CN107109245A

CN107109245A - Method and system for processing of cellulose biomass

Info

Publication number: CN107109245A
Application number: CN201580071861.1A
Authority: CN
Inventors: J·B·鲍威尔; G·C·康姆普林; J·N·驰赫达
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2014-12-30
Filing date: 2015-12-29
Publication date: 2017-08-29
Also published as: EP3240867A1; AU2015374216A1; WO2016109477A1; BR112017014019A2; US20160186067A1

Abstract

The separation for clearing up product of cellulose biomass solid may be challenging because of the various components wherein contained.For processing of cellulose biomass, exactly, include providing the reaction product for being processed further (such as condensation reaction) into non-aqueous logistics the lignin so that the lignin at least partly precipitates and removed the precipitation for processing the method and system containing such as reaction product of the hydro-thermal reaction of phenolic compound lignin derivative products.

Description

Method and system for processing of cellulose biomass

The cross reference of related application

The power of U.S. Provisional Application No. 62/097756 in the application submitted this application claims on December 30th, 2014 Benefit.

Background technology

This section is intended to introduce various aspects that may be related to the exemplary embodiment of the present invention in this area.Believe that this is discussed Stating contributes to offer framework to more fully understand certain aspects of the present disclosure with facility.It is therefore to be understood that should be read with this angle This section, without being considered as any prior art of accreditation.

The disclosure relates generally to the processing of cellulose biomass solid, and more precisely, be related to can for processing With the method and system of the reaction product comprising lignin obtained by the hydro-thermal reaction of cellulose biomass.

A variety of commercially significant materials can be manufactured by the natural origin including biomass.Just For this point, cellulose biomass is particularly advantageous, because a large amount of carbon hydrates taken various forms found wherein Thing has diversity.As used herein, term " cellulose biomass " refers to the biomaterial or once of the work containing cellulose Through being biomaterial living.The lignocellulosic material found in the cell membrane of higher plant is carbon hydrate maximum in the world Thing is originated.The material generally manufactured by cellulose biomass can include for example clearing up obtained paper and slurrying wood via part Material, bio-fuel, including the bio-ethanol produced by fermenting.

Recently, the exploitation from the fossil fuel substitute of renewable resource causes concern.In this regard, fiber Cellulosic biomass especially merits attention, because its rich content and various composition wherein found has diversity, particularly fibre The plain and other carbohydrate of dimension.Although having very much prospect and causing strong interest, the exploitation of biologically based fuels technology and reality Apply and slowed down.So far, existing technology has been produced with low energy densities (such as bio-ethanol) and/or with showing Having engine design and the incomplete compatible fuel of transport infrastructure, (for example methanol, biodiesel, Fei Sheer-Top wish bavin Oily (Fischer-Tropsch diesel), hydrogen and methane).In addition, conventional biological based method has typically produced and has been in Dilute aqueous solution is (by weight>50% water) form intermediate, these intermediates are difficult to be processed further.Being specially required for will Cellulose biomass, which is processed into, constitutes coming with energy and cost-benefit method for the blending of fuel thing similar with fossil fuel Solve the above problems etc..

In addition, in addition to required carbohydrate, other materials are possibly also present in cellulose biomass, these materials can Can especially it be difficult to by being handled with energy and cost-benefit mode.For example, the phase is processed in cellulose biomass Between, a large amount of lignin being present in cellulose biomass may cause process equipment fouling, so as to cause cost high System down time.The cellulose biomass that lignin also results in per unit weight raw material changes into the conversion ratio of working substance It is relatively low.

Proved as described above, by cellulose biomass Efficient Conversion into blending of fuel thing and other materials be one complicated Problem, it is proposed that huge engineering challenge.The disclosure solves these problems and additionally provides related advantages.

The content of the invention

Various compounds are reclaimed because contained therein includes lignin from the product for the reaction for being related to cellulose biomass Various components inside and become challenging.Present disclose provides for processing of cellulose biomass, exactly, it is used for The method and system of the reaction product of the hydro-thermal reaction containing lignin and lignin derivative products is separated, wherein the reaction production Thing is various compounds and the mixture typically in more than a liquid phase.One phase of reaction product is typically water.Steam Although evaporate the reaction product with multiple liquid phases and containing water to obtain multi-products cut is feasible, but may cause product Malsegregation and steam stripping, in the case vapor heavier compound, such as phenols are brought into overhead fraction.Although passing through Distilled in elevated pressures with a temperature of, multiple phases is reduced or be minimized this problem that can solve, but higher pressure Power and temperature band are come the extra charge including equipment cost, and there have product that non-required degraded occurs at relatively high temperatures to be anti- The risk answered.Although the water in reaction product can be before being completely distilled off obtaining product frac by flashing removal, so Steam stripping may also be caused by doing, and thus cause the product separative efficiency in follow-up still-process low.

Therefore it provides a kind of method, methods described includes：

Heating cellulose biomass solid in reactor in the first reaction zone, molecular hydrogen, the catalyst for being catalyzed hydrogen and Solvent is cleared up to produce the first reaction product；

Before providing to Disengagement zone, optionally at least a portion of first reaction product is provided to gas separator In unit, the vapor fraction that normal boiling point is 100 DEG C or lower boiling compound is included to reclaim；Described first reaction is produced At least a portion of thing provides into the Disengagement zone including liquid-liquid phase separation unit or liquid-liquid extraction unit to reclaim aqueous materials Stream and non-aqueous logistics, wherein most of water in the part of the aqueous streams comprising first reaction product；

The aqueous streams are provided into aqueous streams Disengagement zone with by the lightweight at least a portion of the aqueous phase Compound is recovered in overhead fraction, wherein the part Plays boiling point of the overhead fraction comprising the aqueous streams is small In 150 DEG C of majority of compounds；

By a part for the vapor fraction, at least a portion of the aqueous phase overhead fraction and/or the distillate tower At least one of at least a portion of tops is provided to area is processed further, to provide higher hydrocarbon products；

Before providing to distillation unit, at least a portion of the higher hydrocarbon products is provided to the non-aqueous logistics In so that in the logistics lignin at least a portion precipitation, so as to provide slurry stream；And

At least a portion of the slurry stream is provided into distillation unit to reclaim distillate overhead fraction, distillate Midbarrel and distillate tower bottom distillate.

Therefore it provides a kind of method, methods described includes：

At least a portion, molecular hydrogen and the catalysis of first reaction product are heated in reactor in second reaction zone The catalyst of hydrogen is to produce the second reaction product；

Before providing to Disengagement zone, optionally by least one of first reaction product and second reaction product extremely A few part is provided to gas separator unit, and the steam that normal boiling point is 100 DEG C or more low-boiling compound is included to reclaim Cut；

At least a portion of second reaction product is provided to including liquid-liquid phase separation unit or liquid-liquid extraction list To reclaim aqueous streams and at least one non-aqueous logistics in the Disengagement zone of member, wherein the aqueous streams are anti-comprising described second Answer most of water in the part of product；

The aqueous streams are provided to aqueous streams Disengagement zone with by the lighting at least a portion of the aqueous phase Compound is recovered in overhead fraction, wherein the part Plays boiling point of the overhead fraction comprising the aqueous streams is less than 150 DEG C of majority of compounds；

Plant has primary cell wall and secondary cell wall.Primary cell wall contains three kinds of main polysaccharides (cellulose, pectin And hemicellulose) and one group of glycoprotein.Secondary cell wall is also containing the polysaccharide polymer lignin with hemicellulose covalent cross-linking. The complicated ingredient mixture existed jointly with cellulose can be difficult to cellulose, as discussed herein.Specifically, it is wooden Quality is probably especially reluctant composition.

