CN104471144B

CN104471144B - Biomass conversion systems providing integrated stabilization of a hydrolysate using a slurry catalyst and methods for use thereof

Info

Publication number: CN104471144B
Application number: CN201380034071.7A
Authority: CN
Inventors: J·B·鲍威尔
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2012-06-28
Filing date: 2013-06-27
Publication date: 2017-03-01
Anticipated expiration: 2033-06-27
Also published as: AU2013280239B2; CN104471144A; BR112014032113A2; AU2013280239A1; EP2867404A1; AU2013280239C1; CA2877497A1; US20160237359A1; WO2014004842A1; IN2014DN10536A; US20140000154A1

Abstract

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

Description

Biomass transformation system using the integrated stable hydrolyzate of offer of slurry catalyst System and its using method

The quoting of related application

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

Content of the invention

The disclosure relates generally to and produces hydrolysis product using digestion (digestion) process cellulose biomass solid Thing, more specifically, is related to allow to comprise the hydrolyzate of soluble carbohydrate in the digestion phase by using slurry catalyst Between the conversion systems for biomass that is stabilized and its using method.

Background of invention

The material that many has commercial significance can be from natural origin, especially biomass manufacture.Cellulose biomass exists This respect especially has advantage, because the diversified rich in carbohydrate finding wherein in a variety of forms.As herein Used, term " cellulose biomass " refers to comprise the lived of cellulose or lived biomaterial recently.In height It is the source of carbohydrate the abundantest in the world Deng the ligno-cellulosic materials finding in plant cell wall.Generally from fiber The material that cellulosic biomass is obtained includes, for example, the paper obtaining via part digestion and paper pulp, and the biology being obtained by fermentation Ethanol.

Plant cell wall is divided into two parts：Primary cell wall and secondary cell wall.Primary cell wall is expansion cell Structural support is provided, and comprises three kinds of main polysaccharide (cellulose, pectin and hemicellulose) and one group of glycoprotein.Secondary thin Cell wall produces after cell has terminated growth, and it also comprises polysaccharide, and by being polymerized wood with hemicellulose is covalently attached Quality strengthens.Hemicellulose and the usual rich content of pectin, but cellulose is main polysaccharide and carbohydrate the abundantest Source.The complex mixture of the composition coexisting with cellulose can make it be difficult to process, as discussed hereinbelow.

The split Fossil fuel succedaneum aspect rising in Renewable resource has been paid and has been significantly focused on.Cellulose biomass Because it is rich and the multiformity of the Multiple components of wherein discovery (particularly cellulose and other carbohydrates) and in this side Special attention has been won in face.Despite clear and definite and strong interest, but the exploitation of biologically based fuels technology and enforcement are delayed always Slowly.Prior art so far produced the fuel (for example, bio-ethanol) with low energy densities and/or can not with There are electromotor design and the fully compatible fuel of transportation infrastructure (for example, methanol, biodiesel, Fischer-Tropsch bavin Oil, hydrogen and methane).For cellulose biomass being processed into the energy of the fuel mixture with the composition similar to Fossil fuel Amount and cost-effective method would is that ideal for solving aforementioned and other problems.

When cellulose biomass is converted into fuel mixture and other materials, cellulose therein and other complex carbon Hydrate can be extracted and be converted into better simply organic molecule, and the latter can subsequently reform further.Fermentation is can be in the future The complex carbohydrates of authigenic material are converted into a kind of method of more useful form.However, fermentation method is typically slow, need Want large volume reactor, and produce the initial reaction product (ethanol) of the energy density having.Digestion be can by cellulose and Other complex carbohydrates are converted into another kind of method of more useful form.Digestion method can be by the fiber in cellulose biomass Element and other complex carbohydrates are decomposed into and fit through the better simply solvable carbon water that downstream reforming reaction converts further Compound.As used herein, term " soluble carbohydrate " refers to the monosaccharide of dissolving or polysaccharide in digestion method.Although latent Chemistry be understood to digestion cellulose and other complex carbohydrates and further simple carbohydrates be converted into Recall the organic compound for being present in Fossil fuel, not yet develop and be suitable for for cellulose biomass being converted into fuel mixing The digestion method of the high yield of thing and Energy Efficient.At this point, with using digestion and other method, cellulose biomass is turned Turning to the related most basic demand of fuel mixture is to cause the required energy input of conversion not should be greater than product fuel mixing The utilisable energy output of thing.This primary demand result in a lot of secondary problems, and it represents still unsolved pole so far jointly Big industry challenge.

To using digestion by energy and cost-effective in the way of that cellulose biomass is converted into fuel mixture is related Problem is not only complexity, and they are totally different from encountered in conventionally used digestion method in paper and pulp industry Those.Because the purpose of cellulose biomass digestion in paper and pulp industry is to retain solid material (for example, wood pulp), lead to Often carry out the incomplete digestion of suitable short time in low temperature (for example, less than 100 DEG C).On the contrary, it is suitable for turning cellulose biomass Turn to fuel mixture and the digestion method of other materials is desirably disposed to by dissolving as far as possible under high-throughput mode Many pristine fibre cellulosic biomass and make yield maximize.

For a variety of reasons, be difficult to produce via the conventional change of paper and paper pulp digestion method more substantial for fuel Soluble carbohydrate in mixture and other materials.From the perspective of production capacity, simply by paper and pulp industry Digestion method to run the longer time be undesirable to produce more soluble carbohydrate.Using such as highly basic, strong acid or The digestion accelerator of sulphite can increase process costs and complexity to accelerate digestion speed, and this separates after being attributable to process Step and possible protect downstream component from the needs of these reagent (impact).Accelerate digestion speed by improving digestion temperature Yield actually can be reduced, this is attributable to the thermal degradation of soluble carbohydrate that can occur under higher digestion temperature. Produce upon digestion, soluble carbohydrate is high response, and can degrade rapidly, especially in higher temperature bar Under part (for example, higher than 100 DEG C, especially higher than 150 DEG C).In terms of energy efficiency angle, also may be used using higher digestion temperature Can be undesirable.Any economically feasible that can defeat the fuel mixture coming from cellulose biomass in these difficulties Property.

A kind of method path that the soluble carbohydrate in hydrolyzate avoids thermal degradation can be protected to be so that them is experienced Catalytic reduction reaction process, this process may include hydrogenation and/or hydrogenolysis.By carrying out one or more catalytic reduction reaction Make the soluble carbohydrate in hydrolyzate stably can allow the digestion of cellulose biomass with other may compared with higher Temperature without excessive sacrifice yield.In addition, the product of catalytic reduction reaction process can be easy to turn by downstream reforming reaction Turn to fuel mixture and other materials.

It is high because cellulose biomass feeds to cellulose biomass is processed into the related other problems of fuel mixture Be changed into conversion percentages soluble carbohydrate needs generation.Specifically, when cellulose biomass solid is by digestion, Their size is eventually declined to it becomes the degree of the smooth movement of energy.As used herein, can smooth movement cellulose raw The cellulose biomass solid of material solid, particularly a size of 3mm or less, will be referred to as " cellulose biomass particulate ". Cellulose biomass particulate can transport out from the digestion area of the system for converting cellulose biomass and enter one or many Individual wherein solid is undesired and can be in harmful area.For example, cellulose biomass particulate has thromboembolism catalyst bed, defeated Send the possibility of pipeline etc..Although additionally, size is little, cellulose biomass particulate can represent non-the seeking of cellulose biomass charging Often (non-trivial) part, and if they are not converted further as soluble carbohydrate, may affect To the ability being satisfied with conversion percentages.Digestion method due to paper and pulp industry converts percentage with relatively low cellulose biomass Ratio runs it is believed that less amount of cellulose biomass particulate can be generated, and has little effect to those digestion methods.

In addition to required carbohydrate, other materials also are present in cellulose biomass, and they are to energy Process with cost effective manner and be particularly problematic.Sulfur-bearing and/or nitrogenous aminoacid or other catalyst poison there may be In cellulose biomass.If be not removed, these catalyst poisons can affect urging for stable meltable carbohydrate Change reduction reaction, thus leading to the process shutdown phase in order to catalyst regeneration and/or changed and reducing when restarting technique overall Energy efficiency.On the other hand, removing during these catalyst poisons also to affect the energy of biomass conversion process Efficiency, this is due to removing required ion exchange process typically less than producing solvable carbon hydrate by digestion for carrying out it Those temperature of thing are carried out, and thus can introduce heat exchange operation, and this heat exchange operation increased design complexity and possibility Increase running cost.

As confirmed above, cellulose biomass represents extensive engineering challenge to effective conversion of fuel mixture Challenge.The disclosure solves these and challenges and additionally provide associated advantages.

Content of the invention

The disclosure relates generally to and processes cellulose biomass solid using digestion and produce hydrolyzate, more specific and Speech, is related to make the stable life of the hydrolyzate comprising soluble carbohydrate by the use of slurry catalyst in digestion process Material conversion system and its using method.

In some embodiments, the invention provides conversion systems for biomass, it includes：Comprising being capable of anakmetomeres hydrogen Slurry catalyst (" molecular hydrogen actived slurry catalyst ") hydrothermal digestion unit；It is operably connected with hydrothermal digestion unit Optional hydrogen feeding line；With the fluid circulation loop including hydrothermal digestion unit and catalytic reduction reactor unit, this is urged Change reduction reactor unit and also comprise slurry catalyst.

In some embodiments, the invention provides method, it includes：Cellulose raw is provided in hydrothermal digestion unit Material solid, described hydrothermal digestion unit comprises slurry catalyst (" the molecular hydrogen actived slurry catalysis being capable of anakmetomeres hydrogen Agent ")；In the presence of molecular hydrogen in hydrothermal digestion unit heating cellulose biomass solid, make simultaneously slurry catalyst circulate By described hydrothermal digestion unit, thus forming the hydrolyzate comprising soluble carbohydrate in the liquid phase；In solvable carbon water At least partly soluble carbohydrate is converted into product when compound is in hydrothermal digestion unit；With by least part of liquid Soluble carbohydrate, to the catalytic reduction reactor unit also comprising slurry catalyst, is thus converted into by phase transfer further Product.

When having read the explanation of following preferred embodiment, the feature and advantage of the disclosure are for those skilled in the art To be readily visible.

Brief description

The following drawings is comprised so that some aspects of the disclosure to be described, and is not construed as exclusiveness embodiment.Institute Disclosed theme can have sizable modification, change, combination and full scope of equivalents in form and functionally, as this area skill Known and the disclosure the benefit of art personnel is such.

Fig. 1 shows there is the hydrothermal digestion unit being connected with each other in fluid circulation loop and catalytic reduction reactor list The schematic diagram of the conversion systems for biomass of unit, wherein hydrothermal digestion unit and catalytic reduction reactor unit all comprise slurry catalysis Agent.

Specific embodiment

The disclosure relates generally to and processes cellulose biomass solid using digestion and produce hydrolyzate, more specific and Speech, is related to make the life stable including the hydrolyzate of soluble carbohydrate by the use of slurry catalyst in digestion process Material conversion system and its using method.

In embodiment described herein, the digestion speed of cellulose biomass solid can be added in the presence of digestion solvent Hurry up.In some cases, digestion solvent is positively retained under elevated pressures, and described elevated pressures make digestion solvent in its normal boiling point On be maintained as liquid.Although from the point of view of production capacity under conditions of these types faster cellulose biomass Solid digestion speed is probably preferably, but as discussed above, soluble carbohydrate may be easily at relatively high temperatures Degraded.

Related to soluble carbohydrate degraded for solving the problems, such as, present disclose provides digestion cellulose biomass solid Effectively facilitate the heat-staple system and method for the soluble carbohydrate being generated by simultaneously.Specifically, the disclosure provides The system and method that hydrothermal digestion and one or more catalytic reduction reaction occur in the same container.If it has been found that Then most effectively be there is stablizing of soluble carbohydrate in like fashion.The above can be by comprising cellulose biology The hydrothermal digestion unit of matter solid includes being capable of the slurry catalyst of anakmetomeres hydrogen to realize.As used herein, term " Slurry catalyst " refers at least partly to suspend in the liquid phase via air-flow, liquor stream, mechanical agitation or any combination of them Comprise can smooth movement catalyst granules catalyst.There is slurry catalyst can allow at it in hydrothermal digestion unit Middle one or more original position (integrated) catalytic reduction reaction of generation, thus advantageously to the greatest extent may be used after soluble carbohydrate formation Can intercept and convert soluble carbohydrate soon is more stable product.As used herein, term " situ catalytic is also Former reaction " refers to the catalytic reduction reaction occurring in same container with digestion process.The formation of product can reduce in water The amount of the thermal degradation occurring in hot digestion process, so that cellulose biomass solid can be occurred in time to required product High yield conversion.

In addition to soluble carbohydrate immediate stability is product, from the point of view of energy efficiency, carry out one Plant or multiple situ catalytic reduction reaction is also especially beneficial.Specifically, the hydrothermal digestion of cellulose biomass is heat absorption Process, and catalytic reduction reaction is heat release.Therefore, excessive heat produced by situ catalytic reduction reaction can be used for driving hydro-thermal Digestion, thus reduce the amount carrying out the extra heat energy input needed for digestion.Due in embodiment described herein digestion and Catalysis reduction occurs in same container, occurs the probability of heat transfer loss to minimize, if catalytic reduction reaction is independent Heat transfer loss is entered to be about to occur in position.In addition, in such construction, situ catalytic reduction reaction can be in hydrothermal digestion unit The product supply that middle offer gradually increases, it can be used as and/or supplements digestion solvent.Due to product and digestion solvent Can be identical, not separate and circulate the special need of most of digestion solvent before downstream processes product further Will, from the point of view of energy efficiency, this can be favourable further.

Although it is anti-to carry out one or more situ catalytic reduction for stable meltable carbohydrate and realization are thermally integrated Should be ideal, the catalyst poison in cellulose biomass and other materials may make it difficult to carry out such Process.When carrying out situ catalytic reduction reaction, having no chance before the slurry catalyst of catalyst poison contact distribution will It removes.The method that this problem can be solved is slurry catalyst using poisoning resistant, and some of which is discussed below. Another kind of replacement scheme is using when be exposed to can be easily renewable in hydrothermal digestion unit or during the condition of foundation nearby Slurry catalyst.For example, in some embodiments, reproducible slurry catalyst can be by being exposed at least 300 DEG C temperature The water reuse (treatment of degree.

