implemented under the pressure of 70-130bar.In some embodiments, in pressure vessel, heating cellulose biolobic material solid can be implemented under the pressure of 30-130bar.It should be noted that aforementioned pressure refers to routine operating pressure when there is digestion.

Put it briefly, after digesting in hydrothermal digestion device, only have the pristine fibre of less percentage element biolobic material solid to remain and do not digest.In some embodiments, by butt, can by the cellulose series biomass solid of at least 60% digestion to produce hydrolysate.In some embodiments, by butt, can by the cellulose series biomass solid of at least 70% digestion to produce hydrolysate.In some embodiments, by butt, can by the cellulose series biomass solid of at least 80% digestion to produce hydrolysate.In some embodiments, by butt, can by the cellulose series biomass solid of at least 90% digestion to produce hydrolysate.

In some embodiments, can apply in the process resistance to malicious catalyst as the first catalyst, the second catalyst or both.The slurry catalyst of suitable poisoning resistant described above.In some embodiments, can apply in the process Regenrable catalyzed dose as the first catalyst, the second catalyst or both.In some embodiments, Regenrable catalyzed dose can be slurry catalyst.In some embodiments, described method may further include by making slurry catalyst be exposed to temperature is that the water of at least 200 DEG C or at least 250 DEG C or at least 300 DEG C or at least 350 DEG C or at least 400 DEG C makes it regenerate.

In some embodiments, the inventive method may further include and implements being separated of product.In some embodiments, the phase separation mechanism that the outlet that can be applied in the second catalytic reduction reactor device exists afterwards is implemented to be separated.In various embodiments, implement to be separated can comprise be separated double-deck, implement the operation of solvent air lift, implement extraction, implement to filter, implement rectifying etc.In some embodiments, azeotropic distillation can be implemented.

In some embodiments, method described herein may further include conversion reaction product is bio-fuel.In some embodiments, as mentioned previously, conversion reaction product is that bio-fuel can start from catalytic hydrogenolytic cleavage, is converted into the product comprised containing oxygen intermediate with the soluble-carbohydrate produced by hydrothermal digestion.As above further described in described and Fig. 3 and 4, the liquid phase comprising product can be recycled to pressure vessel, with further assist digestion process.In some embodiments, can transform described product further by any amount of further catalytic reforming reaction, described catalytic reforming reaction comprises such as further catalytic reduction reaction (such as hydrogenolysis, hydrogenation reaction, hydrotreatment reaction etc.), condensation reaction, isomerization reaction, desulphurization reaction, dehydration, oligomerization, alkylated reaction etc.The explanation of initial hydrogenolysis and further catalytic reforming reaction is described hereinafter.

Known various procedures is for carrying out the hydrogenolysis of carbohydrate.A kind of applicable method comprises: to comprise containing oxygen intermediate e as under the condition of the product compared with Small molecular or polyalcohol effectively being formed, and makes carbohydrate or stable hydroxy intermediate and optionally contacts with hydrogenolysis catalyst with the hydrogen that diluent gas mixes.Term used herein " comparatively Small molecular or polyalcohol " comprises the lower any molecule of molecular weight, and it can comprise the carbon atom more less than starting carbohydrate quantity or oxygen atom.In some embodiments, product can comprise comparatively Small molecular, such as polyalcohol and alcohol.This respect of hydrogenolysis needs to disconnect carbon-carbon bond.

In some embodiments, can the catalyst of anakmetomeres hydrogen exist under to utilize hydrogenolysis to be converted into by soluble-carbohydrate metastable such as, containing oxygen intermediate, propane diols, 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 and their alloy or any combination, separately or also containing promoter as Au, Ag, Cr, Zn, Mn, Sn, Bi, B, O and their alloy or any combination.In some embodiments, catalyst and promoter can allow hydrogenation and hydrogenolysis simultaneously or occur successively, as carbonyl hydrogen forms alcohol.Described catalyst can also comprise carbon containing pyropolymer catalyst, and this catalyst comprises 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 certain embodiments, described catalyst can comprise and to be combined with alkaline earth oxide or to be attached to any above-mentioned metal on catalytic activity carrier.In certain embodiments, the catalyst described in hydrogenolysis can comprise catalyst carrier.

The condition of carrying out hydrogenolysis can be different based on the type of living beings starting material and required product (such as gasoline or diesel oil).Benefiting from present disclosure, one of ordinary skill in the art would recognize that for carrying out the applicable condition of reacting.Usually, hydrogenolysis can carry out at the temperature of 110-300 DEG C, is preferably 170-300 DEG C, and most preferably is 180-290 DEG C.

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

The 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 the polyalcohol being greater than 25mol% or being alternatively greater than 30mol%, and this conversion ratio being converted into bio-fuel during subsequent treatment can be made to react is higher.

In some embodiments, according to the needs of the hydrolysis accelerated except hydrogenolysis, hydrogenolysis can be carried out under neutrality or acid condition.Such as, the hydrolysis of oligomeric carbohydrate can be combined to generate sugar alcohol with hydrogenation, the latter can carry out hydrogenolysis.

The second aspect of hydrogenolysis needs to disconnect-OH key, as: RC (H) ₂-OH+H ₂→ RCH ₃+ H ₂o.This reaction, also referred to as " hydrogenation deoxidation ", can be carried out with the hydrogenolysis disconnecting C-C key simultaneously.By this reaction, glycol can be converted into single oxygenate.As the result of hydrogenation deoxidation, due to by improve temperature or with time of contact of catalyst and reaction depth is increased, the relative concentration of polyalcohol and glycol may reduce in single oxygenate.C-C is different with catalyst type and formula relative to the selective meeting of C-OH key hydrogenolysis.In subsequent processing steps, also may there is complete deoxidation and generate alkane, if but object generates single oxygenate or glycol and polyalcohol (they can condensation or the oligomeric compound for higher molecular weight), this is normally undesirable.Usually, it is desirable to only single oxygenate or glycol to be delivered to subsequent processing steps, this is because higher polyol may cause forming excess coke in condensation or oligomerization process.Than, alkane, tool is reactive and cannot combine the compound generating more HMW easily substantially in contrast.

Once be formed containing oxygen intermediate by hydrogenolysis, a part of product can be recycled to hydrothermal digestion device to be used as the inner digestion solvent produced.Can extract out another part product and subsequently by further reforming reaction process to form bio-fuel.Before standing further reforming reaction, optionally can be separated into different components by containing oxygen intermediate.Suitable separation can comprise such as be separated, solvent gas stripper, extractor, filter, rectifying etc.In some embodiments, before product is further processed subsequently or is recycled to hydrothermal digestion device, can will contain oxygen intermediate and lignin separation.