The method and system provided in the disclosure at least makes wood in logistics by providing at least a portion of higher hydrocarbon products The part precipitation of quality solves foregoing problems.The lignin of precipitation can enter subsequent distillation unit in slurry form, Then separate, or can be separated at least partially in lignin deposit unit in distillation unit.

It is each to allow each phase each other to separate there is provided liquid-liquid extraction (or solvent extraction) in certain embodiments Independently it is processed further, or provides liquid-liquid phase separation to separate each phase.As used herein, liquid-liquid extraction refers to base In a kind of relative solubility of material in each phase, material is extracted into different liquid phases (for example from a liquid phase (such as aqueous phase) Nonaqueous phase) in.Therefore, liquid-liquid extraction can extract a certain amount of various compounds from aqueous phase.These compounds can include energy It is further processed into some light compounds of fuel product, and can includes the compound that normal boiling point is below about 150 DEG C, Including but not limited to monohydric alcohol (such as single oxygenate), aldehyde, ketone, acid and its any combinations.Liquid-liquid extraction solvent can be by described Various process-streams and product stream in method are provided.

Once separation, you can be flashed to aqueous phase, reduces steam stripping influence, because most of not miscible with water Compound, such as phenol and it is various oil all in nonaqueous phase so that the amount of compound not miscible with water is compared contained by this aqueous phase Reduce in the reaction product with multiple liquid phases.If after the liquid-liquid extraction, still suffering from enough lightings in aqueous phase Compound, then flash distillation aqueous phase can reclaim these light compounds.In order to improve product separation, nonaqueous phase can undergo viscosity drop Low reaction, including one or more lignin depolymerizations close reaction.

The distillation of nonaqueous phase containing less water can realize sufficient product separation at a lower temperature, wherein in distillation Do not go to need higher temperature similar to realize when the reaction product removed water or the reaction product flashed before it is distilled Efficient product separation.The nonaqueous phase of separation can undergo flash steps before being completely distilled off, and light compounds are included to reclaim Overhead fraction and tower bottom distillate if necessary.The remainder of the tower bottom distillate of nonaqueous phase can be provided to and be completely distilled off.

The product frac for being completely distilled off obtaining by nonaqueous phase can at least include the overhead fraction containing light compounds, containing wood The midbarrel (including phenols) of quality and lignin source property product and containing normal boiling point more than about 350 DEG C of heavy compounds Tower bottom distillate.It can be distilled and exceed a kind of midbarrel to provide.For example, distillation can be operated to provide standard boiling Point is about 150 DEG C to 250 DEG C of the first midbarrel and the second midbarrel with 200 DEG C to 350 DEG C of higher boiling point. Distillation can be operated to provide the midbarrel that normal boiling point is about 150 DEG C to 350 DEG C.

The light compounds reclaimed from aqueous phase and nonaqueous phase can optionally merge, to be further processed into can be used for fuel The higher hydrocarbon products of application.These higher hydrocarbons can be provided in the lignin stream of non-aqueous logistics or at least part depolymerization with Make at least a portion lignin deposit and optionally, liquid-liquid extraction can also be provided to for use as one of extractant Point.Higher hydrocarbon, which can optionally distill, obtains different fractions, to realize that optimal liquid-liquid extraction is separated.Such cut may be rich in Aromatic content (such as hydrocarbon-fraction rich in aromatic compound), or with relatively low aromatic content (less aromatic series Compound hydrocarbon-fraction) or other senior hydrocarbon-fractions for being obtained by distillation higher hydrocarbon products (such as condensation reaction products).

Exactly, the disclosure provides a kind of method, and methods described includes：Heated in reactor in the first reaction zone Cellulose biomass solid, molecular hydrogen, the catalyst for being capable of anakmetomeres hydrogen and clear up solvent to produce the first reaction product；

Before providing to Disengagement zone, optionally at least a portion of first reaction product is provided to gas separator In unit, the vapor fraction that normal boiling point is 100 DEG C or lower boiling compound is included to reclaim；Described first reaction is produced At least a portion of thing provides into the Disengagement zone including liquid-liquid phase separation unit or liquid-liquid extraction unit to reclaim aqueous materials Stream and non-aqueous logistics, wherein most of water in the part of the aqueous streams comprising first reaction product；Will The aqueous streams provide into aqueous streams Disengagement zone to reclaim the light compounds at least a portion of the aqueous phase In overhead fraction, wherein the part Plays boiling point of the overhead fraction comprising the aqueous streams is less than 150 DEG C Majority of compounds；By a part for the vapor fraction, at least a portion of the aqueous phase overhead fraction and/or described distillate At least one of at least a portion of thing overhead fraction is provided to area is processed further, to provide higher hydrocarbon products；There is provided To before distillation unit, at least a portion of the higher hydrocarbon products is provided into the non-aqueous logistics so that the logistics At least a portion precipitation of middle lignin, so as to provide slurry stream；And at least a portion of the slurry stream is provided Into distillation unit to reclaim distillate overhead fraction, distillate midbarrel and distillate tower bottom distillate.

In addition, the disclosure also provides another method, methods described includes：Heated in reactor in the first reaction zone Cellulose biomass solid, molecular hydrogen, the catalyst for being capable of anakmetomeres hydrogen and clear up solvent to produce the first reaction product； At least a portion of first reaction product, molecular hydrogen and being capable of anakmetomeres hydrogen are heated in reactor in second reaction zone Catalyst to produce the second reaction product；It is optionally that first reaction product and second is anti-before providing to Disengagement zone Answer at least a portion of at least one of product to provide to gas separator unit, with reclaim comprising normal boiling point be 100 DEG C or The vapor fraction of more low-boiling compound；At least a portion of second reaction product is provided to including liquid-liquid phase separation To reclaim aqueous streams and at least one non-aqueous logistics in the Disengagement zone of unit or liquid-liquid extraction unit, wherein described aqueous Most of water in the part of the logistics comprising second reaction product；The aqueous streams are provided to aqueous materials flow point From area so that the light compounds at least a portion of the aqueous phase are recovered in overhead fraction, wherein the overhead fraction bag The part Plays boiling point containing the aqueous streams is less than 150 DEG C of majority of compounds；By the one of the vapor fraction Partly, at least a portion of the aqueous phase overhead fraction and/or at least a portion of the distillate overhead fraction at least One kind is provided to area is processed further, to provide higher hydrocarbon products；Before providing to distillation unit, by the higher hydrocarbon products At least a portion provide into the non-aqueous logistics so that in the logistics lignin at least a portion precipitation, so as to carry For slurry stream；And at least a portion of the slurry stream is provided into distillation unit evaporated with reclaiming distillate tower top Point, distillate midbarrel and distillate tower bottom distillate.