Once during hydrothermal digestion, soluble carbohydrate is at least partly converted into more stable product, can Molten carbohydrate can be also using described slurry catalyst or be capable of the difference of anakmetomeres hydrogen and urge to the conversion of product Occur in the single catalytic reduction reactor unit of agent.The conversion occurring in catalytic reduction reactor unit may include just Beginning product degree of oxidation further reduce and/or higher conversion from soluble carbohydrate to oxidation intermediates.As this Used by literary composition, alcohol that term " oxidation intermediates " refers to produce from the catalytic reduction reaction of soluble carbohydrate, polyhydric alcohol, Ketone, aldehyde and its mixture.The feature of described conversion systems for biomass can allow the initially dissolved carbohydrate of significant quantity It is converted into the form that suitable following process is bio-fuel, simultaneously in hydrothermal digestion unit or be formed about as a small amount of as possible Caramelan and other catabolites.

The product obtaining from catalytic reduction reactor unit can be recycled to hydrothermal digestion unit, and it can here As digestion solvent, and/or discharge so that subsequent transformation is bio-fuel from catalytic reduction reactor unit.By producing in hydrolysis Soluble carbohydrate is at least partly converted into product, to catalysis reduction before reaching catalytic reduction reactor unit by thing The demand of reactor unit can be reduced and it is possible to realize the higher conversion to product for the soluble carbohydrate.Separately Outward it is possible to use less catalytic reduction reactor unit compared with related process, this is because at least partially soluble carbon Hydrate was converted before reaching catalytic reduction reactor unit.Further, since being urged in hydrothermal digestion unit Change reduction reaction can achieve and is preferably thermally integrated efficiency, may less need product from catalytic reduction reactor unit The technique being recycled to hydrothermal digestion unit to maintain Energy Efficient.Therefore, can be able to be arranged using lower product recycle ratio Go out more product fraction to be subsequently converted into bio-fuel or other materials.Preceding factors also can reduce and turn with biomass Change system and the relevant fund of correlation technique and running cost.

Further with regards to heat integration efficiency, this conversion systems for biomass is also especially beneficial, this is because in some enforcements Hydrothermal digestion unit in system in mode can operate continuously at an elevated temperature and pressure.Continuous high temperature hydrothermal digestion can lead to Cross and conversion systems for biomass realization is constructed as below：Fresh biomass can by continuous and semicontinuous be supplied to hydrothermal digestion unit, with When its with pressurized state operate.In the case of the ability in the hydrothermal digestion unit fresh biomass not being introduced into pressurization, It may happen that the decompression of hydrothermal digestion unit and cooling in biomass adding procedure, significantly reduce conversion process energy and Cost efficiency.As used herein, term " continuous interpolation " and its grammer equivalent components refer to following process：Wherein cellulose raw Material be added to hydrothermal digestion unit in an uninterrupted manner and insufficient make hydrothermal digestion unit reduce pressure.As used herein, Term " semi-continuous interpolation " and its grammer equivalent components refer to that biomass add discontinuously but as needed to hydrothermal digestion unit Plus and insufficient make hydrothermal digestion unit reduce pressure.The solid of the hydrothermal digestion unit that biomass can be supplied to pressurization introduces mechanism Further describe and describe more fully below.

In some embodiments as herein described, slurry catalyst can be simultaneously used for hydrothermal digestion unit and catalysis reduction To adjust soluble carbohydrate to the catalytic reduction reaction of product in reactor unit.Using slurry catalyst, especially It is in hydrothermal digestion unit, can be favourable, this is because fixed bde catalyst in the presence of cellulose biomass solid By very easy thromboembolism.In addition, by catalytic reduction reactor unit using slurry catalyst, because of such as cellulose Thromboembolism probability caused by biomass particulate reduces.Still in addition, in some embodiments, by simultaneously in hydrothermal digestion list Using slurry catalyst in unit and catalytic reduction reactor unit, (sequester) catalyst need not be isolated in any position, its Can freely circulate between.However, in some embodiments, in hydrothermal digestion unit, catalytic reduction reactor unit Or the isolation of catalyst in the two, can be implemented.Due to there is cellulose biomass solid in hydrothermal digestion unit, slurry is catalyzed Agent can be partially left at wherein advantageous by cellulose biomass charging, thus reducing enter as in other slurry catalyst techniques The needs of row catalyst isolation.Reservation in hydrothermal digestion unit for the slurry catalyst also can be aided with can be in biology as herein described Low circulation ratio used in matter conversion system.Anyway, slurry catalyst passes through cellulose biomass in hydrothermal digestion unit The circulation of charging can provide good catalyst distribution, thus allowing soluble carbohydrate after the formation thereof in biomass It is stabilized via catalytic reduction reaction as rapidly as possible.

Because slurry catalyst can be smooth mobile, hydrogen injection, solvent circulation or their combination in any can be used for Slurry catalyst is dispersed throughout cellulose biomass charging distribution in hydrothermal digestion unit.Good catalysis in cellulose biomass Agent distribution can improve yield by intercepting soluble carbohydrate before having mechanism of degradation meeting in soluble carbohydrate.This Outward, can allow more to successfully use fixed bed digestion unit using slurry catalyst, this is because without mechanical agitation or similar Mechanical agitation is to affect catalyst distribution.This can allow per unit compared with possibility person in agitator tank or similar digestion unit construction Volume digestion unit is using higher biomass/solvent ratio.Further, since stirring is not required, do not had before digestion occurs There are the special needs changing biomass solid size.

Unless otherwise specified herein it should be understood that using term " biomass " or " cellulose raw in the explanation of this paper Material " refers to " cellulose biomass solid ".Solid can be any size, shape or form.Cellulose biomass solid is permissible These solids size any, shape or form naturally occur, or it can be in the process that takes a step forward of hydrothermal digestion.Real at some Apply in mode, cellulose biomass solid such as can be chopped into, grind, smashing, pulverizing before hydrothermal digestion at the chi needed for produce Very little.In some or other embodiment, cellulose biomass solid can hydrothermal digestion occur before wash (for example, with water, Acid, alkali and combinations thereof etc.).

When implementing embodiments of the present invention, can be using any kind of suitable biological matter source.Suitable cellulose Biomass source may include, for example, forestry waste wood, agriculture waste wood, herbaceous material, municipal solid rubbish, rubbish and recycled writing paper, paper Slurry and papermaking waste wood and any combination of them.Therefore, in some embodiments, suitable cellulose biomass may include, For example, corn straw, Caulis et Folium Oryzae, bagasse, Miscanthus, Sorghum vulgare Pers. slag, switchgrass, bamboo, Herba Eichhorniae, hardwood, hardwood chip, leaf wood Slurry, cork, cork sheet, softwood pulp and any combination of them.It is biological that leaf, root, seed, straw and shell can be used as cellulose Matter is originated.The general source of cellulose biomass may include, for example, agriculture waste wood (for example, corn straw, Caulis et Folium Oryzae, seed hulls, Bagasse, shuck etc.), timber (for example, timber or bark, sawdust, timber scrap (timber slash), plant wastes (mill scrap) etc.), municipal refuse (for example, waste paper, garden cutting thing (yard clippings) or remains etc.), Yi Jineng Source crop (for example, willow, willow, switchgrass (switch grass), Herba Medicaginiss, grassland Indigo Naturalis (prairie bluestream), Corn and soybean etc.).Cellulose biomass can be based on selection considered below：Such as, for example, cellulose and/or hemicellulose contain Amount, content of lignin, growth time/season, growth position/cost of transportation, growth cost, harvesting cost etc..

The illustrative carbohydrate (carbohydrate) that may be present in cellulose biomass may include, for example, Saccharide (sugar), sugar alcohol, cellulose, lignocellulose, hemicellulose and any combination of them.Upon according to herein Soluble carbohydrate is removed from biomass substrate by described digestion method, and this soluble carbohydrate can via catalysis also Former reaction is converted into the product comprising oxidation intermediates.In some embodiments, the reaction including oxidation intermediates is produced Thing can use further hydrogenolysis, hydrogenation, condensation reaction, isomerization reaction, oligomerization, hydrotreating reaction, alkane Any combinations of glycosylation reaction etc. are further converted to bio-fuel or other materials.In some embodiments, at least partly Oxidation intermediates can be recycled to hydrothermal digestion unit to constitute at least part of digestion solvent.At least partly oxidation intermediates arrive The recirculation of hydrothermal digestion unit be thermally integrated with process efficiency in terms of be also especially beneficial.

In some embodiments, conversion systems for biomass as herein described may include：Comprise to be capable of anakmetomeres hydrogen The hydrothermal digestion unit of slurry catalyst (" molecular hydrogen actived slurry catalyst ")；It is operably connected with hydrothermal digestion unit Optional hydrogen feeding line；With the fluid circulation loop including hydrothermal digestion unit and catalytic reduction reactor unit, this catalysis Reduction reactor unit also comprises slurry catalyst.

In some embodiments, cellulose biomass solid can be continuously introduced into hydrothermal digestion unit.In other reality Apply in mode, cellulose biomass solid can be non-continuously introduced into hydrothermal digestion unit.In multiple embodiments, hydro-thermal is boiled Solution unit can operate continuously generation under pressurized state (for example, at least pressure of 30bar) and include soluble carbohydrate Hydrolyzate, soluble carbohydrate is more stable product through catalytic reduction reaction converted in-situ.Keep pressurized state Can ideally rapid pace promote cellulose biomass solid digestion.In some embodiments, cellulose biomass is solid Body can be added continuously to hydrothermal digestion unit, keep pressurized state simultaneously.In some embodiments, cellulose biomass solid Hydrothermal digestion unit can be semi-continuously added to, keep pressurized state simultaneously.

In multiple embodiments, fluid circulation loop can be configured to set up upwards in catalytic reduction reactor unit Flow of fluid.That is, in conversion systems for biomass as herein described, in such embodiment, catalytic reduction reactor list Unit can operate as bubble tower catalytic reduction reactor.In some embodiments, there may be slurry catalyst isolation (sequestration) mechanism, it can work to be maintained at least part of slurry catalyst in catalytic reduction reactor unit. For example, in some embodiments, catalyst screen or filter can be used with catalytic reduction reactor unit associations.Such Catalyst screen and filter are familiar to those skilled in the art.Catalyst filter or screen cloth may include gauze or burning Knot metal or ceramic filter.Generally there is the solid (such as, for example, sharp sand) of 25% or lower porosity by volume Bed or other solid-filling bed can be configured as catalytic filter to separate slurry catalyst and liquid much filtrate.Configurable all As the external filter of cake filtration device (cake filter), wherein filter medium can be cloth, sintering metal, metallic sieve Or the grain bed of fabric, porous ceramicss, pressed felt or cotton-wool, supatex fabric, filter paper, polymeric film or granular solids.Use The filter of these filter mediums may include cake filtration device, horizontally or vertically leaf filter, filter press, leaf filter, Tubular filter, drum type filteration device, centrifugal discharge filter etc..Centrifuge, hydrocyclone and gravitation settler also can use In separation slurry catalyst and liquid phase and circulation slurry catalyst.Pump, screw rod or conveyer belt, for example, can be used for separation or rich The slurry catalyst of collection is transmitted back to catalytic reduction reactor unit.In other embodiment, catalytic reduction reactor unit The catalyst interrupter of inside can not be comprised, and slurry catalyst simply can be circulated when conversion systems for biomass works Return hydrothermal digestion unit.

In some embodiments, hydrothermal digestion unit can be, for example, the pressure of carbon steel, rustless steel or similar alloy holds Device.In some embodiments, there may be single hydrothermal digestion unit.In other embodiment, can be using parallel operation Two or more hydrothermal digestion units.Suitable hydrothermal digestion unit may include, for example, " PANDIATM Digester " (Voest-Alpine Industrienlagenbau GmbH, Linz, Austria), " DEFIBRATOR Digester " (Sunds Defibrator AB Corporation, Stockholm, Sweden), M＆D (Messing ＆Durkee) Digester (Bauer Brothers Company, Springfield, Ohio, USA) and KAMYR Digester (Andritz Inc., Glens Falls, New York, USA).The suitable constructions of hydrothermal digestion unit may include, for example, trickle bed, heap formula (pile-type), fluid bed contacts (stirred contact) with stirring.Additionally, concurrent flow or counter-current flow may be present in Digestion unit.

In some embodiments, conversion systems for biomass may also include solid retraction mechanism, its operationally with hydro-thermal Digestion unit connects.Solid retraction mechanism can promote cellulose biomass solid to the introducing in digestion unit, and allows When adding other cellulose biomass solid, digestion unit is maintained at pressurized state.In multiple embodiments, solid draws Enter mechanism and may include pressure transition area, it circulates between lower pressure state and elevated pressures state.Implement in some other In mode, solid retraction mechanism may also include atmospheric pressure region.In some embodiments, solid retraction mechanism may include atmospheric pressure Area and the pressure transition area circulated between atmospheric pressure and higher pressure state.The selection whether comprising atmospheric pressure region will be by used Solid retraction mechanism position determining, as institute is discussed in detail herein below.In some embodiments, solid introduces Mechanism can be used for cellulose biomass solid becomes suitable for being introduced into the high pressure shape of pressurized thermal water digestion unit from low-pressure state State.In some embodiments, solid retraction mechanism can be used for by cellulose biomass solid from atmospheric pressure become suitable for for It is introduced into the high pressure conditions of hydrothermal digestion unit.

When it is present, suitable atmospheric pressure region may include, for example, ribbon conveyer, the tubular conveyor that shakes, screw feeder Or transporter, collecting tank, buffer, box allotter etc..Can work cellulose biomass solid with continuous or semi-continuous The suitable pressure transition area being added to pressurization digestion unit may include, for example, pressing screw feeder, pressures cycle room etc., As described in jointly owned U.S. Patent Application Publication 2013/0152457 and 2013/0152458.In some embodiments In, or even when the pressure of cellulose biomass solid is increased to the pressure of rising from atmospheric pressure, atmospheric pressure region also can optionally save Slightly.That is, in such embodiment, cellulose biomass solid can be added directly to pressure transition area and carry out pressure and follow Ring is to be introduced to the digestion unit that pressurizes.