Can process in one or more processing reaction containing oxygen intermediate to generate fuel blends.In some embodiments, condensation reaction can use to generate fuel blends together with other reacts, and can carry out catalysis by comprising acidity, alkali or the catalyst of the two.Usually, be not bound by any particular theory, it is believed that alkaline condensation reaction can comprise series of steps, comprising: the dehydrogenation reaction that (1) is optional; (2) optional can acid catalyzed dehydration; (3) aldol reaction; (4) optional ketonize reaction; (5) optional furans ring-opening reaction; (6) condensation product obtained carries out hydrogenation to form >C ₄hydrocarbon; (7) their any combination.Similarly, acid catalyzed condensation may need optional hydrogenation or dehydrogenation reaction, dehydration and oligomerization.Additional refining reaction can also be used to meet specific fuel standard to make product, and the reaction carried out under being included in hydrogen and hydrogenation catalyst existence to remove functional group from final fuel Products.In some embodiments, also can use base catalyst, comprise acidity and alkaline functional position and optionally comprise metal official can catalyst to implement condensation reaction.

In some embodiments, aldol reaction can be used to generate the fuel blends meeting diesel fuel or jet fuel requirement.Traditional diesel fuel is the petroleum distillate being rich in alkane.Their boiling range is wide reaches 187-417 DEG C, and this is suitable for burning in compression ignition engine is as diesel engine automobiles.ASTM (ASTM) establishes diesel fuel grades according to boiling range and other fuel performance allowed band as Cetane number, cloud point, flash-point, viscosity, aniline point, sulfur content, water content, content of ashes, copper strip corrosion and carbon residue.Therefore, any fuel blends meeting ASTM D975 all may be defined as diesel fuel.

Present invention also offers the method for producing jet fuel.Jet fuel is for being clear to bale of straw.Modal fuel for be categorized as Aeroplane A-1 (by standard ISO produce) unleaded/paraffinic base oil fuel.Jet fuel is the mixture of a large amount of different hydrocarbon (may reach thousand kinds or more).The scope of their size (molecular weight or carbon number) is subject to the restriction of product requirements such as freezing point or smoke point.The carbon number distribution of kerosene type jet fuel (comprising Jet A and Jet A-1) is C ₈-C ₁₆.The carbon number distribution of long distillate or naphtha type aircraft fuel (comprising Jet B) is generally C ₅-C ₁₅.The fuel blends meeting ASTM D1655 all may be defined as jet fuel.

In certain embodiments, two kinds of jet fuels (Jet A and Jet B) all comprise multiple additives.Useful additive includes but not limited to antioxidant, antistatic additive, corrosion inhibitor and fuel system anti-freezing agent (FSII).Antioxidant prevents gelatinize, and usually based on alkylating phenol such as AO-30, AO-31 or AO-37.Antistatic additive static dissipation and prevent spark.An example of antistatic additive as the Stadis 450 of active component containing dinonylnapthyl sulfonic acid (DINNSA).Corrosion inhibitor such as DCI-4A is used for civil and military fuel and DCI-6A is used for military fuel.FSII agent comprises such as Di-EGME.

In some embodiments, the carbonyl containing compound that can participate in base catalyzed condensation reaction can be comprised containing oxygen intermediate.In some embodiments, optional dehydrogenation reaction can be used increase the amount containing carbonyl containing compound in the logistics of oxygen intermediate that will be used as condensation reaction raw material.In these embodiments, can make in the presence of a catalyst containing oxygen intermediate and/or a part of organism-based raw material logistics dehydrogenation.

In some embodiments, for comprise alcohol, glycol and triol containing the logistics of oxygen intermediate, may preferred dehydrogenation.Usually, alcohol can not participate in aldol condensation directly.The hydroxyl existed can be converted into carbonyl (such as aldehyde, ketone etc.) to participate in aldol reaction.Dehydrogenation can be comprised to make any alcohol of existence, glycol and polyalcohol generation dehydrogenation to form ketone and aldehyde.Dehydration catalyst is formed by the identical metal used with hydrogenation, hydrogenolysis or aqueous phase reforming usually.These catalyst as above described in detail.Dehydrogenation yield can be improved by removing or consume the hydrogen formed in course of reaction.Dehydrogenation step can carry out as independent reactions steps before aldol reaction, or dehydrogenation reaction can be carried out with aldol reaction is collaborative.For working in coordination with the dehydrogenation and aldol reaction carried out, dehydrogenation and aldol condensation function can occur on the same catalyst.Such as, metal hydrogenation/dehydrogenation functionalities can be there is in the catalyst comprising basic functionality.

Dehydrogenation reaction can generate carbonyl containing compound.The carbonyl containing compound be applicable to can include but not limited to any compound comprising carbonyl functional group, and described carbonyl functional group can form carbanionic species or can react with carbanionic 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 include but not limited to hydroxy-ketone, cyclic ketones, diketone, acetone, 2-oxopropanal, butanone, butane-2,3-diketone, 3-hydroxybutane-2-ketone, pentanone, cyclopentanone, pentane-2,3-diketone, pentane-2,4-diketone, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecyl ketone, ten diketone, pyroracemic aldehyde, diacetyl, pentanedione, diketone hexane, dihydroxyacetone (DHA) and their isomers.Aldehyde can include but not limited to aldol, acetaldehyde, glyceraldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, octanal, aldehyde C-9, capraldehyde, the hendecanal, lauric aldehyde and their isomers.Carboxylic acid can include but not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid and their isomers and derivative, comprises hydroxylation derivative as 2-hydroxybutyric acid and lactic acid.Furfural includes but not limited to 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.In one embodiment, dehydrogenation reaction can generate carbonyl containing compound, and this carbonyl containing compound is fed to the part containing oxygen intermediate of condensation reaction with being combined into containing oxygen intermediate.

In one embodiment, acid catalyst is optionally used to make at least partially containing oxygen intermediate logistics dehydration.The acid catalyst be applicable to for dehydration can include but not limited to inorganic acid (such as HCl, H ₂sO ₄), solid acid (such as zeolite, ion exchange resin) and acid salt (such as LaCl ₃).Additional acid catalyst can include but not limited to zeolite, carbide, nitride, zirconia, aluminium oxide, silica, alumino-silicate, phosphate, titanium oxide, zinc oxide, vanadium oxide, lanthana, yittrium oxide, scandium oxide, magnesia, cerium oxide, barium monoxide, calcium oxide, hydroxide, heteropoly acid, inorganic acid, acid modified resin, base modified resin and their any combination.In some embodiments, dehydration catalyst can also comprise conditioning agent.The conditioning agent be applicable to can comprise such as La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba and their any combination.Conditioning agent especially to work in coordination with hydrogenation/dehydrogenation reaction and dehydration useful.In some embodiments, dehydration catalyst can also comprise metal.The metal be applicable to can comprise such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, their alloy and any combination.Dehydration catalyst can self-supporting, load is on inert carrier or resin or can dissolve in the solution.

In some embodiments, dehydration can be carried out in the gas phase.In other embodiments, dehydration can be carried out in the liquid phase.For liquid-phase dehydration reaction, the aqueous solution can be used to react.In one embodiment, other solvent in addition to water can also be used to form the aqueous solution.Such as, water-miscible organic solvent can be there is.The solvent be applicable to can include but not limited to hydroxymethylfurfural (HMF), methyl-sulfoxide (DMSO), 1-methyl-n-pyrrolidones (NMP) and their any combination.Other aprotic solvent be applicable to can also be combinationally used separately or with these solvents any.