In addition, the disclosure also provides a kind of system, the system includes：The first reaction zone comprising reactor, it is described anti- Answer device be arranged to heating cellulose biomass solid, molecular hydrogen, the catalyst for being capable of anakmetomeres hydrogen and clear up solvent with Form the first reaction product；Optional gas Disengagement zone, it includes separator unit, and the separator unit is with described the The import that one reaction zone is in fluid communication, wherein the gas separator unit is arranged to remove in first reaction product Normal boiling point is at least a portion of 100 DEG C or lower boiling volatile compound, wherein the gas separator unit First outlet and liquid-liquid phase separation unit or liquid-liquid extraction unit are in fluid communication with by the volatility chemical combination without the removal The reaction product of thing is provided into the liquid-liquid phase separation unit or liquid-liquid extraction unit and the light fraction point Second outlet from device unit is in fluid communication so that the volatile compound is provided to described with the unit that is processed further It is processed further unit；Disengagement zone, the Disengagement zone includes：Liquid-liquid phase separation unit or liquid-liquid extraction unit, its have with The communication of reactor is to receive the import of first reaction product described in first reaction zone, wherein described Liquid-liquid phase separation unit or liquid-liquid extraction unit are configured to provide for aqueous streams and non-aqueous logistics, wherein the aqueous phase Most of water in the part comprising first reaction product；For by the lightweight at least a portion of the aqueous phase Compound is recovered in the aqueous streams Disengagement zone in overhead fraction, wherein the overhead fraction is described comprising the aqueous streams Part Plays boiling point is less than 150 DEG C of majority of compounds, and the aqueous streams Disengagement zone has and the liquid-liquid phase separation The communication of unit or liquid-liquid extraction unit is to receive the import of the aqueous streams；The overhead fraction is with entering one Processing district is walked to be in fluid communication；Lignin deposit unit, the lignin deposit unit and the liquid-liquid phase separation unit or described The communication of liquid-liquid extraction unit with receive the non-aqueous logistics at least a portion and with it is described further plus The communication in work area is to receive at least a portion of the hydrocarbon products；And distillation unit, the distillation unit has Communication with the lignin deposit unit is to receive the import of lignin deposit unit outlet streams, wherein described Distillation unit is configured to provide at least overhead cut, middle distillate cut and the bottomsstream cut；And Area is processed further, it includes being processed further unit, and the unit that is processed further has and at least one following fluid company Logical import：(i) Disengagement zone, at least a portion to receive the overhead fraction from the distillation unit； (ii) the aqueous Disengagement zone, at least a portion to receive first overhead fraction from the aqueous Disengagement zone； And (iii) described gas separator unit, at least a portion of the volatile compound to receive the removal, wherein described It is processed further area and is configured to provide for higher hydrocarbon products.

In addition, the disclosure also provides a kind of system, the system includes：The first reaction zone comprising reactor, it is described anti- Answer device be arranged to heating cellulose biomass solid, molecular hydrogen, the catalyst for being capable of anakmetomeres hydrogen and clear up solvent with Form the first reaction product；Second reaction zone comprising reactor, the reactor described in first reaction zone with reacting The communication of device is to receive the first reaction product, wherein the reactor in the second reaction zone is arranged to heating The second reaction contents comprising the first reaction product, molecular hydrogen and the catalyst for being capable of anakmetomeres hydrogen are to form the second reaction Product；Optional gas Disengagement zone, it includes separator unit, the separator unit with first reaction zone and/ Or the import that the second reaction zone is in fluid communication, wherein the gas separator unit is arranged to remove described first And/or second reaction product Plays boiling point be 100 DEG C or lower boiling volatile compound at least a portion, wherein institute The first outlet of light fraction separator unit and liquid-liquid phase separation unit or liquid-liquid extraction unit is stated to be in fluid communication with will not The reaction product of volatile compound containing the removal is provided to the liquid-liquid phase separation unit or liquid-liquid extraction list The second outlet of first and described light fraction separator unit and it is processed further unit and is in fluid communication with by the volatility Compound provides to described and is processed further unit；Disengagement zone, the Disengagement zone includes：Liquid-liquid phase separation unit or liquid-liquid extraction Unit is taken, it has with the communication of reactor described in the second reaction zone to receive second reaction product Import, wherein the liquid-liquid phase separation unit or the liquid-liquid extraction unit are configured to provide for aqueous streams and non-aqueous Property logistics, wherein the aqueous phase comprising first reaction product the part in most of water；For by the aqueous phase At least a portion in light compounds be recovered in aqueous streams Disengagement zone in overhead fraction, wherein the overhead fraction bag The part Plays boiling point containing the aqueous streams is less than 150 DEG C of majority of compounds, the aqueous streams Disengagement zone With the communication with the liquid-liquid phase separation unit or liquid-liquid extraction unit to receive entering for the aqueous streams Mouthful；The overhead fraction is with being processed further area's fluid communication；Lignin deposit unit, the lignin deposit unit with it is described The communication of liquid-liquid phase separation unit or the liquid-liquid extraction unit is to receive at least the one of the non-aqueous logistics Part and with the communication for being processed further area to receive at least a portion of the hydrocarbon products；And distillation There is unit, the distillation unit communication with the lignin deposit unit to be gone out with receiving lignin deposit unit The import of mouth logistics, wherein the distillation unit is configured to provide at least overhead cut, middle distillate cut And the bottomsstream cut；And area is processed further, it includes being processed further unit, and the unit that is processed further has With the import of at least one following fluid communication：(i) Disengagement zone, to receive the tower top from the distillation unit At least a portion of cut；(ii) the aqueous Disengagement zone, to receive first tower top from the aqueous Disengagement zone At least a portion of cut；And (iii) described gas separator unit, to receive the volatile compound of the removal extremely A few part, wherein the area that is processed further is configured to provide for higher hydrocarbon products.

Again in another embodiment, processing district can comprise additionally in after-fractionating unit, the after-fractionating unit tool There is the communication with the other machining cell to receive the higher hydrocarbon products from the other machining cell At least a portion, wherein the distillation unit be configured to provide at least be rich in aromatic compound hydrocarbon-fraction, optionally The hydrocarbon-fraction of the less aromatic compound in ground and heavy distillat；The import of wherein described after-fractionating unit and lignin deposit unit It is in fluid communication to provide at least a portion rich in the cut of aromatic compound or the hydrocarbon-fraction of less aromatic compound.

Those skilled in the art after following examples explanation is read, by the feature of the embodiment provided the disclosure and Advantage is aobvious and is apparent from.

Brief description of the drawings

Including figures below to illustrate some aspects of the disclosure, and it should not serve to exclusive embodiment.Institute Disclosed theme can carry out significantly changing in form and function aspects, change, combine and equivalent substitution, and this will be this area skill Art personnel are thinkable and have the benefit of the disclosure.

Fig. 1 shows some aspects provided according to the disclosure, and one for processing of cellulose biomass is illustrative to implement The schematic diagram of example.

Fig. 2 shows some aspects provided according to the disclosure, another illustrative implementation for processing of cellulose biomass The schematic diagram of example.

Fig. 3 shows some aspects provided according to the disclosure, involved aqueous Disengagement zone in cellulose biomass processing An illustrative embodiment.

Embodiment

The disclosure is generally provided for cellulose biomass to be processed into fuel product, particularly for processing by hydro-thermal Clear up the method for the reaction product of cellulose biomass solid acquisition.Cellulose biomass is it is particularly advantageous that because wherein It was found that substantial amounts of various forms of carbohydrate there is diversity.As used herein, term " cellulose biomass " is The biomaterial of work of the finger containing cellulose was once biomaterial living.What is found in the cell membrane of higher plant is wooden Fibrous material is one of carbohydrate source maximum in the world.

Unless otherwise indicated, otherwise it will be appreciated that the term " biomass " used or " cellulose biomass " can be synonymous. Cellulose biomass can be any size, shape or form.Cellulose biomass can be in these solids sizes, shape or shape It is any naturally occurring in formula, or its can clear up advance row be processed further.Cellulose biomass can before hydrothermal digestion To be prescinded, be ground, be shredded, be crushed etc. to obtain desired size.Cellulose biomass can be washed before being cleared up (being washed such as with water, acid, alkali, its combination).