In some embodiments, solid retraction mechanism can allow cellulose biomass solid to be introduced into hydrothermal digestion unit Without making digestion unit reduce pressure completely.Before introducing digestion unit, the pressurization of cellulose biomass solid can be allowed digestion list Unit keeps pressurization and operates continuously.This can help to maintain being thermally integrated in biomass digestion process and energy dose-effect as described above Rate.Before digestion, other benefits of cellulose biomass solid pressurization are also discussed below.

In some embodiments, the pressurization in the pressure transition area of solid retraction mechanism can be at least partially by by digestion list At least part of liquid phase in unit introduces pressure transition area to carry out.In some or other embodiment, pressure transition area adds Pressure can be carried out at least partially by introducing a gas in pressure transition area.

In some embodiments, liquid phase may include organic solvent, and it produces as the product of catalytic reduction reaction. In other embodiment, external solvent can be used for pressurizeing in pressure transition area.

Using the liquid phase from digestion unit, the pressurization of cellulose biomass solid be can achieve at least two benefits.First, In the presence of a liquid phase biomass solid pressurization can be made digestion solvent immersion biomass, this can make biomass and boil once introducing Solution unit is just immersed in digestion solvent.Additionally, by adding hydro-thermal phase to the biomass solid in pressure transition area, needing defeated Enter less energy and make biomass reach it to have just enter into temperature during digestion unit.These features all can improve the effect of digestion process Rate.

In some embodiments, slurry catalyst may include poisoning resistant catalyst.Using poisoning resistant catalyst can be Especially desirable, this is because before there is hydrothermal digestion and integrated catalytic reduction not by catalyst poison from cellulose raw Material solid removes.As used herein, " poisoning resistant catalyst " be defined as can anakmetomeres hydrogen but little at least 12 When continuous operation need not because low catalysis activity need regeneration or change catalyst.Can be avoided using poisoning resistant catalyst and be catalyzed Agent regeneration or the shortcoming changing the related process shutdown phase.In addition to the loss production time, when restarting hydrothermal digestion process Considerable energy expenditure may be needed.

In some embodiments, suitable poisoning resistant catalyst may include, for example, the catalyst of sulfuration.It is suitable for activation For example jointly owned U.S. Patent Application Publication 2012/0317872,2012/0317873 He of the catalyst of the sulfuration of molecular hydrogen Described in 2013/0109896.Sulfuration can be carried out in the following way：Use hydrogen sulfide treatment catalyst, simultaneously optionally by catalyst Deposition is on a solid support.In more specifically embodiment, poisoning resistant catalyst may include the cobalt-molybdenum hydrochlorate catalysis of sulfuration Agent.We have found that according to reaction condition, the cobalt-molybdenum phosphate catalyst of sulfuration can produce C₂-C₆Monohydric alcohol, glycol (include sweet Alcohol), triol and combinations thereof, an excess amount of C will not be formed simultaneously₂-C₄Alkane.As used herein, term " monohydric alcohol " refers to wrap Organic molecule containing single alcohol functional group.The monohydric alcohol being formed can via rapid evaporation or liquid-liquid phase separation easily with Water separates, and experiences condensation-oligomerization in a separate step in acid or base catalyst to produce in gasoline, aerial kerosene Liquid biofuel in gasoline or diesel range.Slurry catalyst containing Pt or Pd could be for outstanding in present embodiment For useful poisoning resistant catalyst.

In some embodiments, being suitable for poisoning resistant catalyst in methods described herein can sulfur in the following way Change：Slurry catalyst is dispersed in fluid phase, and is added to vulcanizing agent.Suitable vulcanizing agent may include, for example, organic Sulfoxide (for example, dimethyl sulfoxide), hydrogen sulfide, sulfhydrate salt (for example, NaSH) etc..In some embodiments, slurry catalysis Agent can be enriched in fluid phase after curing and be subsequently added to hydrothermal digestion unit.

In some embodiments, slurry catalyst can be reproducible.For example, in some embodiments, slurry is urged Agent can be regenerated by being exposed to the water that temperature is higher than its normal boiling point.As used herein, " Regenrable catalyzed " or even Still can recover its at least some by regeneration when being poisoned by nitrogen compound impurity, oxidation of sulfur compound impurities or any combination of them Catalysis activity.It is desirable that this Regenrable catalyzed should be regenerated with the minimal amount of process shutdown phase.In some embodiments In, slurry catalyst can be by being exposed to the water reuse (treatment that temperature is at least 200 DEG C.In some embodiments, slurry catalyst Can be by being exposed to the water reuse (treatment that temperature is at least 250 DEG C.In some embodiments, slurry catalyst can by temperature be to Few 300 DEG C of water reuse (treatment.In some embodiments, the water reuse (treatment that slurry catalyst can be at least 350 DEG C by temperature.One In a little embodiments, the water reuse (treatment that slurry catalyst can be at least 400 DEG C by temperature.Water for regeneration slurry catalyst can For subcritical state or supercriticality.Can be by being exposed to the specially suitable slurry that temperature is higher than the water reuse (treatment of its normal boiling point The ruthenium that material catalyst is arranged on solid carrier, such as, for example, ruthenium on the titanium dioxide or the ruthenium on carbon.Other conjunctions Suitable slurry catalyst may include arrangement platinum on a solid support or palladium compound.Most effective for mediation catalytic reduction reaction Catalyst also can regenerate at least partially by carrying out heat treatment with hydrogen.The regeneration of slurry catalyst can betide as needed Hydrothermal digestion unit, catalytic reduction reactor unit or other positions.

In some embodiments, slurry catalyst can work to produce molecular hydrogen.For example, in some embodiments, Can be using the catalyst (that is, APR catalyst) being suitable for aqueous phase reforming.Suitable APR catalyst may include, for example, with ruthenium, Molybdenum, stannum or other metal form alloy or the platiniferous with their modifications, palladium, ruthenium, the catalysis of nickel, cobalt or other group VIII metal Agent.Therefore, it may not be necessary to external hydrogen supplies in some embodiments as herein described.However, in other embodiment In, can be using the external hydrogen supply optionally combined with the internal hydrogen occurring.

In multiple embodiments, slurry catalyst can have 250 microns or less of particle diameter.In some embodiments In, slurry catalyst can have 100 microns or less of particle diameter.In some embodiments, 10 microns of slurry catalyst or more Little particle diameter.In some embodiments, the minimum grain size of slurry catalyst can be 1 micron.In some embodiments, herein Slurry catalyst in methods described may include catalyst fines.As used herein, term " catalyst fines " refers to nominally Particle diameter is 100 microns or less of solid catalyst.Catalyst fines can be produced by Catalyst Production technique, for example, in solid In catalyst extrusion.Catalyst fines also can be by the larger catalyst solid of grinding or in catalyst solid regenerative process Middle generation.The appropriate method producing catalyst fines is described in United States Patent (USP) 6,030,915 and 6,127,299.In some feelings In condition, catalyst fines can remove from solid catalyst production run, this is because they are difficult in some catalytic process Isolation.The technology removing catalyst fines from larger catalyst solid may include, and for example, sieves or similar particle diameter separation side Method.Due to catalyst need not be retained in fixed position in embodiment described herein, catalyst fines especially can be tolerated. Advantageously, because its size is little, catalyst fines can be easy to fluidize and are dispersed throughout cellulose biomass solids distribution.

In some embodiments, the catalysis reduction carrying out in hydrothermal digestion unit and catalytic reduction reactor unit is anti- Should be hydrogenolysis.Hydrogenolysis describe in detail and comprise hereinafter.

In some embodiments, fluid circulation loop can be configured to set up fluid stream upwards in hydrothermal digestion unit Dynamic.As used herein, term " flow of fluid upwards " refers to respect to biomass referred to herein as " counter-current flow " The product introducing the direction of digestion unit enters the direction of hydrothermal digestion unit.By making to comprise the fluid of slurry catalyst Flow up in cellulose biomass charging, slurry catalyst can become well distributed in entirety.Specifically, upwards Flow of fluid can to antigravity cause ground cellulose biomass charging compacting so that the distribution of slurry catalyst is more held Easily.Also can be using other flowing settings, such as, for example, concurrent flow.

In some embodiments, the hydrothermal digestion unit of conversion systems for biomass as herein described can comprise for by fibre The retention mechanism that dimension cellulosic biomass remains at.In some embodiments, the retention mechanism in hydrothermal digestion unit can work Make to retain particle diameter as 3mm or bigger cellulose biomass solid.That is, when there is retention mechanism, cellulose biomass is thin Grain and slurry catalyst freely can circulate in whole conversion systems for biomass, but larger cellulosic biomass particles can be protected Stay in hydrothermal digestion unit.Suitable retention mechanism may include, for example, screen cloth etc..

In some embodiments, there may be the product being in fluid communication with fluid circulation loop and take out pipeline, wherein This product is taken out pipeline and is located between hydrothermal digestion unit and the outlet of catalytic reduction reactor unit.In some embodiments In, there may be and take out, with product, the solid separating mechanism that pipeline is operably connected.Solid seperator in this position Structure can be used for being removed from solid before downstream is further converted to bio-fuel or other materials in product.? In some embodiments, product is taken out pipeline and can be operably connected with hydrothermal digestion unit.Operationally boil with hydro-thermal The product that solution unit connects is taken out pipeline and can be exported it as positioned at hydrothermal digestion unit and catalytic reduction reactor unit Between product take out the replacement of pipeline or supplement and exist.

The product being suitable for inclusion in conversion systems for biomass takes out the solid seperator in pipeline or other positions Structure can relate to any isolation technics known in the art, including, for example, filter, centrifugal force-or the seperator based on centrifugal force Structure (for example, hydrocyclone), subsider, centrifuge etc..Suitable filter may include, for example, surface filter and depth Filter.Surface filter may include, for example, filter paper, film, porosu solid medium etc..Deep filter may include, for example, if It is calculated as in the post of porous media of its cored structure IT solid or plug.In some embodiments, can be used two or more Plant filter, the wherein at least one in filter can be backwashed, and flow of fluid upwards continues through remaining filter simultaneously At least some of.In some embodiments, one or more hydrocyclones can be used.

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

Previously described conversion systems for biomass will be adopted now and examines accompanying drawing and further describe.Fig. 1 shows and follows in fluid There is in loop back path the illustrative biomass transformation system of the hydrothermal digestion unit being connected with each other and catalytic reduction reactor unit The schematic diagram of system, wherein hydrothermal digestion unit and catalytic reduction reactor unit all comprises slurry catalyst.Biomass transformation system System 1 comprises hydrothermal digestion unit 2, and the latter is in fluid communication via fluid circulation loop 10 with catalytic reduction reactor unit 4.As figure Shown, fluid circulation loop 10 is configured to set up flow of fluid upwards in hydrothermal digestion unit 2.With hydrothermal digestion unit 2 Other types of fluid communication also possible.The direction that biomass introduce hydrothermal digestion unit 2 is biological with wherein most The flow direction of matter is as the dotted line arrows.Optional hydrogen feeding line 8 is operationally connected with hydrothermal digestion unit 2.Optionally Hydrogen feeding line can also operationally be connected with catalytic reduction reactor unit 4, but do not draw for clarity.Catalyst Granule 9 and 9' can be respectively present in hydrothermal digestion unit 2 and catalytic reduction reactor unit 4.As painted in Fig. 1, fluid follows Loop back path 10 is configured to make fluid flow in an upward manner by catalytic reduction reactor unit 4.

Cellulose biomass solid can introduce hydrothermal digestion unit 2 by solid retraction mechanism 14, and described solid introduces machine Structure 14 includes atmospheric pressure region 15 and pressure transition area 16.Atmospheric pressure region 15 may include hopper, case etc. and can accommodate introducing water The structure of the cellulose biomass solid of hot digestion unit 2.Pressure transition area 16 may include to improve and is introduced into hydrothermal digestion Any structure of the pressure of the solid in unit 2.Pressure transition area 16 also can circulate between the pressure state of atmospheric pressure and rising. Optionally, solid retraction mechanism 14 can be omitted, and cellulose biomass solid can be directly appended to pressure transition area 16 to draw Enter in hydrothermal digestion unit 2.

Conversion systems for biomass 1 also comprises product and takes out pipeline 18, and it is in catalytic reduction reactor unit 4 outlet It is in fluid communication with fluid circulation loop 10 afterwards.In conversion systems for biomass 1 operating process, product can leave catalysis reduction Reactor unit 4 simultaneously flows by pipeline 20.Now, product subsequently can be taken out pipeline 18 by product and be followed from fluid Loop back path 10 removes or is recycled to hydrothermal digestion unit 2 by pipeline 22.The anti-of pipeline 18 removal is taken out by product Answer product subsequently can experience and be subsequently further converted to bio-fuel.The product that product is taken out in pipeline 18 can have By optional solid separating mechanism 24 by its detached solid.Suitable solid separating mechanism may include, for example, a kind of or many Plant filter, one or more hydrocyclone, centrifuge, film, subsider etc., as being discussed in further detail above.Warp Digestion solvent can be used for example as by the product that pipeline 22 returns to hydrothermal digestion unit 2 or experience is further converted to react Product.

Multiple other optional member may be present in conversion systems for biomass 1.Can be included in conversion systems for biomass 1 A kind of optional member is phase separation mechanism 26, and it is in fluid communication with pipeline 20.Further describe in following article, be separated Mechanism 26 can be used for will be at least partly separated from the water for the organic faciess of product.Other positions for phase separation mechanism 26 It is feasible.

Optional pipeline 30 can be used for shifting liquid phase from hydrothermal digestion unit 2.As painted in Fig. 1, pipeline 30 can be used for Shift liquid phase from hydrothermal digestion unit 2 with the pressure transition area 16 of at least part of solid retraction mechanism 14 of pressurizeing.For pipeline 30 Other constructions be also feasible.Can pressurize and introduce Pressed bio matter to hydrothermal digestion unit 2 before will be biological for cellulose Matter solid is supplied to pressure transition area 16 from atmospheric pressure region 15.By using pressure transition area 16, hydrothermal digestion unit 2 is in fiber Need not reduce pressure completely in cellulosic biomass solid adding procedure, so that digestion process is carried out in substantially unbroken mode.