In one embodiment, processing reaction can comprise optional ketonize reaction.Ketonize reaction can improve at least partially containing the quantity of ketone in oxygen intermediate.Such as, in ketonize reaction, alcohol can be converted into ketone.Ketonize can be carried out under base catalyst exists.Any base catalyst as above described as the basic component of aldol reaction can be used to carry out ketonize reaction.The reaction condition be applicable to is known to those skilled in the art, usually corresponds to as above about the reaction condition listed by aldol reaction.Ketonize reaction can be carried out as independent reactions steps, or can carry out with aldol reaction is collaborative.Aldol condensation catalyst comprises alkaline functional position and can make that ketonize and aldol reaction are collaborative to carry out.

In some embodiments, processing reaction can comprise optional furans ring-opening reaction.Furans ring-opening reaction can make at least partially any comprise furan nucleus containing oxygen converted for have more reactive compound in aldol reaction.Furans ring-opening reaction can be carried out in the presence of acidic.Any acid catalyst as above described as the acidic components of aldol reaction can be used to carry out furans ring-opening reaction.The reaction condition be applicable to is known to those skilled in the art, usually corresponds to as above about the reaction condition listed by aldol reaction.Furans ring-opening reaction can be carried out as independent reactions steps, or can carry out with aldol reaction is collaborative.Aldol condensation catalyst comprises acid function position and can make that furans ring-opening reaction and aldol reaction are collaborative to carry out.This embodiment may be favourable, this is because any furan nucleus all can be opened under acid functional group exists, and reacts in the aldol reaction using basic functionality.This concerted reaction scheme may allow to form more substantial higher hydrocarbon for given containing oxygen intermediate feed.

In some embodiments, >C can be generated by the condensation (aldol condensation can be comprised) containing oxygen intermediate under condensation catalyst existence ₄compound.Aldol condensation generally includes between two kinds of compounds that at least one may comprise carbonyl carries out carbon-to-carbon coupling, to form larger organic molecule.Such as, acetone can react with hydroxymethylfurfural and form C ₉material, C ₉material can form C with another hydroxymethylfurfural molecular reaction subsequently ₁₅material.In various embodiments, reaction is carried out usually under condensation catalyst exists.Condensation reaction can be carried out in gas phase or liquid phase.In one embodiment, according to the reactivity of carbonyl, reaction can be carried out at the temperature of 5-375 DEG C.

Condensation catalyst is generally can by being connected the catalyst that two molecules form more long-chain compound by new carbon-carbon bond, such as base catalyst, there is the multifunctional catalyst of bronsted lowry acids and bases bronsted lowry degree of functionality or in the two, also comprise arbitrary class catalyst of optional metal functionality.In some embodiments, multifunctional catalyst can for having the catalyst of strong acid and highly basic degree of functionality.In some embodiments, aldol condensation 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, aluminosilicate zeolite through alkali treatment, basic resin, basic nitrogen compound, their alloy or any combination.In some embodiments, base catalyst can also 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 comprises mixed oxide base catalyst.The mixed oxide base catalyst be applicable to can comprise the combination of magnesium, zirconium and oxygen, and it can include but not limited to: 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.The different atomic ratios of the combination of other elements various of Mg/Zr or formation mixed oxide catalyst can be 0.01-50.In some embodiments, condensation catalyst may further include metal or alloy, comprises metal 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, their alloy and combination.When dehydrogenation reaction will be carried out with aldol reaction is collaborative, these metals may 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 demonstrating basic functionality.On any one carrier that base catalyst can further describe below for self-supporting or be attached to, comprise and comprise carbon, silica, aluminium oxide, zirconia, titanium oxide, vanadium oxide, cerium oxide, nitride, boron nitride, heteropoly acid, their carrier of alloys and mixts.

In one embodiment, condensation catalyst can derived from MgO and Al ₂o ₃combination to form hydrotalcite material.Another kind of preferred material comprises ZnO and Al ₂o ₃, form is zinc aluminate spinel.Another preferred material is ZnO, Al ₂o ₃with the combination of CuO.Each of these materials can also comprise the additional metal official energy provided as Pd or Pt by group VIIIB metal.When dehydrogenation reaction will be carried out with aldol reaction is collaborative, these metals may be preferred.In some embodiments, base catalyst can for comprising the metal oxide of Cu, Ni, Zn, V, Zr or their mixture.In other embodiments, base catalyst can for comprising the zinc aluminate metal of Pt, Pd Cu, Ni or their mixture.

In some embodiments, the condensation catalyst with acid and basic functionality is used can to carry out the condensation reaction of base catalysis.Acid aldol 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 can also comprise one or more oxides of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P and their combination.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, their alloy or combination.In some embodiments, catalyst also comprises Zn, Cd or phosphate.In some embodiments, condensation catalyst can for comprising the metal oxide of Pd, Pt, Cu or Ni, and be even more preferably and comprise Mg and Cu, the aluminate of Pt, Pd or Ni or zirconium metal oxide.Acid-bast-catalyst can also comprise the hydroxyapatite (HAP) being combined with any one or multiple above-mentioned metal.On any one carrier that Acid-bast-catalyst can further describe below for self-supporting or be attached to, comprise and comprise carbon, silica, aluminium oxide, zirconia, titanium oxide, vanadium oxide, cerium oxide, nitride, boron nitride, heteropoly acid, their carrier of alloys and mixts.

In some embodiments, condensation catalyst can also comprise and comprise IA group compound as the zeolite of Li, Na, K, Cs and Rb and other porous carrier.Preferably, IA race material can exist with the amount in being less than and needed for the acid properties of carrier.Can also by adding group VIIIB metal or Cu, Ga, In, Zn or Sn provide metal official energy.In one embodiment, condensation catalyst can derived from MgO and Al ₂o ₃combination to form hydrotalcite material.Another kind of preferred material can comprise MgO and ZrO ₂combination or ZnO and Al ₂o ₃combination.Each of these materials can also comprise the additional metal official energy provided as Ni, Pd or Pt or aforesaid combination by copper or group VIIIB metal.

Condensation catalyst can for self-supporting (namely catalyst does not need other material as carrier), or may need to be applicable to make catalyst to be suspended in independent carrier in reactant stream.Exemplary carrier is by sol-gel synthesis, precipitates or be fuming that the silica obtained, particularly specific area are high (is greater than 100m ²/ g) silica.In other embodiment, particularly when condensation catalyst is powder, antigravity system can comprise adhesive to contribute to making catalyst form required catalyst shape.Available moulding process can comprise extrude, granulation, oil droplet or other already known processes.Zinc oxide, aluminium oxide and peptizing agent can also be mixed and extrude with producing 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, because reaction condition is overlapping to a certain extent, dehydration catalyst, dehydrogenation and condensation catalyst may reside in identical reactor.In these embodiments, dehydration and/or dehydrogenation reaction can be carried out with condensation reaction substantially simultaneously.In some embodiments, catalyst can comprise the active sites for the dehydration except condensation reaction and/or dehydrogenation reaction.Such as, the site that catalyst can separate on a catalyst comprises the active metal for dehydration and/or dehydrogenation reaction and condensation reaction or alloy.The active element be applicable to can comprise as above about any listed those of dehydration catalyst, dehydrogenation and condensation catalyst.Alternatively, the physical mixture of dehydration, dehydrogenation and condensation catalyst can be used.Do not wish to be bound by theory, it is believed that and use the condensation catalyst comprising metal and/or acid functionality that the aldol reaction of balance restriction can be contributed to have pushed to.Advantageously, this can make intermediate carry out multiple condensation reaction and dehydration and/or dehydrogenation, thus forms (by condensation, dehydration and/or dehydrogenation) and produce the higher oligomer of molecular weight needed for jet fuel or diesel fuel.