Any kind of suitable cellulose biomass source can be used.Example can be included by being adapted to cellulose biomass source Such as forestry defective material, agriculture defective material, herbaceous material, municipal solid wastes, waste paper and recyclable papers, paper pulp and paper mill residue, And its any combinations.Therefore, in certain embodiments, suitable cellulose biomass can include such as cornstalk, straw, sugarcane Slag, Chinese silvergrass, sorghum residue, switchgrass, bamboo, water hyacinth, hardwood, hardwood chip, hard wood pulp, cork, Softwood chips, cork Slurry, duckweed and its any combinations.Leaf, root, seed, handle, crust etc. may be used as the source of cellulose biomass.Cellulose raw The frequent origins of material can include such as agricultural residue (such as cornstalk, straw, seed shell, bagasse, shuck), timber (such as wood or bark, sawdust, waste wood, mill scrap), urban waste (such as waste paper, garden lop or chip) And energy crops (such as white poplar, willow, switchgrass, clover, herbage (prairie bluestream), corn and soybean).It is fine Tieing up cellulosic biomass can be based on such as cellulose and/or hemicellulose level, content of lignin, growth time/season, vegetatively Point/cost of transportation, growth cost, harvest cost etc. Consideration are selected.

When cellulose biomass changes into blending of fuel thing and other materials, cellulose and other complex carbon water therein Compound can be through extracting and being transformed into simpler organic molecule, and hereafter these organic molecules can be further processed into senior Hydrocarbon.Produced higher hydrocarbon can be used for forming transport fuel, such as synthetic gasoline, diesel oil and jet fuel, and industrial chemical. As used herein, term " higher hydrocarbon " refers to that carbon ratio is less than the hydrocarbon of at least one of the biomass material carbon ratio of component. Higher hydrocarbon mainly contains C4 to C30 hydrocarbon, further preferably C6 to C18 hydrocarbon.Higher hydrocarbon can contain aromatic compound and alkane. As used herein, term " hydrocarbon " refers to the main organic compound comprising hydrogen atom and carbon atom, and it is also unsubstituted hydrocarbon. In certain embodiments, hydrocarbon of the invention is also comprising hetero atom (that is, oxygen sulphur, phosphorus or nitrogen) and therefore, and term " hydrocarbon " can also be wrapped Include substituted hydrocarbon.

Clear up is that cellulose and other complex carbohydrates can be changed into a kind of mode of more useful form.Disappear Cellulose in cellulose biomass and other complex carbohydrates can be resolved into simpler soluble carbon by solution technique Hydrate, these carbohydrate are suitable for being processed further reacting and further changing by downstream.It is as used herein, Term " soluble-carbohydrate " refers to the monose or polysaccharide dissolved in technique is cleared up.It may reside in cellulose biomass Exemplary carbohydrate in solid includes such as sugar, sugar alcohol, cellulose, lignocellulosic, hemicellulose and its any group Close.

With with one kind there is energy and cost-benefit mode cellulose biomass is changed into blending of fuel using clearing up The problem of thing (bio-fuel) is related is not only very complicated, and these problems are totally different from paper and pulp wood industry often Clear up those problems run into technique.Because what cellulose biomass was cleared up in paper and pulp wood industry is intended that guarantor Hold solid matter (such as wood pulp), thus generally under low temperature (for example, less than about 200 DEG C) carry out not exclusively clear up one section it is extremely short The temporary time (such as between two hours to four hours).By contrast, it is suitable for cellulose biomass changing into fuel and mixes The technique of clearing up of compound and other materials is desirably configured to by dissolving initial fiber as much as possible in high flux mode Cellulosic biomass feeds to reach maximum yield.Paper and pulp wood clear up technique typically also before paper pulp is formed from crude fibre Biomass removes lignin.Although combining to form blending of fuel thing and other materials being used clears up technique and can equally clear up Preceding removal lignin, but these extra processing steps may influence the energy efficiency and cost of biomass conversion processes.In height The presence of lignin may especially be a problem during the cellulose biomass of conversion ratio is cleared up.

Manufactured via the conventional improvement of technique is cleared up to paper and pulp wood for blending of fuel thing and other materials Soluble-carbohydrate is considered as being not economically feasible due to many reasons.From the angle for the treatment of capacity, it is Manufacture more soluble-carbohydrates, the technique of clearing up of paper and pulp wood industry is simply performed in longer period of time is It is undesirable.Using as highly basic, strong acid or sulphite etc. clear up accelerator accelerate rate of slaking can be due to processing after Separating step and it may need to protect downstream component to increase process costs and complexity from these agents influences.Pass through increase Digestion condition accelerates the rate of slaking actually can be because soluble-carbohydrate is under higher digestion condition, particularly when long It is interior to occur thermal degradation and reduce the yield of bio-fuel.By clearing up after generation, soluble-carbohydrate is great anti- Answering property and can promptly degrade, to produce caramelan and other heavy end catabolites or accessory substance, especially compared with Under the conditions of high-temperature, such as it is more than about 150 DEG C.For the angle of energy efficiency, it can also be not intended to use higher digestion condition.This Any one in a little difficulties can defeat the economic feasibility of the blending of fuel thing from cellulose biomass.

A kind of particularly effective mode for the soluble-carbohydrate that can be formed is by hydrothermal digestion, and wherein The mode that soluble-carbohydrate can change into more stable compound is by carrying out one or more catalysis to it also Original reaction, this can include hydrogenation and/or hydrogenolysis.Make soluble carbon water by carrying out one or more catalytic reduction reactions Compound is stable will not allow the clearing up than with other possibility sides of cellulose biomass in the case of excessive sacrifice yield Occur at the high temperature of formula.Depending on reaction condition used and catalyst because to soluble-carbohydrate carry out one or Reaction product formed by multiple catalytic reduction reactions can include one or more alcohol functional groups, particularly including triol, two Alcohol, monohydric alcohol and its any combinations, some of them can also include remaining carbonyl functional group's (such as aldehydes or ketones).In alcohol component Compound can be described as oxygenatedchemicals, wherein these compounds include one or more oxygen-containing functional groups, such as hydroxyl Or carbonyl.The non-limiting examples of oxygenatedchemicals include aldehyde, ketone, alcohol, furans, ether or its any combinations.Such reaction product Than soluble-carbohydrate more thermal-stable, and reaction can be processed further by carrying out one or more downstreams, held Change places and be transformed into blending of fuel thing and other materials.In addition, the reaction product of aforementioned type is can to carry out hydro-thermal wherein to disappear The good solvent of solution, thus promotes the dissolving of the soluble-carbohydrate as its reaction product.

The hydrothermal digestion of cellulose biomass can be included in molecular hydrogen and be capable of the catalyst of anakmetomeres hydrogen (herein In may also be referred to as the catalyst of hydrogen " activation " or " catalyst of catalysis hydrogen ") in the presence of heating cellulose biomass and clear up molten Agent.In such method, the catalysis reduction of the hydrothermal digestion of cellulose biomass and the soluble-carbohydrate being generated by it It can be carried out in same container, this is properly termed as " situ catalytic reduction reaction method ".Therefore, it is suitable for cellulose biomass The technique of clearing up for changing into blending of fuel thing and other materials is preferably configured to by molten as much as possible in high flux mode Solution initial fiber cellulosic biomass feeds to reach maximum yield.For the angle of energy efficiency, situ catalytic reduction reaction method It is also that it is particularly advantageous that because the hydrothermal digestion of cellulose biomass is an endothermic process, and catalytic reduction reaction is heat release 's.Therefore, the waste heat produced by situ catalytic reduction reaction can be used for driving hydrothermal digestion, the probability for occurring heat transfer loss It is minimum, the amount of the additional thermal energy input needed for thus reduction is cleared up.