In some embodiments, the method processing cellulose biomass solid may include：Comprise being capable of anakmetomeres Cellulose biomass solid is provided in the hydrothermal digestion unit of the slurry catalyst of hydrogen；In hydrothermal digestion list in the presence of molecular hydrogen Heating cellulose biomass solid in unit, makes slurry catalyst cycle through described hydrothermal digestion unit, thus being formed at simultaneously Liquid phase includes the hydrolyzate of soluble carbohydrate；When soluble carbohydrate is in hydrothermal digestion unit by solvable carbon Hydrate is at least partly converted into product；Transfer to the catalysis also comprising slurry catalyst with by least part of liquid phase also Former reactor unit, so that conversion soluble carbohydrate is product further.

In some embodiments, the method processing cellulose biomass solid may include：Conversion systems for biomass is provided, It includes：Comprise to be capable of the hydrothermal digestion unit of the slurry catalyst of anakmetomeres hydrogen, operationally connect with hydrothermal digestion unit The optional hydrogen feeding line connecing, and include hydrothermal digestion unit and the catalytic reduction reactor list also comprising slurry catalyst The fluid circulation loop of unit；In the presence of molecular hydrogen in hydrothermal digestion unit heating cellulose biomass solid, make slurry simultaneously Material catalyst cycles through described hydrothermal digestion unit, thus forming the hydrolysis product including soluble carbohydrate in the liquid phase Thing；When soluble carbohydrate is in hydrothermal digestion unit, soluble carbohydrate is at least partly converted into product； Transfer to catalytic reduction reactor unit with by least part of liquid phase, so that conversion soluble carbohydrate is that reaction is produced further Thing.

In some embodiments, before digestion, cellulose biomass can be washed and/or reduce size and (for example, lead to Cross chopping, broken, peeling etc.) to reach ideal dimensions and the amount for digestion.These operations can remove disturbs solvable carbon aquation The material of further chemical conversion of compound and/or improve the infiltration to biomass for the digestion solvent.In some embodiments, wash Wash and can betide in hydrothermal digestion unit before pressurization.In other embodiment, biomass can be placed in hydro-thermal by washing Occurred before in digestion unit.

Generally, the digestion in hydrothermal digestion unit can occur in the liquid phase.In some embodiments, liquid phase may include bag Include the digestion solvent of water.In some embodiments, liquid phase may also include organic solvent.In some embodiments, You Jirong Agent may include the oxidation intermediates being produced by the catalytic reduction reaction of soluble carbohydrate.For example, in some embodiments, Digestion solvent may include the oxidation intermediates being produced by hydrogenolysis or other catalytic reduction reaction of soluble carbohydrate.? In some embodiments, oxidation intermediates may include by situ catalytic reduction reaction and/or produced by catalytic reduction reactor unit Raw those.In some embodiments, bio-ethanol can be added in water with the oxidation intermediates comprising subsequently to produce Solvent is together as initial digestion solvent.Also miscible with water any other organic solvent can be used as needed as initial Digestion solvent.Generally, there may be the liquid phase of q.s in digestion process so that biological surface keeps moistening.The amount of liquid phase Can be further selected as keeping the soluble carbohydrate of enough high concentrations to keep preferably high in catalytic reduction process Response speed, but will not too high so that be degraded into problem.In some embodiments, the concentration of soluble carbohydrate can be protected Hold the 5wt% less than liquid phase so that degraded minimizes.However, it should be appreciated that in some embodiments can be using higher dense Degree.In some embodiments, organic acid such as acetic acid, oxalic acid, salicylic acid or aspirin can be included in conduct in liquid phase The sour accelerator of digestion process.

In some embodiments, digestion solvent may include the catalytic reduction reaction comprising to derive from soluble carbohydrate The organic solvent of oxidation intermediates.Catalytic reduction reaction can occur in hydrothermal digestion unit and/or catalytic reduction reactor unit In.In some embodiments, organic solvent may include at least one alcohol, ketone or polyhydric alcohol.In alternative embodiment, boil Solution solvent can at least partly be supplied by external source.For example, in some embodiments, bio-ethanol can be used for supplementing organic Solvent.Other organic solvents miscible with water also can use.In some embodiments, digestion solvent can be separated, stored Or provide with the soluble carbohydrate of holding ideal concentration or in hydrothermal digestion unit in Selective implantation hydrothermal digestion unit Temperature adjusting.

In multiple embodiments, digestion can occur within a period of time under the temperature and pressure raising.Real at some Apply in mode, digestion can carry out a period of time in 100 DEG C -240 DEG C of temperature.In some embodiments, time span can be Between 0.25 hour and 24 hours.In some embodiments, the digestion producing soluble carbohydrate can be in 1bar (absolute pressure Power) carry out under pressure between -100bar.Generally, temperature is higher, occurs the time quantum needed for hydrothermal digestion step shorter.Make For example, hydrothermal digestion 180 DEG C -270 DEG C, the temperature that is more typically in 190 DEG C -250 DEG C can carry out 1 hour -10 hours.

In multiple embodiments, suitable biomass digestion technology may include, for example, sour digestion, soda boiling solution, enzyme digestion With using hot pressurized water digestion.

In some embodiments, the method may also include at least part of product from conversion systems for biomass (example As from the outlet of catalytic reduction reactor unit or from fluid circulation loop) discharge.In some embodiments, the method also may be used It is converted into bio-fuel including by product, describe in further detail in following article.In some embodiments, the method May additionally include as described above by product from conversion systems for biomass discharge after from this product separation solid (example As, slurry catalyst, biomass particulate etc.).

In some embodiments, the method may also include and follows at least part of liquid phase from catalytic reduction reactor unit again Ring is to hydrothermal digestion unit.As described above, conversion systems for biomass as herein described is particularly advantageously can be by hydro-thermal Carrying out situ catalytic reduction reaction in digestion unit and promptly at least partly converting soluble carbohydrate is to comprise in oxidation The product of mesosome.Similarly, as described above, the liquid phase comprising product can be recycled to from catalytic reduction reactor unit Hydrothermal digestion unit, here liquid phase can, for example, contribute to regulating and controlling temperature therein, as digestion solvent etc..From catalysis reduction The recirculation of reactor unit to hydrothermal digestion unit can different recycle ratios occur.As used herein, term " recycle ratio " Refer to that the amount being recycled to the liquid phase of hydrothermal digestion unit (for example, in fluid circulation loop) converts with respect to from biomass The amount of the liquid that system (for example, taking out pipeline by product) is discharged.

The special benefit carrying out situ catalytic reduction reaction in hydrothermal digestion unit is to work as liquid phase to be recycled to hydro-thermal Process efficiency and yield can still be kept using relatively low recycle ratio during digestion simultaneously.Specifically, can be less need for from recirculation The digestion process heat supply that product occurs in hydrothermal digestion unit, because there occurs the catalysis reduction of heat release wherein instead Should.Therefore, the relatively a high proportion of liquid phase leaving catalytic reduction reactor unit can discharge from conversion systems for biomass so that Subsequent transformation is bio-fuel.Relatively low recycle ratio also allows for using less reactor volume because hydrothermal digestion unit and Total flow rate of liquid in catalytic reduction reactor reduces.High circulation can cause excessive pressure drop, high pump energy than with high flow rate of liquid Amount and size requirements and other unfavorable feature.The time of staying can not be made minimum before carrying out via catalytic reduction reaction stablizing Change and may result in compared with low-yield.Due to the benefit of the disclosure, those skilled in the art will can determine that the conjunction of the amount of being thermally integrated needed for realization The recycle ratio of suitable liquid phase recirculation, the ideal velocity that balance downstream bio-fuel produces simultaneously.In some embodiments, liquid Hydrothermal digestion unit is recycled to from catalytic reduction reactor unit with the recycle ratio of 0.2-10.In some embodiments, Liquid phase can be with 1-10, or 1-5, or 0.2-2, or 0.5-2, or 1-2, or 0.2-1, or the recycle ratio of 0.5-1 is anti-from catalysis reduction Device unit is answered to be recycled to hydrothermal digestion unit.In some embodiments, liquid phase can with 2 or lower recycle ratio from catalysis also Former reactor unit is recycled to hydrothermal digestion unit.In some embodiments, liquid phase can be with 1 or lower recycle ratio from urging Change reduction reactor unit and be recycled to hydrothermal digestion unit.In some embodiments, liquid phase can be from catalytic reduction reactor Unit is recycled to hydrothermal digestion unit, so that setting up flow of fluid upwards in hydrothermal digestion unit.In other reality Apply in mode, also can set up other types of flow in hydrothermal digestion unit, including such as concurrent flow.

In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can be at least 30bar's Occur under pressure.It is maintained at digestion at least under the pressure of 30bar and can ensure that digestion is carried out with satisfactory rate.In some embodiments In, in hydrothermal digestion unit, heating cellulose biomass solid can be carried out under at least pressure of 60bar.In some embodiment party In formula, in hydrothermal digestion unit, heating cellulose biomass solid can be carried out under at least pressure of 90bar.In some enforcements In mode, in hydrothermal digestion unit, heating cellulose biomass solid can be carried out under the pressure of 30bar-430bar.One In a little embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can enter under the pressure of 50bar-330bar OK.In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can be in the pressure of 70bar-130bar Carry out under power.In some embodiments, in hydrothermal digestion unit, heating cellulose biomass solid can be in 30bar- Carry out under the pressure of 130bar.It should be noted that pressure when aforementioned pressure refers to that digestion is carried out.That is, aforementioned pressure is hydrothermal digestion list The routine operating pressure of unit.

Due to the present invention conversion systems for biomass by carry out in hydrothermal digestion unit situ catalytic reduction reaction Lai There is provided stablizing of soluble carbohydrate, longer time of contact is more feasible, this is because the fall of soluble carbohydrate Solve less correlation.In some embodiments, time of contact can be 1 hour or more.In some embodiments, time of contact Can be 2 hours or more, or 4 hours or more, or 6 hours or more, or 8 hours or more, or 10 hours or more, or 12 Hour or more, or 24 hours or more.Especially, the time of 1 hour -24 hours can for batch processing, be used.

Generally, after the digestion in hydrothermal digestion unit occurs, only a small amount of initial fiber cellulosic biomass solid can keep Not by digestion.In some embodiments, after being to heat in hydrothermal digestion unit (for example, in second temperature and second Between), can be kept not by digestion based on the cellulose biomass solid less than 40% for the dry weight.In some embodiments, it is After heating in hydrothermal digestion unit, can be kept not by digestion less than 30% cellulose biomass solid based on dry weight.One In a little embodiments, after being heating in hydrothermal digestion unit, can less than 20% cellulose biomass solid based on dry weight Keep not by digestion.In some embodiments, after being heating in hydrothermal digestion unit, fine less than 10% based on dry weight Dimension cellulosic biomass solid can keep not by digestion.

In some embodiments, poisoning resistant slurry catalyst can be used for the method.Suitable poisoning resistant slurry catalyst Have been described above.In some embodiments, reproducible catalyst can be used for the method.In some embodiments, should Method may also include regeneration slurry catalyst.In some embodiments, the method may also include by being exposed to temperature at least For 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 of water reuse (treatment slurry catalyst.

In some embodiments, the method for the present invention may also include and carries out being separated of product.In some enforcements In mode, the phase separation mechanism being usable in existing after the outlet of catalytic reduction reactor unit that is separated is carried out.In multiple realities Apply in mode, separated enforcement may include double-deck (bilayer) and separates, implement solvent-stripping operation, implement extraction, implemented Filter, implements distillation etc..In some embodiments, azeotropic distillation can be carried out.

In some embodiments, methods described herein may also include and are converted into product is bio-fuel.At some In embodiment, product can start with can by produce from hydrothermal digestion from catalytic hydrogenolytic cleavage to the conversion of bio-fuel The molten carbohydrate-modifying product for comprising oxidation intermediates, as mentioned above.As further described above, comprise anti- The liquid phase answering product can be recycled to hydrothermal digestion unit to assist digestion process further.In some embodiments, instead Answer product can convert further by the further catalytic reforming reaction of any quantity, described further catalytic reforming reaction bag Include, for example, other catalytic reduction reaction (for example, hydrogenolysis, hydrogenation, hydrotreating reaction etc.), condensation reaction, different Structureization is reacted, desulphurization reaction, dehydration, oligomerization, alkylated reaction etc..Initial hydrogenolysis and further catalysis Reforming reaction is described below.

Multiple methods that carbohydrate is carried out with hydrogenolysis are known.A kind of suitable method is included carbohydrate Or stable hydroxy intermediate is being effectively formed in the middle of including oxidation with the hydrogen optionally being mixed with diluent gas and hydrogenolysis catalyst Contact under conditions of the product of body (such as, for example, compared with small molecule or polyhydric alcohol).As used herein, less point of term " Son or polyhydric alcohol " includes any molecule with lower molecular weight, and it may include more minority compared with initial carbohydrate Purpose carbon atom or oxygen atom.In some embodiments, product may include the relatively small molecule of such as polyhydric alcohol and alcohol.Hydrogen On the one hand solve this needs to destroy carbon-carbon bond.

In some embodiments, soluble carbohydrate can be using hydrogenolysis in the catalyst being capable of anakmetomeres hydrogen In the presence of be converted into metastable oxidation intermediates, such as, for example, propylene glycol, ethylene glycol and glycerol.Suitable catalyst can Including, for example, individually or with such as Au, Ag, Cr, Zn, Mn, Sn, Bi, B, O and their alloy or any combination of promotion Agent Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, Os together and their alloy or any group Close.In some embodiments, catalyst and accelerator can allow hydrogenation and hydrogenolysis concurrently or consecutively to occur, such as carbonyl Hydrogenation is to form alcohol.Catalyst may also comprise and comprises transition metal (for example, chromium, molybdenum, tungsten, rhenium, manganese, copper and cadmium) or group VIII The carbonaceous pyropolymer catalyst of metal (for example, ferrum, cobalt, nickel, platinum, palladium, rhodium, ruthenium, iridium and osmium).In some embodiments In, catalyst may include any of above metal combining or adhering to catalysis activity carrier with alkaline earth oxide.Some In embodiment, the catalyst described in hydrogenolysis may include catalyst carrier.