The concrete >C generated in the condensation reaction ₄compound may depend on various factors, includes but not limited in reactant stream containing the type of oxygen intermediate, condensation temp, condensation pressure, the reactivity of catalyst and the flow of reactant stream.Usually, condensation reaction can be carried out at the temperature of the favorable thermodynamics to plan reaction.For condensation phase liquid reactions, the pressure in reactor can be enough to make reactant at least partially keep condensation liquid phase at reactor inlet place.For gas-phase reaction, reaction can the vapour pressure of oxygenate be at least 0.1bar and to reaction favorable thermodynamics temperature under carry out.Condensation temp is concrete different containing oxygen intermediate according to what use, but can be 75-500 DEG C usually for the reaction carried out in the gas phase, is more preferably 125-450 DEG C.For liquid phase reactor, condensation temp can be 5-475 DEG C, and condensation pressure can be 0.01-100bar.Preferably, condensation temp can be 15-300 DEG C or 15-250 DEG C.

Change above-mentioned and other factors and usually can change >C ₄the concrete composition of compound and yield.Such as, the temperature of altering reactor system and/or pressure or specific catalyst formulation, can generate >C ₄alcohol and/or ketone instead of >C ₄hydrocarbon.>C ₄hydrocarbon products also can comprise the alkane (being generally branched paraffin) of various alkene and all size.According to condensation catalyst used, hydrocarbon products also can comprise aromatic hydrocarbons and cyclic hydrocarbon compound.>C ₄hydrocarbon products also may comprise undesirable high olefin(e) centent, and this can cause producing coke or deposit in combustion engine, or other undesirable hydrocarbon products.In this case, hydrocarbon can optionally hydrogenation with by ketone body powder for alcohol and hydrocarbon, and alcohol and olefin(e) can be reduced to alkane, form the hydrocarbon products of more wishing of alkene, aromatic hydrocarbons or the alcohol content with reduction thus.

Condensation reaction can be carried out in any reactor of applicable design, comprise Continuous Flow, intermittently, semi-batch or multisystem reactor, not by the restriction of design, size, geometry, flow etc.Reactor assembly also can use fluid catalytic bed system, shaking table 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 to carry out condensation reaction.

In continuous-flow system, reactor assembly can comprise be suitable for generating through dehydrogenation the optional dehydrogenation bed containing oxygen intermediate, be suitable for generating through dehydration the optional dehydration bed containing oxygen intermediate and be suitable for generating >C by containing oxygen intermediate ₄the condensation bed of compound.Needed for dehydrogenation bed can be set to receive reactant stream and generate containing oxygen intermediate, it can have the carbonyl containing compound content of raising.Needed for dehydration bed can be set to receive reactant stream and generate containing oxygen intermediate.Condensation bed can be set to receive containing oxygen intermediate with the >C needed for contacting with condensation catalyst and generating ₄compound.For the system with one or more purification step, the additional reaction bed for carrying out subtractive process can be comprised 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 arranged in identical reactor vessel, or in the reactor vessel separated of fluid communication with each other.Each reactor vessel preferably can comprise the outlet being suitable for removing product stream from reactor vessel.For the system with one or more purification step, refining reaction bed can with condensation bed in identical reactor vessel, or in the independent reactor vessel be communicated with the reactor vessel fluid with condensation bed.

In some embodiments, reactor assembly can also comprise additional outlet to allow to remove the logistics of partial reaction thing thus promote further or guide the product needed for reaction generation, and allows to collect and reclaim the other parts of byproduct of reaction for system.In some embodiments, reactor assembly can also comprise additional entrance with allow to introduce supplement material thus promote further or guide reaction generate needed for product, and allow to reclaim byproduct of reaction and react for other.

In some embodiments, reactor assembly can also comprise the element allowing reactant stream to be separated into different component, and described different component may be used for different reaction scheme or the reaction just needed for promotion.Such as, separator can be installed before condensation step if phase separator, extractor, purifier or destilling tower to remove water from reactant stream, thus promote that condensation reaction is beneficial to generate higher hydrocarbon.In some embodiments, separator can be installed to remove specific intermediate, thus allow to generate and comprise the hydrocarbon of carbon number in particular range or be used as end product or for the product stream needed for other system or process.It is C that condensation reaction can generate carbon number ₄-C ₃₀or the compound of larger wide region.Exemplary compound can comprise such as >C ₄alkane, >C ₄alkene, >C ₅cycloalkane, >C ₅cycloolefin, aromatic hydrocarbons, condensed aromatics, >C ₄alcohol, >C ₄ketone and their mixture.>C ₄alkane and >C ₄alkene can have 4-30 carbon atom (i.e. C ₄-C ₃₀alkane and C ₄-C ₃₀alkene) and can be side chain or linear paraffin or alkene.>C ₄alkane and >C ₄alkene can also comprise C respectively ₇-C ₁₄, C ₁₂-C ₂₄alkane and olefine fraction, wherein C ₇-C ₁₄cut relates to jet fuel blend, and C ₁₂-C ₂₄cut relates to diesel fuel blend and other commercial Application.Various >C ₄alkane and >C ₄the example of alkene includes but not limited to 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.

>C ₅cycloalkane and >C ₅cycloolefin can have 5-30 carbon atom and can for not replacing, monosubstituted or polysubstituted.When monosubstituted and polysubstitution compound, substituting group can comprise side chain >C ₃alkyl, straight chain >C ₁alkyl, side chain >C ₃alkylidene, straight chain >C ₁alkylidene, straight chain >C ₂alkylidene, aryl or their combination.In one embodiment, at least one substituting group can comprise side chain C ₃-C ₁₂alkyl, straight chain C ₁-C ₁₂alkyl, side chain C ₃-C ₁₂alkylidene, straight chain C ₁-C ₁₂alkylidene, straight chain C ₂-C ₁₂alkylidene, aryl or their combination.In another other embodiment, at least one substituting group can comprise side chain C ₃-C ₄alkyl, straight chain C ₁-C ₄alkyl, side chain C ₃-C ₄alkylidene, straight chain C ₁-C ₄alkylidene, straight chain C ₂-C ₄alkylidene, aryl or their combination.Required >C ₅cycloalkane and >C ₅the example of cycloolefin can include but not limited to pentamethylene, cyclopentene, cyclohexane, cyclohexene, methyl cyclopentane, methyl cyclopentene, ethyl cyclopentane, ethylcyclopentene, ethyl cyclohexane, ethyl-cyclohexene and their isomers.