Typically, the hydro-thermal reaction of the cellulose biomass including hydrothermal digestion and catalysis reduction is produced containing a variety of The reaction product of component, scope is from the lighter compound such as such as alcohol component to including lignin and lignin-derived compounds (example Such as aldehydes matter) including heavier compound, and various compounds between the two.Depending on some conditions, such as temperature and Pressure, reaction product can also be present in more than one phase., will be some because reaction product is the mixture of compound Product needed for compound is further processed into will have challenge.For example, at least from the point of view of Viewpoint of Economics, in reaction product Some light compounds be further processed into needed for fuel Products can have challenge because simultaneous other middle boiling points Compound, such as lignin and lignin-derived compounds can be processed further selection by each component in limited reactions product.

Optionally, the first reaction product and/or the second reaction product can undergo base catalysis before Disengagement zone is entered Depolymerization reaction is to produce the reaction product of depolymerization.Base catalysis for lignin depolymerization can decompose lignin, to reclaim Phenols and other aromatic compounds.Nonrestrictive suitable base catalyst includes NaOH, KOH, Ca (OH) 2, Mg (OH) 2, consolidated Body base catalyst and its any combinations.

For example, process equipment fouling can be caused by being present in the lignin in reaction product, so as to cause cost High system down time.Reaction product is the mixture of various compounds and typically in more than one liquid phase.Reaction One phase of product is typically water.Although obtain multi-products cut be feasible to reaction product of the distillation containing water, but with containing The reaction product of less water is compared, and typically needs higher temperature and pressure.Additional energy needed for higher temperature and pressure can To be converted into extra cost.Although the water in reaction product can be before distillation obtains product frac by flashing removal, this Sample, which is done, can cause steam stripping, in the case, and vapor carries some phenol into overhead fraction.The removal of phenol during flashing It can make it that the separation of product in subsequent still-process is less efficient.

The method and system that the disclosure is provided at least makes non-aqueous logistics or at least by providing at least a portion higher hydrocarbon At least a portion lignin deposit in the lignin stream of part depolymerization solves foregoing problems.The lignin of precipitation can be in slurry Liquid form enters subsequent distillation unit, is then separated in distillation unit, or can be at least partially in lignin deposit list Separated in member.Lignin can pass through filtering, centrifugation, hydrocyclone, subsider (or gravitational settler), dual flash vessel (wherein in the presence of more than one flash vessel to evaporate the lignin in flash vessel, and one of another flash vessel is used for precipitation and separation Lignin) etc. separated.A kind of such lignin separation method is described in detail in co-pending U.S. Application No. 14/ In 485869.Have found, the lignin in the logistics is after addition higher hydrocarbon products, exactly rich in aromatic compound At least partly precipitated in the presence of the hydrocarbon stream of thing, thus promote to remove lignin to reduce equipment incrustation from the logistics.Although Be not wishing to be bound by theory, but think higher hydrocarbon products induce the characteristic of heavier molecular weight component precipitation may be attributed to its relative to The relatively low polarity of the biomass components of the stronger partial oxidation of polarity, compared with low-dielectric.

In one embodiment, can provide liquid-liquid phase separation allows each phase to separate each phase, thus independently of one another It is processed further.Reaction product can include aqueous phase and one or more nonaqueous phases, each mutually to be mixed each other in emulsion. The two kinds of logistics obtained by liquid liquid phase separation process include the non-aqueous logistics containing most of nonaqueous phase and containing most of water The aqueous streams of phase.Or, extractant can be provided into liquid-liquid extraction to separate each phase, thus make each phase can be with that This is independently processed further.Reaction product can include aqueous phase and one or more nonaqueous phases, each to be in each other mutually Emulsion is mixed.In liquid-liquid separation, extractant is added in reaction product, with the various compounds in aqueous phase extracted.By Two kinds of logistics that liquid-liquid extraction process is obtained include：(i) non-aqueous containing most of nonaqueous phase and most of extractant Stream, it contains the compound of extraction；And (ii) contains the aqueous streams of most of aqueous phase.Therefore, aqueous streams are produced comprising reaction Most of water present in thing, rather than aqueous streams include the water of tiny segment present in reaction product.Term " major part " Or its grammer equivalents refers to more than 50 weight %, including 55 weight % or bigger, 60 weight % or bigger, 70 weight % or Bigger, 75 weight % or bigger, 80 weight % or bigger, 85 weight % or bigger, 90 weight % or bigger and 95 weight % or It is bigger.Term " tiny segment " or its grammer equivalents are meant at most 50 weight %, are included in 0.1 weight % and at most 50 weight %, at most 45 weight %, at most 40 weight %, at most 35 weight %, at most 30 weight %, at most 25 weight %, extremely Amount in the range of many 20 weight %, at most 15 weight %, at most 10 weight % or at most 5 weight %.

Once separation, you can be flashed to aqueous streams, reduces steam stripping influence, can not be with water because most of Miscible compound (such as phenol) is all in non-aqueous logistics so that the amount of compound not miscible with water contained by this aqueous streams Reduce compared to the reaction product with multiple liquid phases.If after the liquid-liquid extraction, still suffered from aqueous streams enough Light compounds, then flash distillation aqueous streams can reclaim light compounds.As mentioned, light compounds can include Normal boiling point is below about 150 DEG C of compound, includes but is not limited to, monohydric alcohol, aldehyde, ketone, acid and its any combinations.Term is " light Matter ", " middle boiling point " and " heavy " or its grammatical variants refer to be based on normal boiling point, various chemical combination relative to each other Thing.

The selection of the contact mechanism of solvent, operating condition and solvent with reaction product allows the level for controlling compound extraction Or degree.Specifically, the amount for the extractant being added in reaction product be extracted into solvent phase from aqueous phase in compound Amount it is related.For example, compared to the situation for making larger amount of solvent be contacted with aqueous phase, such as per about 9 parts of solvents of a aqueous phase Mixture, in the reaction product and the mixture of extractant of the solvent containing relatively small amount, such as every about 1 part of 9 parts of aqueous phases In the mixture of solvent phase, the compound being extracted into solvent is less.That is, extraction degree is with liquid-liquid extraction process The increase of the amount of the middle extractant used and increase.Therefore, liquid-liquid extraction process can be configured to the big portion in aqueous phase extracted The compound divided, which reaches, may not be needed further to dispose aqueous phase to reclaim additional product (flash distillations as reclaimed light compounds) Degree.The addition of extractant can also promote each phase coalescence of reaction product by helping to destroy emulsion.

If using extractant, then at least a portion of extractant may come to be evaporated by being processed further steam Point at least a portion, at least a portion of at least a portion of non-aqueous logistics and/or distillate overhead fraction to be to enter one Walk and higher hydrocarbon products obtained from higher hydrocarbon products are provided in processing district.At least a portion of the higher hydrocarbon products can be provided Into liquid-liquid extraction unit, wherein extractant is in addition to for making lignin deposit, the portion also comprising higher hydrocarbon products Point.In another embodiment, at least a portion of the extractant may come from the midbarrel obtained by distillation unit At least a portion.In another embodiment, at least a portion of non-aqueous logistics can be flashed to reclaim comprising light The overhead fraction of matter compound and the tower bottom distillate comprising alkyl cyclohexanol, the Part I of the tower bottom distillate can provide to In liquid-liquid extraction unit.The Part II of the tower bottom distillate obtained by flash distillation can be provided into distillation unit.Obtained by flash distillation Overhead fraction such part Plays boiling point for containing non-aqueous logistics be less than 150 DEG C of majority of compounds, and by flashing Obtained tower bottom distillate contains the compound that normal boiling point is 150 DEG C or higher.