The condition carrying out hydrogenolysis can be according to such as biomass parent material and required product (such as gasoline or diesel oil) Type and change.Those skilled in the art will be appreciated that the suitable bar for carrying out this reaction based on the benefit of the disclosure Part.Generally, hydrogenolysis can be carried out in 110 DEG C -300 DEG C of temperature, preferably 170 DEG C -300 DEG C, most preferably 180 DEG C -290 DEG C.

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

In hydrogenolysis, hydrogen used may include external hydrogen, recycle hydrogen, generated in-situ hydrogen or any combination of them.

In some embodiments, the product of hydrogenolysis may include more than 25mol%, or alternatively, is more than The polyhydric alcohol of 30mol%, this may result in and is more converted into bio-fuel in subsequent treatment reaction.

In some embodiments, hydrogenolysis can be carried out under neutrality or acid condition, because in addition to hydrogenolysis also Need to promote hydrolysis.For example, the hydrolysis of oligomeric carbohydrate can combine generation sugar alcohol with hydrogenation, and the latter can experience hydrogen Solution.

The second aspect of hydrogenolysis needs to destroy-OH key, such as：RC(H)₂-OH+H₂→RCH₃+H₂O.This reaction is also designated as " hydrogenation deoxidation ", and can occur parallel with the hydrogenolysis of C-C key destruction.Glycol can be converted into single oxygen-containing chemical combination via this reaction Thing.The order of severity due to reacting is raised with temperature or is increased with catalyst contact time and increase, and polyhydric alcohol is relative with glycol Concentration in single oxygenatedchemicalss can reduce because of hydrogenation deoxidation.The selectivity that C-C key hydrogenolysis contrasts C-OH key hydrogenolysis will be with urging Agent type and formula and become.It can also happen that complete deoxidation is alkane, but if being intended that single oxygenatedchemicalss of generation or can Subsequent processing steps can be condensed or the glycol of the oligomeric compound for higher molecular weight and polyhydric alcohol, this is typically undesirable 's.General it will often be desirable to only single oxygenatedchemicalss or glycol are sent to subsequent processing steps, because higher polyol may be in contracting Excessive coke formation is led in conjunction or oligomerization process.On the contrary, alkane is substantially nonreactive, and can not easily combine generation The compound of higher molecular weight.

After forming oxidation intermediates upon hydrogenolysis, a part of product can be recycled to hydrothermal digestion Unit is for use as the digestion solvent being internally generated.Another part of product can be discharged and subsequently pass through to reform further instead Answer and process formation bio-fuel.After experiencing further reforming reaction, oxidation intermediates are optionally separated into different groups Point.Suitable separation may include, and for example, is separated, solvent stripper, extractor, filter, distillation etc..In some embodiment party In formula, lignin is separated with oxidation intermediates and subsequently processing product further or can be recycled to hydrothermal digestion list Carry out before unit.

Oxidation intermediates can be processed in one or more process in reaction to produce fuel mixture.In some enforcements In mode, condensation reaction can be used together with other reactions to generate fuel mixture, and can by includes sour, alkali or the two Catalyst.Generally, it is not only restricted to any particular theory it is believed that alkaline condensation reaction can relate to a series of step： (1) optional dehydrogenation reaction；(2) optional dehydration, it can be acid catalyzed；(3) aldol reaction；(4) optional Assimilation is reacted；(5) optional furan nucleuss ring-opening reaction；(6) gained condensation product hydrogenation is formed>C4 hydrocarbon；(7) theirs is any Combination.Acid catalyzed condensation can be similarly limited optional hydrogenation or dehydrogenation reaction, dehydration and oligomerization.Also can be using extra Refining reaction so that product meets specific fuel standard, including the reaction carrying out in the presence of hydrogen and hydrogenation catalyst with from Final fuel Products remove functional group.In some embodiments, base catalyst, there is bronsted lowry acids and bases bronsted lowry functional site simultaneously urge Agent (optionally comprising metal function) can be used for realizing condensation reaction.

In some embodiments, aldol reaction can be used for generation and meets diesel fuel or aerial kerosene demanded fuel Fuel mixture.Traditional diesel fuel is enriched in the petroleum distillate of alkane.Their boiling point is wide to reach 187 DEG C -417 DEG C, it is suitable for burning, such as diesel-engine road vehicle in compression ignition engine.U.S. material and test association (ASTM) root According to boiling spread and with other fuel performances (such as Cetane number, cloud point, flash-point, viscosity, aniline point, sulfur content, aqueous Amount, dust burdening, copper strip corrosion and carbon residue) allowable range establish diesel fuel grades.Therefore, meet appointing of ASTM D975 What fuel mixture can be defined as diesel fuel.

The disclosure additionally provides the method preparing aerial kerosene fuel.Aerial kerosene fuel is transparent to festucine.? Common fuel is classified as the unleaded/paraffinic base oil fuel of Aeroplane A-1, and it produces to meet International standardization rule Lattice group.Aerial kerosene fuel is the mixture of a large amount of different hydrocarbons, may up to thousands of kinds or more.Its size (molecular weight or Carbon number) scope by product need limited, for example, freezing point or smoke point.Kerosene-type aircraft fuel (includes Jet A and Jet A- 1) there is the carbon number distribution between C8-C16.Long distillate or Petroleum-type aircraft fuel (including JetB) generally have Jie Carbon number distribution between C5-C15.The fuel mixture meeting ASTM D1655 may be defined as aerial kerosene fuel.

In some embodiments, two kinds of aircraft fuels (Jet A and Jet B) all comprise multiple additives.Available add Plus agent includes, but not limited to antioxidant, antistatic additive, corrosion inhibitor and fuel system icing suppression (FSII) agent.Antioxygen Agent prevents cementing, and is typically based on alkylating phenol, for example, AO-30, AO-31 or AO-37.Antistatic additive static dissipation is simultaneously Prevent sparking.The Stadis 450 having dinonylnaphthalene sulfonic acid (DINNSA) as active component is an example.Corrosion suppression Preparation (for example, DCI-4A) is used for civil and military fuel, and DC I-6A is used for military fuel.FSII agent includes, for example, Di- EGME.

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

In some embodiments, dehydrogenation is preferably used for the oxidation intermediates thing comprising alcohol, glycol and triol Stream.Generally, alcohol can not directly participate in aldol condensation.The oh group existing or multiple oh group can be converted into carbonyl (example As aldehyde, ketone etc.) to participate in aldol reaction.Dehydrogenation can be comprised to realize the de- of alcohol, glycol or the polyhydric alcohol of presence Hydrogen is to form ketone and aldehyde.Dehydration catalyst generally by for hydrogenating, the same metal of hydrogenolysis or aqueous phase reforming formed.These catalysis Agent describes in further detail above.Dehydrogenation yield can be carried by removing it when forming hydrogen during the course of the reaction or consuming High.Dehydrogenation step can be carried out as single reactions steps before aldol reaction, or dehydrogenation reaction can be with alcohol al Close reaction and work in coordination with mutually and carry out.For the dehydrogenation worked in coordination with mutually and aldol reaction, dehydrogenation and aldol condensation function can be in phases Occur with catalyst.For example, metal hydrogenation/dehydrogenation degree of functionality may be present in including on the catalyst of basic functionality.

Dehydrogenation reaction may result in generation carbonyl containing compound.Suitable carbonyl containing compound may include, but is not limited to, can shape Become ionic species or any compound of the inclusion carbonyl functional group that can react in the condensation reaction with ionic species.One In individual embodiment, carbonyl containing compound may include, but is not limited to, ketone, aldehyde, furfural, hydroxy carboxylic acid and carboxylic acid.Ketone can be without limiting System ground inclusion, hydroxy-ketone, cyclic ketones, diketone, acetone (acetone), acetone (propanone), 2-oxo-propanal, butanone, butyl- 2,3- Diketone, 3- hydroxyl butyl- 2- ketone, pentanone, Ketocyclopentane, amyl- 2,3- diketone, amyl- 2,4- diketone, hexanone, Ketohexamethylene, 2- methyl-ring Pentanone, heptanone, octanone, nonanone, decanone, undecyl ketone, ten diketone, methyl-glyoxal, diacetyl, pentanedione, diketone hexane, dihydroxy Benzylacetone and their isomer.Aldehyde can be without limit include, aldol, acetaldehyde, glyceraldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, Enanthaldehyde, octanal, aldehyde C-9, capraldehyde, the hendecanal, lauric aldehyde and their isomer.Carboxylic acid can be without including formic acid, second with limiting Acid, propanoic acid, butanoic acid, valeric acid, caproic acid, enanthic acid and their isomer and derivant, including hydroxylation derivative, such as 2- hydroxyl Butanoic acid and lactic acid.Furfural can be without including Hydroxymethylfurfural, 5- methylol -2 (5H)-furanone, dihydro -5- (hydroxyl first with limiting Base) -2 (3H)-furanones, tetrahydrochysene -2- furancarboxylic acid, dihydro -5- (methylol) -2 (3H)-furanone, tetrahydrofurfuryl alcohol, 1- (2- furan Base) ethanol, methylol tetrahydrofurfural and their isomer.In one embodiment, dehydrogenation reaction may result in generation to contain carbonyl Based compound, it is combined into a part for the oxidation intermediates being fed into condensation reaction with oxidation intermediates.

In one embodiment, acid catalyst can be used for optionally being dehydrated at least part of oxidation intermediates logistics.With Suitable acid catalyst in dehydration may include, but is not limited to, mineral acid (for example, HCl, H₂SO₄), solid acid is (for example, Zeolite, ion exchange resin) and hydrochlorate (for example, LaCl₃).Other acid catalysts can be without including with limiting, zeolite, carbonization Thing, nitride, zirconium oxide, aluminium oxide, silicon dioxide, aluminosilicate, phosphate, titanium dioxide, zinc oxide, vanadium oxide, oxidation Lanthanum, yittrium oxide, Scia, magnesium oxide, ceria, Barium monoxide, calcium oxide, hydroxide, heteropoly acid, mineral acid, acid are modified Resin, base modified resin and any combination of them.In some embodiments, dehydration catalyst also can comprise modifying agent.Close Suitable modifying agent may include, for example, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba and their any group Close.The hydrogenation/dehydrogenation that modifying agent is used especially for carrying out working in coordination with mutually with dehydration is reacted.In some embodiments, take off Water catalyst also can comprise metal.Suitable metal may include, for example, Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os and their alloy or any combinations.Dehydration catalyst can be self-supporting, It is supported on inert carrier or resin, or it can dissolve in the solution.

In some embodiments, dehydration can occur in vapor phase.In other embodiment, dehydration Can occur in the liquid phase.For liquid-phase dehydration reaction, aqueous solution can be used for being reacted.In one embodiment, eliminating water it Outer other solvents can be used for forming aqueous solution.For example, there may be water-miscible organic solvent.Suitable solvent may include, but not It is limited to, Hydroxymethylfurfural (HMF), dimethyl sulfoxide (DMSO), 1- methyl-n- ketopyrrolidine (NMP) and any combination of them. Other suitable aprotic solvent also can individually or with these solvent combinations any use.

In one embodiment, process reaction and may include optional assimilation reaction.Assimilation reaction can improve at least partly Ketone number in oxidation intermediates.For example, alcohol can be converted into ketone in assimilation reaction.Assimilation can exist in base catalyst Under carry out.Any base catalyst of the basic component as aldol reaction recited above can be used for carrying out assimilation anti- Should.Suitable reaction condition is well known by persons skilled in the art, and generally correspond to listed above with regard to aldol condensation The reaction condition of reaction.Assimilation reaction can be carried out as single reactions steps, or it can be assisted mutually with aldol reaction Carry out together.Alkaline functional site is comprised on aldol condensation catalyst and may result in collaborative assimilation and aldol reaction.

In some embodiments, process reaction and may include optional furan nucleuss ring-opening reaction.Furan nucleuss ring-opening reaction can Lead to any include furan nucleuss oxidation intermediates at least a portion be converted into more reactive in aldol reaction Compound.Furan nucleuss ring-opening reaction can be carried out in the presence of acidic.Acid as aldol reaction recited above Any acid catalyst of component can be used for carrying out furan nucleuss ring-opening reaction.Suitable reaction condition is known to those skilled in the art , and generally correspond to the reaction condition with regard to aldol reaction listed above.Furan nucleuss ring-opening reaction can be used as list Only reactions steps are carried out, or it can be worked in coordination with aldol reaction and carry out.Sour sense is comprised on aldol condensation catalyst Site may result in the furan nucleuss ring-opening reaction worked in coordination with mutually and aldol reaction.Such embodiment can be favourable, Because any furan nucleuss can be reacted in aldol reaction in open loop in the presence of acid functionality and using basic functionality.For For specified oxidation intermediates charging, such collaborative reaction scheme can allow to produce more substantial higher hydrocarbon to be formed.

In some embodiments,>The generation of C4 compound can be occurred by condensation, and described condensation may include urges in condensation The aldol condensation of the oxidation intermediates in the presence of agent.Alcohol aldehyde-condensation is usually directed to two kinds of compounds, and (wherein at least one can be wrapped Carbonyl group-containing groups) between carbon-to-carbon be coupled to form bigger organic molecule.For example, acetone can react shape with Hydroxymethylfurfural Become C9 species, the latter subsequently can react formation C15 species with another Hydroxymethylfurfural molecule.In multiple embodiments, reaction Carry out generally in the presence of condensation catalyst.Condensation reaction can be carried out in steam or liquid phase.In one embodiment, react Can occur in 5 DEG C -375 DEG C of temperature, this depends on the reactivity of carbonyl group.