Aromatic hydrocarbons comprises the aromatic hydrocarbons not replacing (phenyl), monosubstituted or polysubstituted form.When monosubstituted and polysubstitution compound, substituting group can comprise side chain >C ₃alkyl, straight chain >C ₁alkyl, side chain >C ₃alkylidene, straight chain >C ₂alkylidene, phenyl or their combination.In some embodiments, at least one substituting group can comprise side chain C ₃-C ₁₂alkyl, straight chain C ₁-C ₁₂alkyl, side chain C ₃-C ₁₂alkylidene, straight chain C ₂-C ₁₂alkylidene, phenyl or their any combination.In another other embodiment, at least one substituting group can comprise side chain C ₃-C ₄alkyl, straight chain C ₁-C ₄alkyl, side chain C ₃-C ₄alkylidene, straight chain C ₂-C ₄alkylidene, phenyl or their any combination.The example of various aromatic compound can include but not limited to benzene,toluene,xylene (dimethyl benzene), ethylbenzene, paraxylene, meta-xylene, ortho-xylene and C ₉aromatic hydrocarbons.

Condensed aromatics comprise do not replace, two rings of monosubstituted or polysubstituted form or polycyclic aromatic hydrocarbon.When monosubstituted and polysubstitution compound, substituting group can comprise side chain >C ₃alkyl, straight chain >C ₁alkyl, side chain >C ₃alkylidene, straight chain >C ₂alkylidene, phenyl or their combination.In other embodiments, at least one substituting group can comprise side chain C ₃-C ₄alkyl, straight chain C ₁-C ₄alkyl, side chain C ₃-C ₄alkylidene, straight chain C ₂-C ₄alkylidene, phenyl or their any combination.The example of various condensed aromatics can include but not limited to naphthalene, anthracene, tetrahydronaphthalene and decahydronaphthalenes, indane, indenes and their isomers.

Medium cut is as C ₇-C ₁₄can be separated as jet fuel, and comparatively heavy distillat (such as C ₁₂-C ₂₄) can be separated and use as diesel oil.Most heavy distillat can be used as lubricant or through cracking to generate additional gasoline and/or diesel oil distillate.>C ₄compound can also be used as industrial chemical, no matter is as intermediate or end product.Such as, aromatic hydrocarbons toluene, dimethylbenzene, ethylbenzene, paraxylene, meta-xylene and ortho-xylene can be used as the chemical intermediate producing plastics and other products.Meanwhile, C ₉aromatic hydrocarbons and condensed aromatics such as naphthalene, anthracene, tetrahydronaphthalene and decahydronaphthalenes can be used as solvent in industrial processes.

In some embodiments, additional process process fuel blends can be used to remove some component or to make fuel blends meet diesel oil or jet fuel standard further.The technology be applicable to can comprise hydrotreatment to reduce the amount of remaining oxygen, sulphur or nitrogen in fuel blends or to remove these materials.The condition of hydrotreatment hydrocarbon stream is known to those skilled in the art.

In some embodiments, hydrogenation can replace hydroprocessing processes or carry out making at least some alkene key saturated thereafter.In some embodiments, by metal functional group is included in aldol condensation catalyst, hydrogenation reaction and aldol reaction can be made to work in coordination with and to carry out.Carrying out this hydrogenation can make fuel blends meet specific fuel standard (such as diesel fuel standard or jet fuel standard).The hydrogenation of fuel blends logistics can carry out according to known procedure, adopts continuation method or discontinuous method.Hydrogenation reaction can be used to remove remaining carbonyl or/or hydroxyl.In this case, above-mentioned any hydrogenation catalyst can be used.Usually, purification step can be carried out under the extraction temperature of 80-250 DEG C, and refining pressure can be 5-150bar.In some embodiments, purification step can be carried out in gas phase or liquid phase, and uses external hydrogen, recycle hydrogen or their combination as required.

In some embodiments, isomerization process fuel blends can be used to introduce branching or other shape selectivity of required degree at least some component in fuel blends.Before hydrocarbon contacts with isomerization catalyst, remove any impurity also may be useful.Isomerization steps can comprise optional stripping step, wherein by with steam or applicable gas as light hydrocarbon, nitrogen or hydrogen stripped can purifying from the fuel blends of oligomerization.Optional stripping step can carry out with counter-flow pattern in the device of isomerization catalyst upstream, and wherein gas and liquid contact with each other, or before real isomerization reactor, utilize reflux type to carry out in independent stripper plant.

After optional stripping step, fuel blends can be delivered to and comprise in the reactive isomerization unit of one or more catalyst bed.The catalyst bed of isomerization unit can with also stream or reflux type operation.In isomerization unit, pressure can be 20-150bar, and be preferably 20-100bar, temperature range is 195-500 DEG C, is preferably 300-400 DEG C.In isomerization unit, any isomerization catalyst known in the art can be used.In some embodiments, the isomerization catalyst be applicable to can comprise molecular sieve and/or VII race metal 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 Al ₂o ₃or SiO ₂.Typical isomerization catalyst can comprise such as 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 such as water or the unwanted concentration containing oxygen intermediate also may affect >C ₄the activity of the composition of compound and yield and condensation catalyst and stability.In this case, process can comprise dehydration to remove a part of water before condensation reaction and/or optional dehydration, or separator is unwanted containing oxygen intermediate to remove.Such as, separator can be installed before condensation reactor as phase separator, extractor, purifier or destilling tower, thus remove a part of water from the reactant stream comprised containing oxygen intermediate.Can also install separator with remove specific containing oxygen intermediate to allow to generate the hydrocarbon that comprises and there is specific carbon number range or as end product or for the product stream needed for other system or process.

Therefore, in some embodiments, the fuel blends generated by process described here can be meet the hydrocarbon mixture that jet fuel requires (such as meeting ASTM D1655).In other embodiments, the product of process described here can be meet the hydrocarbon mixture that diesel fuel requires (such as meeting ASTM D975).

In other embodiments, the fuel blends (i.e. Fuel Petroleum) comprising gasoline hydrocarbon can be produced." gasoline hydrocarbon " refers to mainly containing C _5-9hydrocarbon (such as C _6-8hydrocarbon) and there are the various hydrocarbon of boiling range of 32-204 DEG C (90-400 ℉).Gasoline hydrocarbon can include but not limited to direct steaming gasoline, naphtha, fluidisation or hot catalytic cracking gasoline, VB gasoline and coker gasoline.Gasoline hydrocarbon content is determined by ASTM method D2887.

In another other embodiment, comprise >C by making in the presence of a dehydration catalyst to generate containing oxygen intermediate catalytic reaction under dehydration temperaturre and dewatering pressure ₂the reaction logistics of alkene and generate >C ₂alkene.>C ₂alkene can comprise the straight or branched hydrocarbon containing one or more carbon-to-carbon double bond.Usually, >C ₂alkene can comprise 2-8 carbon atom, is more preferably 3-5 carbon atom.In some embodiments, alkene can comprise propylene, butylene, amylene, aforesaid isomers and two or more mixture aforementioned.In other embodiments, >C ₂alkene can comprise by making a part of >C ₂the >C that alkene generates through olefin isomerization catalyst catalytic reaction ₄alkene.