The reaction product of water is eliminated by flash distillation compared to the reaction product containing more water or before it is distilled, containing less The non-aqueous logistics of water can undergo flash distillation, and with the steam stripping effect reduced.Product frac from non-aqueous logistics The overhead fraction containing light compounds can at least be included, (including cyclic alcohol and phenol exist containing lignin and lignin derivative products It is interior) midbarrel and tower bottom distillate containing discarded object.Non-aqueous logistics can also be formed comprising a certain amount of by carbohydrate Longer glycol and single oxygen compound (such as with the compound more than C4), it can be recovered in midbarrel.It can enter Row distillation exceedes a kind of midbarrel to provide.For example, distillation can be operated to provide the mark with about 150 to 250 DEG C First midbarrel of quasi- boiling point and the second midbarrel with 200 to 350 DEG C of higher standard boiling point.Steaming can also be operated Evaporate to provide the midbarrel with about 150 to 350 DEG C of normal boiling point.

As known to persons of ordinary skill in the art, overlapping in the normal boiling point range of midbarrel is at least attributed to The distribution of compound during still-process.For example, it can be found that the lightweight of trace in midbarrel and/or tower bottom distillate Compound, and vice versa, it can be found that the heavy compounds of trace in overhead fraction and/or midbarrel.Equally, super Cross compound in a kind of midbarrel there will be it is overlapping, if it is present the overlapping of the normal boiling point of midbarrel can be caused.

Distilled for first time, in general, the first midbarrel is properly termed as phenols cut, because it often catches Normal boiling point is about the compound of the normal boiling point of phenolic compound.It will be appreciated that the first midbarrel can contain from the Compound of the other compounds and normal boiling point of two midbarrels outside about 150 to 250 DEG C as discussed above.It is similar Ground, the second midbarrel is properly termed as lignin oligomeric fraction, because it often catches normal boiling point about lignin The compound of the normal boiling point of oligomer.It will be appreciated that the second midbarrel can contain otherization from the first midbarrel The compound of compound and normal boiling point outside about 200 to 350 DEG C as discussed above.Midbarrel, either one kind evaporate Divide or more than a kind of cut, all containing the most of phenols being fed in the reaction product of still-process.

The light compounds for flowing back to receipts from aqueous streams and non-aqueous can optionally merge to be further processed into height Level hydrocarbon or fuel Products.The midbarrel for flowing back to receipts from non-aqueous can be recycled in this process.Midbarrel can be with Additionally comprise lignin oligomer.Optionally, to improve the product separation of non-aqueous logistics, non-aqueous logistics can undergo viscosity Reduction reaction, includes the reaction of one or more lignin depolymerizations.Therefore, the method and system described in the disclosure can be improved Yield simultaneously reduces cost, including makes to be reduced or dropped to most the need for processing reaction product using expensive high pressure distillation and separation It is low.

Term " distillation " has its general sense, refers to reclaiming one kind side of volatile compound based on normal boiling point Method.Distillation can divide a stage or multiple stages to carry out.One stage of single-stage distillation is properly termed as " flash distillation " or grammer equivalents, including " flash distillation (flash) " or " flash vessel (flasher) " (flashing).Flash distillation produces tower top and evaporated Divide and tower bottom distillate, and do not produce intermediate product cut typically.Multistage distillation produces various product fracs, including tower top evaporates Divide and tower bottom distillate and one or more midbarrels.It can be flashed or the mode of multistage distillation is the common skill in this area Known to art personnel.

Unless otherwise indicated, otherwise it will be appreciated that the various components mentioned in the disclosure, such as compound, product, mutually evaporating Point, part, logistics etc., refer to such component " at least a portion ", regardless of whether therewith include phrase " at least one Point "." hydrocarbon compound " in the reaction product of term second refers to the compound comprising hydrogen atom and carbon atom, and the compound is not With phenols functional group, phenols functional group is the hydroxyl (- OH) for being bonded to aromatic hydrocarbyl.Exemplary non-limiting hydrocarbonylation is closed Thing include being suitable for alkane, alkene, cycloalkane and its alkyl substituent in the fuel composition such as gasoline or diesel oil or Derivative, and cycloolefin and its alkyl substituent or derivative.For example, exemplary hydrocarbon compound can include but not limit In following any：Hexamethylene, cyclohexene, propyl group pentamethylene, propyl group cyclopentene, propyl cyclohexane, cyclohexyl alkene, benzene first Ether, propylbenzene, methyl-propyl benzene, and oxygen-containing hydrocarbon, such as cyclohexanone or methyl cyclohexanone.

Method and system described in the disclosure can realize lignin conversion, such as lignin conversion into phenols, with And the phenolic compound derived from lignin changes into hydrocarbon.As mentioned, the processing of cellulose biomass can include hydro-thermal Clear up cellulose biomass and carry out the catalytic reduction reaction of soluble-carbohydrate, be included in a reactor.This can To be realized via situ catalytic reduction reaction, situ catalytic reduction reaction is related in molecular hydrogen and is capable of urging for anakmetomeres hydrogen Heating cellulose biomass and solvent is cleared up in the presence of agent.Hydrothermal digestion and catalysis reduction can produce the first reaction product, First reaction product includes the phenolic compound for the lignin being derived from cellulose biomass and by derived from cellulose The alcohol component of the catalytic reduction reaction formation of the soluble-carbohydrate of biomass.

Term " alcohol component " refers to such a oxygenatedchemicals, wherein the oxygenate can be monohydric alcohol, glycol Or dihydric alcohol, triol or its any combinations.As used herein, term " glycol (glycol) " or dihydric alcohol (diol) contain finger There are two alcohol functional groups, two alcohol functional groups and a carbonyl functional group or its any combination of compound.It will be appreciated that alcohols group Dividing also includes the carboxyl with carbonyl functional group.As used herein, term " carbonyl functional group " is by Zhi Quan functional groups or ketone official Can group.In certain embodiments, glycol may be constructed a large portion of reaction product.Although glycol may be constructed reaction production A large portion of thing, it is to be understood that also likely to be present other alcohol, including such as triol and monohydric alcohol, and other contains The ketone equivalent of oxygen compound, as described alcohol.In addition, any of these alcohol can comprise additionally in carbonyl functional group.

As used herein, term " triol ", which will refer to, contains three alcohol functional groups, three alcohol functional groups and a carbonyl official Can group and its any combination of compound.As used herein, term " monohydric alcohol " will refer to containing alcohol functional group, an alcohol Functional group and one and carbonyl functional group and its any combination of compound.Term " phenolic compound " or " phenols " have its common Implication, generally refers to a class compound of the hydroxyl (- OH) containing bond to aromatic hydrocarbyl.Term " lignin oligomer " is Refer to more than one lignin monomer, two or more aromatic rings and molecular weight is at most 300,000 dalton A class compound.It will be appreciated that lignin is a kind of complicated three-dimensional amorphous polymer with the structure based on phenyl-propane. The molecular structure of lignin changes according to source (such as the type of plant), and is such complicated and rich change, so that Never completely described in its molecular structure.Therefore, lignin monomer and polymer can have various molecular structures.Generally Known lignin monomer is included to tonquinol, coniferyl alcohol and sinapinic alcohol.