Condensation catalyst usually can be by forming longer chain compound with new bonded two molecules of carbon-to-carbon Catalyst, such as base catalyst, have the multifunctional catalyst of bronsted lowry acids and bases bronsted lowry degree of functionality simultaneously, or also comprise optional metal official Any kind catalyst of energy degree.In some embodiments, multifunctional catalyst can be for having strong acid and highly basic sense simultaneously The catalyst of degree.In some embodiments, alcohol aldehyde catalyst may include Li, Na, K, Cs, B, Rb, Mg, Ca, Sr, Si, Ba, Al, Zn, Ce, La, Y, Sc, Y, Zr, Ti, brucite, zinc-aluminate, phosphate, the aluminosilicate zeolites of alkali process, alkalescence tree Fat, basic nitrogen compound and their alloy or any combinations.In some embodiments, base catalyst may also include Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Co, Ni, Si, Cu, Zn, Sn, Cd, Mg, P, Fe or the oxygen of any combination of them Compound.In some embodiments, condensation catalyst may include mixed oxide base catalyst.Suitable mixed oxidization alkaloids are urged Agent may include the combination of magnesium, zirconium and oxygen, and it can be without including with limiting：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 group Close.Constitute mixed oxide catalyst Mg/Zr or multiple other element the different atomic ratios of combination can be with 0.01-50's Scope uses.In some embodiments, condensation catalyst also can comprise metal or the alloy comprising various metals, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Bi, Pb, Os, its alloy or Combination.When dehydrogenation reaction and aldol reaction are worked in coordination with when carrying out, such metal can be preferred.In some embodiments In, preferred group ia material may include Li, Na, K, Cs and Rb.In some embodiments, it is preferred group iia material can Including Mg, Ca, Sr and Ba.In some embodiments, group iib material may include Zn and Cd.In some embodiments, IIIB race material may include Y and La.Basic resin may include the resin of display basic functionality.Base catalyst can be self-supporting , or on any carrier of being discussed further below of adhesion, including comprising carbon, silicon dioxide, aluminium oxide, oxidation Zirconium, titanium dioxide, vanadium oxide, ceria, nitride, boron nitride, heteropoly acid, the carrier of its alloys and mixts.

In one embodiment, condensation catalyst may originate from forming MgO and Al of hydrotalcite material₂O₃Combination.Another Plant ZnO and Al that preferred material comprises zinc aluminate spinel form₂O₃.Still another kind of preferred material is ZnO, Al₂O₃And CuO Combination.Another kind of metal functionality being provided by group viii b metal, such as Pd also can be provided in each in these materials Or Pt.When dehydrogenation reaction and aldol reaction are worked in coordination with when carrying out, such metal can be preferred.In some embodiments In, base catalyst can be for comprising Cu, Ni, Zn, V, Zr or the metal-oxide of their mixture.In other embodiment In, base catalyst can be the 23K-S metal comprising Pt, Pd, Cu, Ni or their mixture.

In some embodiments, the condensation reaction of base catalysiss can be using the condensation with acid and basic functionality Catalyst is carried out.Sour -ol aldehyde condensation catalyst may include brucite, zinc-aluminate, phosphate, Li, Na, K, Cs, B, Rb, Mg, Si, Ca, Sr, Ba, Al, Ce, La, Sc, Y, Zr, Ti, Zn, Cr or any combination of them.In further embodiment, Acid-bast-catalyst also can comprise one or more be selected from Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, The oxide of Ir, Ni, Si, Cu, Zn, Sn, Cd, P and combinations thereof.In some embodiments, Acid-bast-catalyst may include by Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, its alloy or combination The metal functionality providing.In some embodiments, catalyst may also include Zn, Cd or phosphate.In some embodiments In, condensation catalyst can be the metal-oxide comprising Pd, Pt, Cu or Ni, even more preferably comprises Mg and Cu, Pt, Pd or Ni Aluminate or zirconium metal-oxide.Acid-bast-catalyst also can comprise and any one of above-mentioned metal or multiple combination Hydroxyapatite (HAP).Acid-bast-catalyst can be self-supporting, or adheres to any being discussed further below Plant on carrier, including carbon containing, silicon dioxide, aluminium oxide, zirconium oxide, titanium dioxide, vanadium oxide, ceria, nitride, nitridation Boron, heteropoly acid, the carrier of its alloys and mixts.

In some embodiments, condensation catalyst also can comprise zeolite and comprise group ia compound (such as, Li, Na, K, Cs and Rb) the many porous carriers of other.Preferably, group ia material can be deposited less than the amount needed for neutralization support acidity property ?.Also metal function can be provided by adding group viii b metal or Cu, Ga, In, Zn or Sn.In one embodiment, Condensation catalyst may originate from forming MgO and Al of hydrotalcite material₂O₃Combination.Another kind of preferred material can comprise MgO and ZrO₂ Combination, or ZnO and Al₂O₃Combination.By copper or group viii b metal (such as, each of these materials also can comprise Ni, Pd, Pt or the combination of aforementioned substances) another kind of metal function that provides.

Condensation catalyst can be (that is, catalyst need not be used as another kind of material of carrier) of self-supporting, or can need It is suitable for independent carrier catalyst being suspended in reactant stream.A kind of exemplary carrier is silicon dioxide, especially logical That crosses sol-gel synthesis, precipitation or pyrolysismethod acquisition has high surface (more than 100m²/ g) silicon dioxide.In addition Embodiment in, particularly when condensation catalyst is powder, antigravity system may include binding agent to help catalyst It is configured to preferable catalyst shape.Applicable forming method may include extrusion, granulation, oil dripping or other known method.Oxidation Zinc, aluminium oxide and gelatinizing agent also can be mixed together and extrude to make moulding material.After drying, this material can be suitable Close to be formed and calcine at a temperature of catalysis activity phase.Also can be using other catalyst carrier well known by persons skilled in the art.

In some embodiments, when reaction condition overlaps each other to a certain extent, dehydration catalyst, catalysis dehydrogenation Agent and condensation catalyst may be present in same reactor.In these embodiments, dehydration and/or dehydrogenation reaction can be with Condensation reaction occurs substantially simultaneously.In some embodiments, catalyst may include being used in addition to for condensation reaction Dehydration and/or the avtive spot of dehydrogenation reaction.For example, catalyst may include independent site on a catalyst or work For alloy for dehydration and/or dehydrogenation reaction and condensation reaction active metal.Suitable active element may include Any species with regard to dehydration catalyst, in those of dehydrogenation and condensation catalyst listed above.Or, can use The physical mixture of dehydration, dehydrogenation and condensation catalyst.While not wishing to be bound by theory it is believed that using comprise metal and/or The condensation catalyst of acid functionality can help to promote the aldol reaction direction that balance limits to complete to develop.Advantageously, this Can be used for carrying out the multiple condensation reaction with intermediate dehydration and/or dehydrogenation, formed (via condensation, to be dehydrated and/or de- Hydrogen) higher molecular weight oligomer, as producing desired by aerial kerosene or diesel fuel.

Produce in condensation reaction is specific>C4 compound may depend on many factors, includes, but not limited to reactant The type of oxidation intermediates, condensation temp, the flow velocity of condensation pressure, the reactivity of catalyst and reactant stream in logistics.Logical Often, condensation reaction can be carried out at the thermodynamic (al) temperature being conducive to proposed reaction.For condensation phase liquid reactions, reaction The pressure of device can be enough to remain condensation liquid phase by least part of reactant at reactor inlet.For vapor-phase reaction, instead Should carry out at following temperature：At such a temperature, the vapour pressure of oxygenatedchemicalss is at least 0.1bar, and this temperature is beneficial to instead The thermodynamics answered.Condensation temp will depend upon that concrete oxidation intermediates used become, but anti-for occur in vapor phase Should, generally in the range of 75 DEG C -500 DEG C, more preferably in the range of 125 DEG C -450 DEG C.For liquid phase reactor, condensation temp can be Between 5 DEG C -475 DEG C, condensation pressure can be between 0.01bar-100bar.Preferably, condensation temp can 15 DEG C -300 DEG C it Between, or between 15 DEG C -250 DEG C.

Change and generally will be led to first-class factor>The concrete composition of C4 compound and the change of yield.For example, change reaction The temperature of device system and/or pressure or specific catalyst formulation, may result in generation>C4 alcohol and/or ketone rather than>C4 hydrocarbon.>C4 Hydrocarbon products also can comprise multiple various sizes of alkene and alkane (usually branched paraffin).Depending on used condensation catalysis Agent, hydrocarbon products also can comprise aromatic hydrocarbons and cyclic hydrocarbon compound.>C4 hydrocarbon products also can comprise undesirable high-level alkene, and it may Coking or deposition is led in internal combustion engine, or other undesirable hydrocarbon products.In this case, hydrocarbon be optionally hydrogenated with Ketone is reduced to alcohol and hydrocarbon, alcohol and alkene can be reduced to alkane simultaneously, thus formed that more preferably there is relatively low alkene, aromatic hydrocarbons Or the hydrocarbon products of alcohol level.

Condensation reaction can be carried out in the reactor of any suitable design, including continuous-flow-type, batch-type, semi-batch Formula or multisystem reactor, do not limit for design, size, geometry, flow velocity etc..Reactor assembly also can be using fluidisation Catalysis bed system, shake bed system, fixed bed system, mobile bed system or combinations of the above.In some embodiments, biphase (for example, liquid-liquid) and three-phase (for example, Gu liquid-liquid -) reactor can be used for carrying out condensation reaction.

In continuous flowing type system, reactor assembly may include optional dehydrogenation bed and (is applied to the oxidation producing dehydrogenation Intermediate), optional dehydration bed (being applied to the oxidation intermediates producing dehydration) and condensation bed (be applied to from oxidation intermediates product Raw>C4 compound).Dehydrogenation bed can be configured to receive reactant stream and produce required oxidation intermediates, and the latter can have and contains The raising of carbonyl compound amount.Dehydration bed can be configured to receive reactant stream and produce required oxidation intermediates.Condensation bed Can be configured to receive oxidation intermediates to contact with condensation catalyst and to produce required>C4 compound.For have one or The system of multiple refined (finishing) steps, can comprise another after condensation bed and be used for carrying out purification step or multiple The reaction bed of purification step.

In some embodiments, optional dehydration, optional dehydrogenation reaction, optional assimilation reaction, optional Ring-opening reaction and condensation catalyst bed can be disposed in same reactor vessel or be arranged in the list of fluid communication with each other Solely in reactor vessel.Each reactor vessel preferably may include be applied to removing product stream from reactor vessel Outlet.For the system with one or more purification step, refining reaction bed or multiple refined bed can together with condensation bed In same reactor vessel, or in the single reactor vessel being in fluid communication with the reactor vessel with condensation bed.

In some embodiments, reactor assembly may also include other outlets with allow to remove partial reaction thing logistics with Promote further or guiding reaction is moved towards required product and permission is collected and circular response by-product is for system Other parts in.In some embodiments, reactor assembly may also include other entrances with allow introduce supplementary material with Promote further or guiding reaction is moved towards required product and allowed circular response by-product in other reactions.

In some embodiments, reactor assembly may also include the unit allowing that reactant stream is separated into different component Part, it can find purposes or reaction needed for simply for promoting in differential responses scheme.For example, can be before condensation step Setting separator unit (such as phase separator, extractor, purifier or distillation column) removing water from reactant stream thus Condensation reaction is promoted to be beneficial to the generation of higher hydrocarbon.In some embodiments, separative element can be arranged to remove specific centre Body is to allow to produce the required product stream comprising the hydrocarbon in the range of specific carbon number, or as end-product or is used for other systems System or method.It is C that condensation reaction can produce carbon number₄-C₃₀Or more multiple compounds.Exemplary compounds may include, for example, >C4 alkane,>C4 alkene,>C5 cycloalkane,>C5 cycloolefins, aryl compound, thick aryl compound,>C4 alcohol,>C4 ketone and its mixed Compound.>C4 alkane and>C4 alkene can be (the i.e. C of 4-30 carbon atom₄-C₃₀Alkane and C₄-C₃₀Alkene), and can for side chain or The alkane of straight chain or alkene.>C4 alkane and>C4 alkene also can comprise C respectively₇-C₁₄、C₁₂-C₂₄Alkane and hydrocarbon fraction, wherein C₇-C₁₄Part refers to aerial kerosene fuel mixture, and C₁₂-C₂₄Part is related to diesel fuel blends and other is industrial On the way.Multiple>C4 alkane and>The example of C4 alkene can be without limit include, 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, nonyl Alkene, 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 they Isomer.

>C5 cycloalkane and>C5 cycloolefins can have 5-30 carbon atom, and can be unsubstituted, monosubstituted or polysubstituted 's.In the case of monosubstituted and polysubstitution compound, substituted radical may include side chain>C3 alkyl, straight chain>C1 alkyl, side chain> C3 alkylidene, straight chain>C1 alkylidene, straight chain>C2 alkylidene, aromatic yl group or combinations thereof.In one embodiment, extremely A few substituent group may include side chain C3-C12 alkyl, straight chain C 1-C12 alkyl, side chain C3-C12 alkylidene, straight chain C 1-C12 Asia Alkyl, straight chain C 2-C12 alkylidene, aromatic yl group or combinations thereof.In still other embodiment, at least one takes May include side chain C3-C4 alkyl, straight chain C 1-C4 alkyl, side chain C3-C4 alkylidene, straight chain C 1-C4 alkylidene, straight chain for group C2-C4 alkylidene, aromatic yl group or any combination of them.Preferably>C5 cycloalkane and>The example of C5 cycloolefins can be without limiting System ground includes, Pentamethylene., cyclopentenes, hexamethylene, cyclohexene, methyl cyclopentane, methyl cyclopentene, ethyl cyclopentane, ethyl ring Amylene, ethyl cyclohexane, ethyl-cyclohexene and their isomer.

Aromatic yl group comprises the armaticity alkyl of unsubstituted (as phenyl), monosubstituted or polysubstituted form.Monosubstituted and In the case of polysubstitution compound, substituent group may include side chain>C3 alkyl, straight chain>C1 alkyl, side chain>C3 alkylidene, straight chain> C2 alkylidene, phenyl group or combinations thereof.In some embodiments, at least one substituted radical may include side chain C3- C12 alkyl, straight chain C 1-C12 alkyl, side chain C3-C12 alkylidene, straight chain C 2-C12 alkylidene, phenyl group or theirs is any Combination.In still other embodiment, at least one substituted radical may include side chain C3-C4 alkyl, straight chain C 1-C4 alkane Base, side chain C3-C4 alkylidene, straight chain C 2-C4 alkylidene, phenyl group or any combination of them.Various aryl compounds Example can be without limit include, benzene,toluene,xylene (dimethyl benzene), ethylbenzene, p-xylene, meta-xylene, o- two Toluene and C9 aromatic hydrocarbons.