Dehydration catalyst can comprise and is selected from following member: acidic alumina, aluminum phosphate, di(2-ethylhexyl)phosphate silica-alumina, amorphous silica-alumina, alumino-silicate, 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 two or more combination arbitrarily.In some embodiments, dehydration catalyst can comprise conditioning agent further, and described conditioning agent is selected from Ce, Y, Sc, La, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi and aforementioned arbitrarily two or more combination.In other embodiments, dehydration catalyst can the oxide of containing element further, and described element is 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 aforementioned two or more combination arbitrarily.In another other embodiment, dehydration catalyst can comprise metal further, and described metal is 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 arbitrarily two or more alloy and aforementioned two or more combination arbitrarily.

In another other embodiment, dehydration catalyst can comprise aluminosilicate zeolite.In some embodiments, dehydration catalyst can comprise conditioning agent further, and described conditioning agent is selected from Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned arbitrarily two or more combination.In some embodiments, dehydration catalyst can comprise metal further, and described metal is 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 arbitrarily two or more alloy and aforementioned two or more combination arbitrarily.

In other embodiments, dehydration catalyst can comprise containing the pentacyclic aluminosilicate zeolite of difunctionality height silicon.In some embodiments, dehydration catalyst can comprise conditioning agent further, and described conditioning agent is selected from Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned arbitrarily two or more combination.In some embodiments, dehydration catalyst can comprise metal further, and described metal is 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 arbitrarily two or more alloy and aforementioned two or more combination arbitrarily.

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

Under alkylation temperature and alkylation pressures, >C is made under existing at alkylation catalyst ₂alkene and >C ₄the logistics catalytic reaction of isoparaffin can generate and comprise >C ₆the product stream of alkane and produce >C ₆alkane.>C ₄isoparaffin can comprise and has 4-7 carbon atom alkane and cycloalkane as iso-butane, isopentane, cycloalkane with have the higher homologue (such as 2-methybutane and 2,4-dimethyl pentane) of tertiary carbon atom, aforesaid isomers and aforementioned two or more mixture arbitrarily.In some embodiments, >C ₄isoparaffin logistics can comprise the inner >C produced ₄isoparaffin, outside >C ₄isoparaffin, circulation >C ₄isoparaffin or aforementioned arbitrarily two or more combination.

>C ₆alkane can be branched paraffin, but also can comprise normal paraffin hydrocarbons.In one form, >C ₆alkane comprises and is selected from following member: side chain C _6-10alkane, side chain C ₆alkane, side chain C ₇alkane, side chain C ₈alkane, side chain C ₉alkane, side chain C ₁₀alkane or aforementioned arbitrarily two or more mixture.In one form, >C ₆alkane can comprise such as dimethylbutane, 2,2-dimethylbutanes, 2,3-dimethylbutanes, methylpentane, 2-methylpentane, 3-methylpentane, dimethyl pentane, 2,3-dimethyl pentane, 2,4-dimethyl pentanes, methyl hexane, 2,3-dimethylhexanes, 2,3,4-trimethylpentane, 2,2,4-trimethylpentanes, 2,2,3-trimethylpentane, 2,3,3-trimethylpentanes, dimethylhexane or aforementioned arbitrarily two or more mixture.

Alkylation catalyst can comprise and is selected from following member: sulfuric acid, hydrofluoric acid, aluminium chloride, boron trifluoride, solid phosphoric acid, chlorinated aluminas, acidic alumina, aluminum phosphate, di(2-ethylhexyl)phosphate silica-alumina, amorphous silica-alumina, alumino-silicate, aluminosilicate zeolite, 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 arbitrarily two or more combination.Alkylation catalyst can also comprise inorganic acid and the Friedel-Crafts metal halide mixture as aluminium bromide and other proton donor.

In some embodiments, alkylation catalyst can comprise aluminosilicate zeolite.In some embodiments, alkylation catalyst can comprise conditioning agent further, and described conditioning agent is selected from Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned arbitrarily two or more combination.In some embodiments, alkylation catalyst can comprise metal further, and described metal is 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 arbitrarily two or more alloy and aforementioned two or more combination arbitrarily.

In some embodiments, alkylation catalyst can comprise the difunctional pentasil zeolites containing aluminosilicate.In some embodiments, dehydration catalyst can comprise conditioning agent further, and described conditioning agent is selected from Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned arbitrarily two or more combination.In some embodiments, alkylation catalyst can comprise metal further, and described metal is 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 arbitrarily two or more alloy and aforementioned two or more combination arbitrarily.In one form, dehydration catalyst can be identical on atom with alkylation catalyst.

Alkylated reaction can be conducive to carrying out at thermodynamic (al) temperature.Usually, alkylation temperature can be-20-300 DEG C, and alkylation pressures can be 1-80bar (absolute pressure).In some embodiments, alkylation temperature can be 100-300 DEG C.In another form, alkylation temperature can be 0-100 DEG C.In still another embodiment, alkylation temperature can be 0-50 DEG C.In still another embodiment, alkylation temperature can be 70-250 DEG C, and alkylation pressures can be 5-80bar.In some embodiments, alkylation catalyst can comprise inorganic acid or strong acid.In other embodiments, alkylation catalyst can comprise zeolite, and alkylation temperature can be greater than 100 DEG C.

In some embodiments, olefin oligomerization can be implemented.Described oligomerization can be implemented in any suitable reactor structure.Suitable structure can include but not limited to that batch reactor, scale semi-batch reactor or flow reactor design, such as, with the fluidized-bed reactor of external regeneration vessels.Reactor design can include but not limited to tubular reactor, fixed bed reactors or be applicable to implementing other type of reactor any of oligomerization.In some embodiments, the olefin feed stream using oligomerization reactor to make to comprise the short-chain olefin with 2-8 carbon atom chain length contacts to transform short-chain olefin for the fuel blends in diesel boiling range with zeolite catalyst at high temperature and pressure, can implement the continuous oligomerization method of the hydrocarbon for the production of diesel oil and jet fuel boiling range.Oligomerization reactor can operate at the temperature of the relatively high pressure of 20-100bar and 150-300 DEG C, preferably 200-250 DEG C.

The oligomeric logistics of gained forms the fuel blends may with multi-products, comprises containing C ₅-C ₂₄the product of hydrocarbon.Additional process can be applied obtain the fuel blends meeting required standard.Initial process step can be applied produce the fuel blends with narrower carbon number range.In some embodiments, separation process such as distillation process generation can be applied and comprise C ₁₂-C ₂₄the fuel blends of hydrocarbon is used for process further.Remaining hydrocarbon may be used for producing Fuel Petroleum blend, be circulated to oligomerization reactor or in additional process.Such as, kerosene distillate can obtain together with diesel oil distillate, and can be used as illumination alkane, be used as jet fuel blend component or be used as reactant (particularly C in the process of producing LAB (linear alkylbenzene (LAB)) in conventional crude or the derivative jet fuel of synthesis ₁₀-C ₁₃cut).After hydrotreatment, naphtha cut can be caused heat cracker for the production of ethene and propylene, or cause cat cracker to produce ethene, propylene and gasoline.