Situ catalytic reduction reaction can be considered as the first hydro-thermal reaction step, and its generation is also referred to as clearing up product First reaction product.At least a portion of phenolic compound in first reaction product can be optionally by the second hydro-thermal reaction Step changes into hydrocarbon compound, wherein in molecular hydrogen and being capable of the reaction production of heating first in the presence of the catalyst of anakmetomeres hydrogen Thing.Reaction product from the second hydro-thermal reaction step is properly termed as the second reaction product.Unless otherwise indicated, otherwise term " reaction product " can refer to the first reaction product or the second reaction product.Optionally, at least some alcohol in the first reaction product Class component, such as glycol or triol, including carboxyl, monohydric alcohol can also be changed into the second hydro-thermal reaction step.

Unconverted phenolic compound, i.e., the phenolic compound for not yet changing into hydrocarbon (means still containing bond to fragrance The compound of the hydroxyl of race's alkyl), it can recycle or return in the first hydro-thermal reaction step and the second hydro-thermal reaction step At least one in.Phenols can serve as the part for clearing up solvent in the first hydro-thermal reaction step, and/or phenols can be Hydrocarbon is further converted into second hydro-thermal reaction step.If it has been found that using second with low phenolic compound concentration Hydro-thermal reaction step, then compared with the phenolic compound of high concentration, this is more preferably produced the yield of hydrocarbon by providing by phenols, high The amount of available water and other single oxygen compounds in the phenolic compound limited reactions of concentration.That is, relative to phenol generalization The higher situation of compound concentration, when the concentration of phenolic compound in the reaction contents of the second hydro-thermal reaction step is relatively low, wood Mediated conversion is more preferably.For example, the low phenolic compound concentration in the second hydro-thermal reaction step is with the second hydro-thermal reaction step Inclusion gross weight meter be at most 50 weight % concentration.Reaction contents in second hydro-thermal reaction step it is unrestricted Property exemplary phenolic compound concentration in terms of total weight of inclusions of the second hydro-thermal reaction step can about 0.1 weight % with extremely In the range of many 50 weight %, and can be any amount between the two, including at most 45 weight %, at most 40 weight %, At most 35 weight %, at most 30 weight %, at most 25 weight %, at most 20 weight %, at most 15 weight %, at most 10 weight % Or at most 5 weight %.It will be appreciated that mentioned any phenolic compound concentration amount between 0.1 weight % to 50 weight % Including at least 5 weight %, at least 10 weight %, at least 15 weight %, at least 20 weight %, at least 25 weight %, at least 30 weights Measure %, at least 35 weight %, at least 40 weight %, at least 45 weight % or at least 50 weight %.

If realizing conversion in the presence of water, then can improve lignin conversion, including lignin conversion into phenols and/ Or phenolic compound changes into hydrocarbon compound.That is, in terms of the weight of the inclusion of the second hydro-thermal reaction step 50% or Overall phenolic compound concentration in the second less hydro-thermal reaction step can be realized at least partially by water.For example, Water concentration in two hydro-thermal reaction steps can be at least 10 weights with the gross weight meter of the inclusion of the second hydro-thermal reaction step Measure %.The non-limiting exemplary water concentration of reaction contents in second hydro-thermal reaction step is with the second hydro-thermal reaction step Total weight of inclusions meter can be at least 10 weight %, at least 15 weight %, at least 20 weight %, at least 25 weight %, at least 30 weight %, at least 35 weight % or at least 40 weight %.It should be understood that being carried for the first or second hydro-thermal reaction inclusion And concentration be not limited to single liquid phase.All phases present in reactor out of the ordinary are taken in fact, the concentration provided corresponds to The concentration of the water of average value, in the reactor, it is observed that two or sometimes three or more than three liquid phases.Have and concern And the additional detail of the system and method for lignin conversion be found in that September in 2015 submits on the 29th entitled be used to process fiber The method and system (METHODS AND SYSTEMS FOR PROCESSING CELLULOSIC BIOMASS) of cellulosic biomass U.S. Application No. 14/868,426, the application requires the priority for the application number 62/058440 submitted on October 1st, 2014.

At least a portion of first and/or second reaction product can be provided to Disengagement zone, the Disengagement zone provides anti- The liquid-liquid extraction of product is answered to be reclaimed with each product mutually independent of each other.Optionally, before providing to Disengagement zone, it can remove anti- Answer the excessive gas in product.Liquid-liquid extraction uses extractant to extract various compounds to provide containing aqueous phase from aqueous phase The non-aqueous of remainder in aqueous streams and compound, solvent and reaction product containing extraction not in aqueous streams Stream.At least a portion for the extractant in liquid-liquid extraction comes from reaction product in itself, exactly, from higher hydrocarbon Product or its distillate cut.Can use reaction product can be assigned to it is any suitable in aqueous streams and non-aqueous logistics The liquid-liquid extraction method and system of conjunction.These methods can be by batch mode, half point batch mode, continuous mode or its any group Closing operation.

The equipment for the suitable type that can be used in liquid-liquid extraction includes classification-type extractor or differential extraction device.Classification One example of type extractor is blender-settler equipment, and the equipment typically comprises the mixing for being couple to sedimentation vessel Groove is to allow each phase coalescence.In general, blender-settler equipment can be used in batch mode, or multiple blenders-heavy Drop device equipment can be operated in continuously or semi-continuously schema hierarchy.Another classification-type extractor is centrifuge contactor.It is similarly suitable Different types of differential extraction device (also known as " continuously contacting extractor ") include but is not limited to, centrifuge contactor and contact Tower, such as plate column, spray tower, packed column, rotary-disk contactor and pulse-column.

Liquid-liquid extraction process can also relate to allow or promote the equipment of each phase coalescence, including horizontal subsider, one or Multiple fishgarths, centrifuge or hydraulic cyclone type device, fibre conglomerates pad or packed bed coalescer.

Leave liquid-liquid extraction aqueous streams (extract remainder can be referred to as again) inclusion depend on extraction level or Degree, scope is from low to high.It will be appreciated that extraction levels can be between low extreme value and high extreme value any value in the range of.Such as Fruit extraction levels are relatively low, then aqueous streams still can be included and water miscible compound to a certain degree, including lightweight Compound, intermediate boiling compounds and heavy compounds, and water soluble salt, ash content, tar and other discarded objects.Lightweight chemical combination Thing includes the compound that normal boiling point is less than 150 DEG C, including monohydric alcohol, aldehyde, ketone, acid and its any combinations.It may reside in water Intermediate boiling compounds in property logistics, such as normal boiling point is 150 to 350 DEG C of compound, including glycol and phenols.Heaviness Compound includes compound normal boiling point more than 350 DEG C.Light compounds and middle boiler can be reclaimed from aqueous streams Thing is used to further dispose, including light compounds are further processed into fuel Products and intermediate boiling compounds as solvent again Circulation.

In compound miscible with water of the liquid-liquid extraction typically in aqueous streams and non-aqueous logistics can not be with Obvious boundary is not provided between the miscible compound of water.The amount of the compound extracted from aqueous phase depends on ordinary skill people Member's various factors apparent easy to know, including extraction type and extractor device type, type of solvent and solvent ratio.