Fused-aryl compound may include bicyclo- and the polycyclic aromatic hydrocarbon of unsubstituted, monosubstituted or polysubstituted form.In list In the case of replacement and polysubstitution compound, substituted radical may include side chain>C3 alkyl, straight chain>C1 alkyl, side chain>C3 alkylene Base, straight chain>C2 alkylidene, phenyl group or combinations thereof.In other embodiment, at least one substituted radical can wrap Include side chain C3-C4 alkyl, straight chain C 1-C4 alkyl, side chain C3-C4 alkylidene, straight chain C 2-C4 alkylidene, phenyl group or they Any combinations.The example of multiple fused-aryl compounds can be without including with limiting, naphthalene, anthracene, tetrahydronaphthalene and decahydronaphthalenes, Dihydroindene, indenes and their isomer.

The midbarrel (moderate fractions) of such as C7-C14 separable for aerial kerosene fuel, and such as The heavier fraction of C12-C24 separable for diesel oil purposes.Fraction the heaviest can be used as lubricant or cracking is other to produce Gasoline and/or diesel oil distillate.>C4 compound is it is also seen that be used as industrial chemical, either as intermediate or conduct End-product.For example, aryl compound toluene, dimethylbenzene, ethylbenzene, xylol, meta-xylene and o-Dimethylbenzene can find to be used as Produce plastics and the chemical intermediate of other product.Meanwhile, C9 phenolic compound and fused-aryl compound (such as naphthalene, anthracene, Tetrahydronaphthalene and decahydronaphthalenes) can find as the solvent in industrial process.

In some embodiments, some components can be removed using other processes process fuel mixtures or make further Fuel mixture meets diesel oil or aerial kerosene fuel standard.Suitable technology may include hydrotreating to reduce fuel mixture In the amount of any remaining oxygen, sulfur or nitrogen or remove it.The condition of hydrocarbon stream hydrotreating is known to those skilled in the art 's.

In some embodiments, hydrogenation can substitute hydroprocessing processes or carry out after hydroprocessing processes so that At least some ethylene linkage saturation.In some embodiments, hydrogenation can be by including metal official on aldol condensation catalyst Can roll into a ball and work in coordination with aldol reaction and carry out.Such hydrogenation can be carried out so that fuel mixture meets specific fuel standard (for example, diesel fuel standard or aerial kerosene fuel standard).The hydrogenation of fuel mixture logistics can be carried out according to known procedure, Using continuous or batch processes.Hydrogenation can be used for removing remaining carbonyl group and/or oh group.In this situation In, can be using any hydrogenation catalyst as above.Generally, purification step can be carried out in 80 DEG C -250 DEG C of extraction temperature, And refined pressure can be between 5bar-150bar.In some embodiments, purification step can be entered in vapor phase or liquid phase OK, and when necessary using external hydrogen, recycle hydrogen or combinations thereof.

In some embodiments, isomerization can be used for processing fuel mixture with least some of to fuel mixture Component introduces the branched or other shapes selectivity of desirable degree.Useful was also had before contacted hydrocarbon with isomerization catalyst Remove any impurity.Isomerization steps may include optional stripping step, and the fuel mixture being wherein derived from oligomerization can lead to Cross to be purified with vapor or suitable gas (such as lighter hydrocarbons, nitrogen or hydrogen).Optional stripping step can be in a counter-current configuration in isomery Carry out in the unit (wherein gas and liquid contact with each other) changing catalyst upstream, or before actual isomerization reactor Single steam stripping unit using countercurrent action is carried out.

After optional stripping step, fuel mixture can be made to be passed through the reactivity including one or more catalyst beds Isomerization unit.The catalyst bed of isomerization unit can be operated in cocurrent or countercurrent mode.In isomerization unit, pressure can be Between 20bar-150bar change, preferably 20bar-100bar, temperature between 195 DEG C -500 DEG C, preferably 300 DEG C -400 ℃.In isomerization unit, any isomerization catalyst known in the art can be used.In some embodiments, suitably Isomerization catalyst can comprise molecular sieve and/or the metal from VII race and/or carrier.In some embodiments, isomery Change catalyst and can comprise SAPO-11 or SAPO41 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and A1₂O₃ Or SiO₂.Typical isomerization catalyst may include, for example, Pt/SAPO-11/Al₂O₃、Pt/ZSM-22/Al₂O₃、Pt/ZSM- 23/Al₂O₃And Pt/SAPO-11/SiO₂.

Other factorses, the such as concentration of water or unwanted oxidation intermediates are it is also possible to affect>The composition of C4 compound and Yield, and the activity of condensation catalyst and stability.In this case, the method may include in condensation reaction and/or appoints The dehydration of a part of water is removed before the dehydration of choosing, or for removing the separation list of unwanted oxidation intermediates Unit.For example, before separator unit, such as phase separator, extractor, purifier or distillation column may be disposed at condensation reactor To remove a part of water from the reactant stream comprising oxidation intermediates.Separative element also can be installed as removing specific oxidation Intermediate allowing to produce the required product stream comprising the hydrocarbon in the range of particular carbon, or as end-product or for other systems Or method.

Therefore, in some embodiments, the fuel mixture being produced by methods described herein can be for meeting aviation coal The hydrocarbon mixture (for example, meeting ASTM D1655) that oil fuel requires.In other embodiment, the product of methods described herein Thing can for comprise to meet the fuel mixture of diesel fuel requirement hydrocarbon mixture (for example, meeting ASTM D975).

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

In still other embodiment,>C2 alkene can be by existing oxidation intermediates in the presence of a dehydration catalyst Carry out catalytic reaction under dehydration temperaturre and dewatering pressure and prepare, comprised with producing>The reaction stream of C2 alkene.>C2 alkene can Including the straight or branched hydrocarbon comprising one or more carbon-to-carbon double bonds.Generally,>C2 alkene can comprise 2-8 carbon atom, more excellent Select 3-5 carbon atom.In some embodiments, alkene may include propylene, butylene, amylene, the isomer of aforementioned substances and front State any two or more kinds of mixture in material.In other embodiment,>C2 alkene may include by will at least portion Point>C2 alkene carries out catalytic reaction through olefin isomerization catalyst and produces>C4 alkene.

Dehydration catalyst may include selected from acidic alumina, aluminum phosphate, silica-aluminophosphates (alumina Phosphate), amorphous silica-alumina, aluminosilicate, zirconium oxide, sulfated zirconia, tungstated zirco, carbon Change tungsten, molybdenum carbide, titanium dioxide, sulphation carbon, phosphorylation carbon, phosphated silica, phosphated alumina, acidic resins, Any two or more kinds of combinations in heteropoly acid, mineral acid and aforementioned substances.In some embodiments, dehydration catalyst is also May include in Ce, Y, Sc, La, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi and aforementioned substances any two or more The modifying agent of multiple combinations.In other embodiment, dehydration catalyst may also include element oxide, described element choosing 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 substances Middle any two or more kinds of combinations.In still other embodiment, dehydration catalyst may also include selected from Cu, Ag, Any two in Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, aforementioned substances Or in more kinds of alloys and aforementioned substances any two or more kinds of combinations metal.

In still other embodiment, dehydration catalyst may include aluminosilicate zeolites.In some embodiments, Dehydration catalyst may also include in Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned substances Any two or the modifying agent of more kinds of combinations.In some embodiments, dehydration catalyst may also include selected from Cu, Ag, Any two in Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, aforementioned substances Or in more kinds of alloys and aforementioned substances any two or more kinds of combinations metal.

In other embodiment, dehydration catalyst may include the aluminosilicate comprising difunctional five yuan of silica-rich zeolite rings Zeolite.In some embodiments, dehydration catalyst may also include selected from Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, The modifying agent of any two or more kinds of combinations in Ta, lanthanide series and aforementioned substances.In some embodiments, dehydration is urged Agent may also include selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, The gold of any two or more kinds of combinations in any two or more kinds of alloys and aforementioned substances in Sn, Os, aforementioned substances Belong to.

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

>C6 alkane can produce in the following way：Will>C2 alkene with>C4 isoparaffin logistics is in alkylation catalyst In the presence of under alkylation temperature and alkylation pressures catalytic reaction comprised with producing>The product stream of C6 alkane.>The different chain of C4 Alkane may include the alkane with 4-7 carbon atom and cycloalkane, such as iso-butane, isopentane, cycloalkane and to have tertiary carbon former In the higher homologue (for example, 2- methybutane and 2,4- dimethyl pentane) of son, the isomer of aforementioned substances and aforementioned substances Any two or more kinds of mixture.In some embodiments,>The logistics of C4 isoparaffin may include and is internally generated> C4 isoparaffin, outside>C4 isoparaffin, circulation>Any two or more kinds of combinations in C4 isoparaffin or aforementioned substances.

>C6 alkane can be branched-chain alkane, but also can comprise normal paraffin hydrocarbons.In one aspect,>C6 alkane may include Selected from side chain C6-10 alkane, side chain C6 alkane, side chain C7 alkane, side chain C8 alkane, side chain C9 alkane, side chain C10 alkane or front State the member of any two or more kinds of mixture in material.In one aspect,>C6 alkane may include, for example, dimethyl Butane, 2,2- dimethylbutane, 2,3- dimethylbutane, methylpentane, 2- methylpentane, 3- methylpentane, dimethyl pentane, 2,3- dimethyl pentane, 2,4- dimethyl pentane, methyl hexane, 2,3- dimethylhexane, 2,3,4- trimethylpentane, 2,2,4- In trimethylpentane, 2,2,3- trimethylpentane, 2,3,3- trimethylpentane, dimethylhexane or aforementioned substances any two or More kinds of mixture.

Alkylation catalyst may include selected from sulphuric acid, Fluohydric acid., aluminum chloride, boron trifluoride, solid phosphoric acid, chloride-oxidation Aluminum, acidic alumina, aluminum phosphate, silica-aluminophosphates, amorphous silica-alumina, aluminosilicate, aluminum silicate Salt zeolite, zirconium oxide, sulfated zirconia, tungstated zirco, tungsten carbide, molybdenum carbide, titanium dioxide, sulphation carbon, phosphoric acid Change carbon, phosphated silica, phosphated alumina, acidic resins, heteropoly acid, in mineral acid and aforementioned substances any two or The member of more kinds of combinations.Alkylation catalyst also can comprise mineral acid with Friedel-Crafts metal chloride (such as Aluminium bromide) and other proton donor mixture.

In some embodiments, alkylation catalyst may include aluminosilicate zeolites.In some embodiments, alkyl Change catalyst may also include appoints in Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, lanthanide series and aforementioned substances The modifying agent of what combination of two or more.In some embodiments, alkylation catalyst may also include selected from Cu, Ag, Any two in Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, aforementioned substances Or in more kinds of alloys and aforementioned substances any two or more kinds of combinations metal.

In some embodiments, alkylation catalyst may include the aluminosilicate comprising difunctional five yuan of silica-rich zeolite rings Zeolite.In some embodiments, alkylation catalyst may also include selected from Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Modifying agent in any two or more kinds of combinations in Ta, lanthanide series and aforementioned substances.In some embodiments, alkyl Change catalyst may also include selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, Any two or more kinds of combinations in any two or more kinds of alloys and aforementioned substances in W, Sn, Os, aforementioned substances Metal.In one aspect, dehydration catalyst and alkylation catalyst can be atom identical.

Alkylated reaction can carried out beneficial to thermodynamic (al) temperature.Generally, alkylation temperature can -20 DEG C to 300 DEG C it Between, alkylation pressures can be between 1bar (absolute pressure) -80bar.In some embodiments, alkylation temperature can be 100 Between DEG C -300 DEG C.On the other hand, alkylation temperature can be between 0 DEG C -100 DEG C.In still other embodiment, alkane Base temperature can be between 0 DEG C -50 DEG C.In still other embodiment, alkylation temperature can be between 70 DEG C -250 DEG C, alkane Base pressure can be between 5bar-80bar.In some embodiments, alkylation catalyst may include mineral acid or strong acid.? In other embodiment, alkylation catalyst may include zeolite, and alkylation temperature can be higher than 100 DEG C.

In some embodiments, olefin oligomerization can be carried out.Oligomerization can be in any suitable reactor configuration In carry out.Suitable construction may include, but is not limited to, and batch-type reactor, semi-batch reactor or flow reactor set Meter, such as, for example, has the fluidized-bed reactor of external regeneration vessels.Reactor design may include, but is not limited to pipe reaction Device, fixed bed reactors or any other type of reactor being appropriate to oligomerization.In some embodiments, for giving birth to The continuous oligomerization method producing the hydrocarbon of diesel oil and aerial kerosene fuel boiling range can be carried out using oligomerization reactor, wherein will comprise There is the olefin feed stream of short-chain olefin of 2-8 carbon atom chain length with zeolite catalyst at an elevated temperature and pressure The fuel mixture to be converted into this short-chain olefin in diesel boiling range for the contact.Oligomerization reactor can be in 20bar-100bar Relatively high pressure under operate, temperature between 150 DEG C -300 DEG C, between preferably 200 DEG C -250 DEG C.

The oligomer stream of gained results in the fuel mixture can with multi-products, and described product includes C5-C24 Hydrocarbon.Other process can be used for obtaining the fuel mixture meeting required standard.Initial process step can be used for generation to be had relatively The fuel mixture of narrow carbon number range.In some embodiments, the separation method such as way of distillation can be used for generation and is used for into one The fuel mixture of the inclusion C12-C24 hydrocarbon that step is processed.Remaining hydrocarbon can be used for generation be used for being recycled to oligomerization reactor or Fuel mixture for the gasoline in other methods.For example, kerosene distillate can be produced together with diesel oil distillate, and can be used as Illumination (illuminating) alkane, as routine is rough or aerial kerosene fuel in aerial kerosene fuel derived from synthesis Blending constituent, or as the reactant (especially C10-C13 fraction) in the method producing LAB (linear alkylbenzene (LAB)).Stone brain Oil distillate can be sent to heat cracker producing ethylene and propylene after hydrotreating, or is sent to cat cracker to produce Raw ethylene, propylene and gasoline.