Additional process process fuel blends can be used to remove some component or to make fuel blends meet diesel oil or jet fuel standard further.The technology be applicable to can comprise hydrotreatment to remove any remaining oxygen, sulphur or nitrogen in fuel blends.Hydrogenation can be implemented to make at least some olefinic bonds saturated after hydroprocessing processes.This hydrogenation can be implemented and meet concrete fuel standard (such as diesel fuel standard or jet fuel standard) to make fuel blends.The hydrogenation step of fuel blends logistics can by known program with pattern enforcement continuously or intermittently.

For contributing to understanding the present invention better, provide the embodiment of preferred embodiment below.Never the following example should be read as limitation of the scope of the invention or restriction.

Embodiment

Intermittent reaction research is implemented in Parr 5000Hastelloy multi reactor unit, and described multi reactor unit has at pressure 135bar and temperature parallel operation at 275 DEG C at the most at the most, the reactor of 6 75ml that stirs with magnetic stirring bar.

Embodiment 1: determine the minimum gas velocity that fluidized slurry catalyst needs.100ml graduated cylinder is filled, under remaining on 23 DEG C and normal pressure by the deionized water of the nickel-molybdenum/aluminium oxide slurry catalyst of 1 gram of nominal 1-25 μm and 50 grams.Knot is burnt injection stone (ACE glass) be placed on the bottom of graduated cylinder and use 1/8-inch Teflon pipe to be connected to N ₂supply.Change N ₂flow determines the minimum line speed that complete fluidized slurry catalyst needs to fluid column top.Corresponding fluidisation completely and mixed serum are 0.037cm/s to the linear velocity at liquid level top.

Embodiment 2: the digestion of cellulose series biomass solid.1 inch diameter × 12 inch high digester-reactor tube is furnished with the ring-type mozzle plug-in unit of 0.5 inch diameter.By making plug-in unit placed in the middle apart from each end 2cm place welding two 1.16 inches × 1.5cm thin slices.The bottom of relative pipe diametrically cut out two 1cm high × 6mm v-shaped groove flows to mozzle inside to allow solid and liquid in the clear from external rings.The metallic plate of nominal 0.89 inch diameter is arranged on the bottom of 1 inch of external diameter pipe, is used for keeping inner loop and prevents from solid from falling into being used in pipe and the pipe fitting of digester-reactor bottom.1/8 inch of stainless steel gas dispersion pipe is inserted from bottom, upwards enters ring-type mozzle to the position higher than v-type kerve top 1cm by base plate and extension 0.5 inch.Mozzle extends in digester-reactor tube top overfall 3.5 feet, makes, once establish the driving force of air-flow by inner loop, can be overflowed by the liquids and gases stream of inner loop and be returned component bottom by external rings.

Digester-reactor nickel-molybdenum/aluminium oxide slurry catalyst of 0.762 gram of nominal 1-25 micron is filled, and this catalyst adds bottom and keeps with metallic plate.Inner loop is filled with the southern pine small pieces (moisture content of 39%) of 4.794 grams of nominal size 6mm × 5mm × 3mm.Opposite outer ring diametrically places the glass tampon that two amount to 0.035 gram apart from 3cm place, inner loop top, be used for trapping the component loops solid in digester-reactor assembly.

Digester-reactor is filled to the position higher than 1.5 inches, inner loop top with solvent (1,2-PD, 5% ethylene glycol with 45wt% in the deionized water of 0.05wt% potash buffering).Hydrogen stream is introduced at digester-reactor bottom, and is imported by pressure regulator and remain in the high pressure product container of 70bar, afterwards under normal pressure and room temperature (23 DEG C) with 94ml/min emptying.Be 0.049cm/s by mozzle superficial linear vilocity as calculated, it has exceeded the minimum line speed of complete mixed serum catalyst in embodiment 1.When there is not mozzle, linear gas velocities is only 0.013cm/s or is less than 1/3rd of speed slurry catalyst being mixed completely and required for suspending.Then by band heater (Gaumer) hot digestion device-reactor to 190 DEG C.After 1.5 hours, heating temperatures to 230 DEG C keeps 2 hours, and rise to 250 DEG C subsequently and keep 3 hours, total run time is 6.5 hours.

The wood chip having digested 59% is shown at the remaining wood chip height of last mensuration run.ICP solid analysis (this solid retains the mineral wool that extracts from external rings after operation beyond the Great Wall) shows the existence of nickel and molybdenum, corresponding to the catalyst being present on two filtering plugs 2.2 and 2.9wt%.Result shows that motive force that nickel-molybdate catalyst is sprayed by gas moves to the top of external rings from the bottom of mozzle.

(single oxygenatedchemicals, ethylene glycol, glycol, alkane and acid) is formed by gas-chromatography monitoring product.Application 60m × 0.32mm ID DB-5 chromatographic column pillar the furnace temperature of 40 DEG C (1 μm of thick, the split ratio of 50:1, helium flow amount of 2ml/min and) implements gas chromatographic analysis 8 minutes, is warming up to 285 DEG C subsequently and the retention time is 53.5 minutes with 10 DEG C/min.Injector temperature is set to 250 DEG C, and detector temperature is set to 300 DEG C.

Analyze the collection liquid of discharging from digester-reactor and show that elution component all thus shows the time of staying being less than sorbierite (C6 sugar alcohol) for the product of 1.68wt% being had to be formed from the component of GC elution under the injector temperature of 375 DEG C.If it is enough little of the product liquid from GC elution that all hemicelluloses and cellulose carbohydrate are optionally converted into molecular weight, the desired value that this product corresponding to 1.66wt% is formed.Therefore, desired product yield for selective conversion carbohydrate desired by lower molecular weight intermediate yield 102%.

Embodiment 3-5: catalyst is on the impact of yield.In embodiment 3, digester-reactor 2-propyl alcohol deionized water solution of 20.0 grams of 50wt%, the sodium carbonate buffer of 0.30 gram and 0.504 gram of cobalt sulfide-molybdate catalyst (DC2534 being crushed to granularity and being less than 100 microns, containing cobalt oxide and the molybdenum trioxide (high to 30wt%) of 1-10% on alumina, and be less than the Criterion Catalyst & Technologies L.P of nickel of 2%).Make this catalyst as prevulcanization described in U.S. Patent Application Publication 20100236988.Then, reactor 2.7 grams of Southern Pine wood chips (being pulverized by shredding machine) containing 39% moisture content are filled, and use the H of 50-51bar afterwards ₂pressurize and be heated with stirring to 240 DEG C and keep 5 hours.Repetitive cycling adds wood chip three times.