Other method can be used for processing fuel mixture to remove some components or to make fuel mixture meet further Diesel oil or aerial kerosene fuel standard.It is any remaining in fuel mixture to remove that suitable technology may include hydrotreating Oxygen, sulfur or nitrogen.Hydrogenation can be carried out to make at least some ethylene linkage saturation after hydrotreating.Such hydrogenation can carry out so that Fuel mixture meets specific fuel standard (for example, diesel fuel standard or aerial kerosene fuel standard).Fuel mixture The step of hydrogenation of logistics can be carried out with continuous or batch mode according to program known in the art.

For contributing to more fully understanding the present invention, provide the example of following preferred embodiment.Following examples should be with Any mode is read as limiting or defining the scope of the present invention.

Embodiment

Unless hereinafter in addition shown, reaction is carried out in Parr 5000HASTELLOY multiple reactor unit, its bag Reactor containing 6x75mL, is operated in parallel at a temperature of the at most pressure of 135bar and at most 275 DEG C, is stirred with magnetic stirring bar Mix.Other research is carried out in 100mL Parr 4590 reactor, and with the mixing of drive-type shaft impeller, it also can Reach the pressure of 135bar and 275 DEG C of temperature.Liquid-phase chromatographic analysis are carried out by HPLC, using Bio-Rad Aminex HPX-87H post (300mmx7.8mm), flow velocity is 0.6mL/min, using 5mM sulfuric acid/water, 30 DEG C of case temperature.Run time is 70 points Clock.

Gas chromatographic analysiss are carried out using the 60mx0.32mm ID DB-5 post of 1 μ m thick, and split ratio is 50:1, helium flow speed For 2ml/min, 40 DEG C of post case temperature is run 8 minutes, then gradually rises to 285 DEG C with 10 DEG C/min, and retention time is 53.5 points Clock.Injector temperature is set to 250 DEG C, and detector temperature is set to 300 DEG C.

Embodiment 1：The paste of high-cellulose biomass solid carrying capacity is formed.11.3% will be comprised in cylinder with a scale The pine wood sawdust that the 2.08g of moisture is levigate is added in 25.5g deionized water.After mixing and allowing wood flour balance, with note Emitter removes 10.4g water from wood flour bed top.Subsequently cylinder is tilted to be decanted off extra water, but only removal 1g is extra Water, has obtained final water:Dry solid is than for 8.3:1.Add the slurry catalyst that 0.1g particle diameter is 1-25 micron, and by falling Cylinder is mixed by revolution.Because levigate wood flour defines paste, it is practically without observing the mixed of slurry catalyst and wood flour Close.

Embodiment 2：The effect to digestion speed for the biomass particle diameter.Multiple Parr 5000 reactor in parallel is loaded into 20.0g 2- propanol/deionized water (50%), wherein comprises 0.05g sodium carbonate.2.70g is contained the cork Masson Pine of 39% moisture Piece is added in each reactor.In first reactor, add the wood chip of single 1 inch of x1 inch x3mm.At second In reactor, Masson Pine is become the small pieces of several 1/4 inch of x1/4 inch x3mm with handss strip off.In the 3rd reactor, by pine Wood is ground into full-size in coffee grinder and is nominally 3mm.

All three reactor all uses H₂It is pressurized to 51bar, be heated to 190 DEG C and keep 1 hour, be subsequently gradually increased to 240 DEG C to complete 5 hours periods.Reactor content passes through Whatman GF/F filter paper filtering, and the paper with solid is in 90 DEG C Vacuum drying oven is dried overnight.On the anhydrous basis, the wood in first reactor has dissolved 78wt%, and two other is anti- Answer the dissolving that the relatively spile in device has obtained 72wt%.Believe that the test error of these results is essentially identical, digestion speed base This is not affected by wood plate size.

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

Digestion unit is full of with 50% 2- propanol/deionized water from bottom, with 0.3wt% sodium carbonate buffering.Persistently add Plus digestion solvent, until the hole of wood chip bed is filled and just obtains the liquid level higher than 0.5 inch in bed.Molten in packed bed Agent is less than 5.8 with the ratio of dry timber:1.Subsequently terminate liquid flowing.Subsequently by digestion unit H₂It is pressurized to 70bar, in standard Under room temperature and atmospheric pressure (STP), continuous hydrogen stream is added and from top discharge from digestion unit bottom with the flow velocity of 95ml/min.This One flow velocity is equivalent to hydrogen stream and passes through digestion unit with the apparent linear speed of 0.05cm/ second.Bottom inlet is outside nominal size 3mm The pipe in footpath (2mm internal diameter), accordingly acts as the nozzle of bubble formation.

Subsequently digestion unit is heated to 190 DEG C and keeps 1.5 hours, be subsequently heated to 240 DEG C and keep 3.5 hours. In off-test, discharge 9.24g product liquid from digestion unit.Also from the 7.8g condensation with the hydrogen overflow collection that causes of injection Product liquid.Product liquid analysis shows based on carbohydrate quantity present in the charging of initial timber, with the expectancy theory The 82% of yield obtains oxidation product mixture (including monohydric alcohol and glycol).Do not have remaining timber solid at the end of the digestion phase Body.

Embodiment 4:Digestion cellulose biomass in the presence of top loading slurry catalyst.Repeat the test of embodiment 3, Difference is 0.600g catalyst is placed under wood flour bed top rather than wood flour bed.The initial ratio of solvent and dry timber Less than 5.5：1.After digestion, discharge 10.1g product liquid, and the liquid from overflow collection 7.28g condensation from digestion unit Product.Equally, there is no observable timber solid residue at the end of the digestion phase.It is loaded under wood flour bed with catalyst (it produces relatively high yield) is different, and catalyst is loaded in wood flour bed top and only creates the 28% of theoretical yield.Liquid produces The LC/MS analysis display of thing there may be the oligomeric side-products that molecular weight is more than 300, its molecular weight too high so that gas cannot be passed through Phase chromatograph detects.

Embodiment 5：Digestion cellulose biomass in the presence of bottom loaded formula slurry catalyst at low pressures.Use 6.05g Southern Pine wood chip and the test of 15.4mL digestion solvent repetition embodiment 3, add from bottom, until there be not wood chip completely Bed.In this case, with respect to being 32bar with the solvent vapour pressure estimated, digestion unit is only pressurized to 37bar.Discharge Hydrogen flow velocity is 97mL/min, and the digestion solvent of 50% 2- propanol/deionized water is from digestion unit bottom with 0.05mL/min's Flow velocity feeds jointly.Digestion unit is heated to 190 DEG C and keeps 1.5 hours, is subsequently heated to 240 DEG C and keeps 5 hours, and hydrogen It is maintained at same level with digestion solvent flow rate.In end of run, 18.53g product liquid is discharged from overflow, and 8.17g is from boiling Solution unit is discharged.Need 5.167g wood chip that digestion unit is refilled its previous level.This result is shown in digestion condition Under minimum there occurs 85% digestion.Gas chromatographic analysiss show that only 31% is converted into required product.This result and the ratio of embodiment 3 Relatively show that the hydrogen pressure of raising promotes stablizing of soluble carbohydrate in the way of more high yield.

Embodiment 6：Hydrogen stream digestion cellulose biomass is not used in the presence of bottom loaded formula slurry catalyst.With The initial press of 70bar hydrogen repeats the test of embodiment 5, but only keeps not making by the digestion solvent stream of cellulose biomass Use hydrogen stream.In end of run, discharge 17.45g product liquid from overflow, and discharged 7.4g liquid from digestion unit and produced Thing.Also have collected the timber of the non-digestion of 8ml after running, show 50% conversion ratio.Gas chromatographic analysiss are shown in liquid and produce There is the required product of 27% yield in thing.Meanwhile, when by terminating hydrogen flowing minimizing available hydrogen amount, there occurs poor Stable.

Embodiment 7：The digestion cellulose biomass when there is not slurry catalyst.Weight after adding 6.76g pine sheet The test of multiple embodiment 3, but do not include slurry catalyst.The digestion in 6.5 hours although all timber feed, GC analysis display Only define 3% required product.

Embodiment 8：Use air-flow and liquor stream digestion cellulose raw in room temperature in the presence of bottom loaded formula slurry catalyst Material.Add 5.29g Southern Pine wood chip, repeat the test of embodiment 3, but digestion unit is maintained at 23.5 DEG C during exposure. Discharge 7.597g product liquid in end of run from digestion unit.The wood chip bed analysis carrying out after removing product liquid Display catalyst is dispersed throughout the whole high uniformity dispersion of cellulose biomass bed, thus show air-flow and liquor stream can effectively by Slurry catalyst is distributed in cellulose biomass solid.

Embodiment 9：In room temperature only using liquor stream digestion cellulose biomass in the presence of bottom loaded formula slurry catalyst. Repeat the test of embodiment 8 with 7.13g pine sheet after again being filled, difference is not use flowing up of hydrogen, Only exist the flowing up of digestion solvent of 0.05mL/min.Discharge 1.36g product liquid from overflow, and obtain from digestion unit 10.67g product liquid.The analysis display catalyst of the wood chip bed carrying out after removing product liquid is distributed only over wood chip bed In bottom about 20%, do not find the catalyst being distributed on wood chip charging top.

Embodiment 10：Measure the minimum gas velocity making slurry catalyst fluidize.To load in cylinder with a scale for 100mL The NiMo/ alumina slurry catalyst of nominal 1-25 μm of 1g and 50g deionized water.Bubbling stone (fritted will be sintered Sparging stone) (ACE Glass) be placed in bottom of cylinder with a scale and with the N using 1/8- inch Teflon pipe₂Supply Connect.Change N₂Flow velocity makes slurry catalyst fluidize the lowest speed reaching needed for liquid column top completely to measure.Using this The gas linear speed corresponding to fluidisation completely that method measures is the 0.037cm/ second.When using in embodiment above, Hydrogen flow rate has exceeded this makes catalyst fluidization and the minimum speed suspending.

Therefore, the present invention be highly suitable for realizing being previously mentioned and wherein intrinsic target and advantage.Disclosed above Particular implementation is only illustrative, and the present invention can for having the those skilled in the art of the interests instructed herein not Same but equivalent mode is modified and is implemented.Additionally, except described in claims which follow, to structure illustrated herein or set The details of meter does not have any restriction.Therefore, provable specific illustrated embodiment disclosed above can change, combines or repair Change, and all such variations can be considered within the scope and spirit of.Property invention disclosed described herein can Implement in the case of there is not any element being not specifically disclosed herein and/or any optional member disclosed herein. Although compositionss and method be described as " inclusion ", "comprising" or " containing " multiple different components or step, compositionss and side Method also substantially can be made up of these components and step or is made up of them.All numerals disclosed above and scope can have necessarily Amount changes.No matter properly disclose the numerical range with lower limit and the upper limit, also the clearly open any number falling in the range of this Word and any comprise scope.Particularly, each numerical range disclosed herein (includes following form：" from a to b (a-b) ", or Equally, " from substantially a to b ", or equally, " from substantially a-b ") be interpreted as elaborating comprising in broader numerical every One numeral and scope.Meanwhile, unless be in addition expressly understood that definition by patentee, it is general that the term in claim has it All over general implication.And, when using in the claims, indefinite article " a or an (//a kind of /) " is at this By representing a kind of one or more/one or more rather than one/key element that it is introduced defined in literary composition.If in description Word or use and one or more patents cited herein of term or other file have any conflict, should using and this The consistent definition of description.

Claims

1. a kind of method, including：

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

Heat described cellulose biomass solid in the presence of molecular hydrogen in described hydrothermal digestion unit, make described slurry simultaneously Catalyst cycles through described hydrothermal digestion unit, thus forming the hydrolyzate comprising soluble carbohydrate in the liquid phase；

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

At least partly described liquid phase is transferred in the catalytic reduction reactor unit also comprising molecular hydrogen actived slurry catalyst, Wherein the slurry catalyst in hydrothermal digestion unit and catalytic reduction reactor unit has 250 microns or less of particle diameter；

Heat at least liquid phase to convert further in catalytic reduction reactor unit in the presence of molecular hydrogen and slurry catalyst Described soluble carbohydrate is described product；With

Via include the fluid circulation loop of hydrothermal digestion unit and catalytic reduction reactor unit by least a portion liquid phase from Catalytic reduction reactor unit is recycled to hydrothermal digestion unit, and wherein liquid phase is recycled to hydro-thermal with the recycle ratio of 0.2-10 and boils Solution unit.

2. method according to claim 1, also includes：

Convert further described soluble carbohydrate be described product after, will partly described product from described Catalytic reduction reactor unit is discharged, and wherein said discharge at least takes via with the product that fluid circulation loop is in fluid communication Go out pipeline to realize, described product is taken out pipeline and is located between hydrothermal digestion unit and the outlet of catalytic reduction reactor unit； With

Described product is converted into bio-fuel.

3. method according to claim 1, also includes：

Separate solid after discharge from described product, wherein said separation takes out pipeline using with described product The solid separating mechanism being operably connected is realized.

4. the method for claim 1, also includes：

Form described product further in described catalytic reduction reactor unit.

5. the method for claim 1, wherein hydrothermal digestion unit include flow of fluid upwards.

6. the method for claim 1, also includes：

The cellulose biomass solid that particle diameter is 3mm or bigger is retained in hydrothermal digestion unit；With

The cellulose biomass solid that particle diameter is less than 3mm is made to leave hydrothermal digestion unit.

7. the method for claim 1, wherein said slurry catalyst includes poisoning resistant catalyst.

8. the method for claim 1, wherein slurry catalyst can be again by being exposed to the water that temperature is at least 200 DEG C Raw.

9. the method for claim 1, wherein slurry catalyst can work to produce molecular hydrogen.

10. cellulose biomass solid is wherein provided and includes utilizing to hydrothermal digestion unit by the method for claim 1 The solid retraction mechanism being operably connected with described hydrothermal digestion unit, described solid retraction mechanism include atmospheric pressure region and The pressure transition area of circulation between atmospheric pressure and higher pressure state.