After cooling and pressure-emptying, extracted liquid sample is used for GC and analyzes.By WhatmanGF/F Filter paper filtering reactor content, the filter paper with solid is dried at 90 DEG C in a vacuum furnace assesses indigested solid yesterday.GC analyzes and shows to exist intermediate desired by the 6.3wt% oxygen-containing component of sorbierite (time of staying be less than).This value correspond to the quality relative to the carbohydrate being filled into reactor as timber and estimate 79% title intermediate yield, or filling timber digestibility 90% relative to 88% is selective.

For embodiment 4, repeat experiment, 3 circulations add timber, use the 2-propyl alcohol deionized water solution of 25wt% as solvent and identical cobalt-molybdenum phosphate catalyst.GC analyzes the total amount shown relative to the carbohydrate of filling, and the yield of desired intermediate is 78%.

For embodiment 5, repeat experiment, use the ethanol of 25% as solvent, but do not use catalyst.The yield of the bright title intermediate of GC analytical table only 23%, and the timber feedstock conversion of 36wt% is bottoms tar layer, this tar layer can not flow when being again heated to 100 DEG C.

Therefore, the present invention performs well in reaching mentioned and intrinsic various object and advantage.Above-disclosed specific embodiments is descriptive, because after benefiting from the instruction provided herein, the present invention can carry out adjusting and implementing in mode different but equivalent to those skilled in the art.In addition, except described in claims which follow, do not intend to limit the details of given construction or design here.Therefore, clearly specific descriptions embodiment disclosed above can carry out changing, combine or adjusting, and all these changes it is believed that all in the scope of the invention and essence.Here descriptive invention disclosed can suitably do not exist here with no specific disclosure of any element and/or any optional elements disclosed herein time implement.Although the mode of each composition and method all " comprising ", " containing " or " comprising " various component or step describes, each composition and method also can substantially by or " be made up of " various component and step.Disclosed all numerical value and scope all can change to a certain extent above.When openly having the number range of lower limit and the upper limit, the scope all specifically disclosing any number in the scope of dropping on and comprise arbitrarily.Particularly, each number range disclosed herein (being " about a-b " form of " a to b " or equivalence) is all interpreted as being included in all numerical value in described broader numerical and scope.In addition, unless patentee clearly and clearly defines in addition, the term in claim is understood according to their basic conventional implications.In addition, applied in the claims indefinite article is here defined as and refers to the one or more of the element that they refer to.If this description and one or more word that may use in the patent of reference here or other document or term exist any conflict, then should adopt the definition consistent with this description.

Claims

1. a conversion systems for biomass, comprising:

Comprise the pressure vessel of first paragraph and second segment, described first paragraph comprises hydrothermal digestion device and described second segment and comprises the first catalytic reduction reactor device containing the first hydrogenation catalyst catalyst, wherein hydrothermal digestion device and the first catalytic reduction reactor device fluid communication with each other;

Operate with pressure vessel the living beings feeding mechanism be connected, cellulose series biomass solid can be introduced pressure vessel and also can from the first catalytic reduction reactor device extraction product by described living beings feeding mechanism; With

The hydrogen feeding line be connected is operated with the first catalytic reduction reactor device.

2. the conversion systems for biomass of claim 1, wherein said pressure vessel comprises circulus, and described first paragraph forms the exterior section of circulus and the interior section of described second segment formation circulus.

3. the conversion systems for biomass of claim 1 or 2, wherein said first paragraph and second segment are each other and come in pressure vessel.

4. the conversion systems for biomass of any one of claim 1-3, also comprises:

The fluid circulation loop that fluid is communicated with is set up between the fluid intake of pressure vessel and the fluid issuing of living beings feeding mechanism.

5. the conversion systems for biomass of claim 4, wherein said fluid circulation loop also comprises the second catalytic reduction reactor device containing the second hydrogenation catalyst catalyst.

6. the conversion systems for biomass of claim 5, wherein said first catalyst is identical with the second catalyst.

7. the conversion systems for biomass of claim 5, also comprises:

Be positioned at the solid separating mechanism between the fluid issuing of fluid circulation loop endogenous substance feeding mechanism and the fluid intake of the second catalytic reduction reactor device.

8. the conversion systems for biomass of claim 5, also comprises:

The product be communicated with fluid circulation loop fluid extracts pipeline out, and described product is extracted pipeline out and is positioned between the fluid intake of pressure vessel and the fluid issuing of the second catalytic reduction reactor device.

9. the conversion systems for biomass of aforementioned any one of claim, wherein living beings feeding mechanism can keep, during pressurization state, cellulose series biomass solid is introduced pressure vessel at pressure vessel;

Also comprise fluid circulation loop, described fluid circulation loop comprises pressure vessel and the second catalytic reduction reactor device containing the second hydrogenation catalyst catalyst.

10. the conversion systems for biomass of claim 9, wherein said fluid circulation loop also comprises living beings feeding mechanism, and described fluid circulation loop is set up fluid and is communicated with between the fluid intake of pressure vessel and the fluid issuing of living beings feeding mechanism.

The conversion systems for biomass of 11. claims 9, also comprises:

Be positioned at the solid separating mechanism between the fluid issuing of fluid circulation loop inner pressure vessel and the fluid intake of the second catalytic reduction reactor device.

The conversion systems for biomass of 12. claims 9, also comprises:

13. 1 kinds of methods, comprising:

The pressure vessel comprising first paragraph and second segment is provided, described first paragraph comprises hydrothermal digestion device and second segment and comprises the first catalytic reduction reactor device containing the first hydrogenation catalyst catalyst, wherein hydrothermal digestion device and the first catalytic reduction reactor device fluid communication with each other;

Cellulose series biomass solid is added in pressure vessel;

Cellulose series biomass solid in the hydrothermal digestion device of heated pressure container, is formed in liquid phase the hydrolysate comprising soluble-carbohydrate thus;

Under molecular hydrogen exists, conveying liquid is mutually by the first catalytic reduction reactor device, thus described soluble-carbohydrate is converted into product at least partly; With

At least part of described liquid phase is delivered to the second catalytic reduction reactor device containing the second hydrogenation catalyst catalyst from pressure vessel, thus soluble-carbohydrate is further converted to product.

The method of 14. claim l3, also comprises:

At least part of described liquid phase is recycled to pressure vessel from the second catalytic reduction reactor device.

The method of 15. claims 13 or 14, wherein by described liquid phase with recycle ratio 2 or be lowlyer recycled to pressure vessel.

The method of 16. any one of claim 13-15, wherein makes cellulose series biomass solid (butt) digestion of at least 90% to produce hydrolysate.

The method of 17. any one of claim 13-15, also comprises:

After soluble-carbohydrate is further converted to product, from the outlet extraction section product of the second catalytic reduction reactor device; With

Product is converted into bio-fuel.

The method of 18. any one of claim 13-17, wherein said first catalyst comprises slurry catalyst.

The method of 19. claims 18, also comprises:

By be exposed at least 200 DEG C temperature water reuse (treatment described in slurry catalyst.

The method of 20. any one of claim 13-19, wherein said first paragraph and second segment are each other and come in pressure vessel.