If extraction levels are of a relatively high, then aqueous streams may only include these compounds of trace, because this A little compounds are extracted from aqueous phase, and it leaves liquid-liquid extraction in non-aqueous logistics.Therefore, in such as distillation etc. The compound of extraction can be reclaimed in the subsequent disposal of non-aqueous logistics.In such situations, aqueous phase experience such as flashes product Recycling step may not be cost-effective.Therefore, aqueous phase can as discarded object various modes known to those of ordinary skill, Those modes including being referred in the disclosure are handled.

Non-aqueous logistics includes the tiny segment water in the reaction product in liquid-liquid extraction unit.Although non-aqueous logistics Still may contain some water, but be referred to as " non-aqueous " with by itself and the aqueous streams phase region containing generally more water Point.In addition to a small amount of water, because some light compounds are mutually mixed with non-aqueous, therefore non-aqueous logistics is also included in the middle of most and boiled Point compound and less amount of light compounds.After liquid-liquid extraction, non-aqueous logistics can be distilled and obtain various product fracs, Including the overhead fraction containing light compounds, containing intermediate boiling compounds (including cyclic alcohol, phenols and lignin oligomer) Midbarrel, and the tower bottom distillate containing the most heavy compound in reaction product, these most heavy compounds are often viewed as giving up Gurry or as utility fuel.Obtain exceeding a kind of midbarrel besides or furthermore, non-aqueous logistics can be distilled.

The light compounds for flowing back to receipts by distillation non-aqueous can be further processed into higher hydrocarbon products or fuel Products. Midbarrel can be recycled at least one in the first hydro-thermal reaction step and the second hydro-thermal reaction step.Citing comes Say, the solvent in the first hydro-thermal reaction step can be served as including the various compounds in the midbarrel including phenols.Or Or in addition, can be walked including the various compounds in the midbarrel including phenols and lignin oligomer in the second hydro-thermal reaction Further hydrotreating in rapid.For example, the phenols in midbarrel can change into hydrocarbon in the second hydro-thermal reaction step, And the lignin oligomer in midbarrel can be exactly further in the presence of water in the second hydro-thermal reaction step Change into phenols.It is not preferred although lignin oligomer can be provided into the first hydro-thermal reaction step.

As described, at least a portion of extractant can come from from being processed further reaction during liquid-liquid extraction Product or its cut and the product reclaimed.The recycling extractant of any suitable amount can be provided.In some cases, liquid- The amount of extractant used is the ratio of reaction product during liquid-liquid extraction in liquid extraction process.For example there is provided extraction Take solvent can be in the ratio in the range of than 9 parts reaction products of 1 part of solvent to than 1 part reaction product of 9 parts of solvents.It is unrestricted Property illustrate sex rate include than 9 parts reaction products (1 of 1 part of solvent:9), than 8 parts reaction products (1 of 1 part of solvent:8), 1 part of solvent ratio 7 parts of reaction products (1:7), than 6 parts reaction products (1 of 1 part of solvent:6), than 5 parts reaction products (1 of 1 part of solvent:5), 1 part of solvent Than 4 parts reaction products (1:4), than 3 parts reaction products (1 of 1 part of solvent:3), than 2 parts reaction products (1 of 1 part of solvent:2), 1 part it is molten Than 1 part reaction product (1 of agent:1), than 1 part reaction product (2 of 2 parts of solvents:1), than 1 part reaction product (3 of 3 parts of solvents:1), 4 parts Than 1 part reaction product (4 of solvent:1), than 1 part reaction product (5 of 5 parts of solvents:1), than 1 part reaction product (6 of 6 parts of solvents:1)、7 Part than 1 part reaction product (7 of solvent:1), than 1 part reaction product (8 of 8 parts of solvents:1), than 1 part reaction product (9 of 9 parts of solvents:1)、 Than 1 part reaction product (10 of 10 parts of solvents:, and its any combinations 1).

As described by, the phenols that solvent is served as in the first hydro-thermal reaction step can come from the production reclaimed from reaction product Thing.The recycling phenols of any suitable amount, the i.e. phenols from reaction product can be provided.There is provided in some cases The amount of the phenols of one hydro-thermal reaction step and the amount of lignin that provides thereto are into ratio.For example there is provided phenols can With in than 2 parts lignin (1 of at least 1 part phenols:2) ratio, is included in than 2 parts lignin (1 of 1 part of phenols:2) to 10 parts of phenols Than 1 part lignin (10:1) ratio in the range of, or both between any ratio.Non-limiting illustration sex rate is included at least Than 1 part lignin (1 of 1 part of phenols:1), than 1 part lignin (2 of 2 parts of phenols:1), than 1 part lignin of 3 parts of phenols, 4 parts of phenols compare 1 Part lignin (4:1), than 1 part lignin (5 of 5 parts of phenols:1), than 1 part lignin (6 of 6 parts of phenols:1), than 1 part wood of 7 parts of phenols Quality (7:1), than 1 part lignin (8 of 8 parts of phenols:1), than 1 part lignin (9 of 9 parts of phenols:1), than 1 part lignin of 10 parts of phenols (10:, and its any combinations 1).It will be appreciated that lignin is the component that is fed as biomass or via the technique containing lignin The recycling of logistics is provided.

If there is the second hydro-thermal reaction step, then the glycol reclaimed from reaction product, phenols can be provided thereto And/or lignin oligomer.The recycling phenols and/or lignin oligomer of any suitable amount can be provided, met with above The gross weight meter of the inclusion for the second hydro-thermal reaction step discussed at most 50 weight % low phenolic compound concentration.Term " recycling " refers to the compound reclaimed from reaction product.

Optionally, non-aqueous logistics can undergo one or more lignin depolymerization reactions before it is distilled, non-aqueous to reduce Property logistics viscosity, thus improve distillation during product frac separation.Any suitable lignin depolymerization reaction can make With.In general, HMW lignin oligomer is changed into lower molecular weight compound by lignin depolymerization reaction, such as lighter Lignin oligomer and/or lignin monomer, so as to reduce viscosity.The depolymerization of lignin provides lignin list in non-aqueous logistics Body, thus promotes phenolic compound with lignin oligomer and even more weighs the separation of compound.Lignin monomer can become Cutting agent (cutting agent) is to reduce the viscosity of HMW lignin oligomer.Distill what is obtained from non-aqueous logistics Midbarrel comprising phenols and/or lignin oligomer is steamed also to provide into lignin depolymerization reaction with further reduction The viscosity of the charging in unit is evaporated, thus promotes product separation.It should be understood that this step must may be directed to use with it is less Water, and it is optionally possible to carried out in the absence of under catalyst, so that through thus step, being effectively converted into lignin relatively low The smaller fragment of viscosity may need higher temperature (more than 300 DEG C).

Paragraphs below is provided on being provided for cellulose biomass to be processed into fuel Products, exactly, is used The additional detail of the method and system of the reaction product obtained in processing from the hydro-thermal reaction of cellulose biomass solid.As above Mentioned, the hydro-thermal reaction of cellulose biomass can include situ catalytic reduction, situ catalytic reduction be related in molecular hydrogen and Heating cellulose biomass and solvent can be cleared up in the presence of the catalyst of anakmetomeres hydrogen.Any kind of of hydrogen can be activated Suitable catalyst may be used to be adapted to selecting what is be used together for the catalyst of the first and/or second hydro-thermal reaction step In any reactor.For example, at least one in the first and second hydro-thermal reaction steps, which can be used, fluidly moves Dynamic catalyst particle is carried out, and the catalyst particle can flow via gas in the reactor, liquid flows, mechanical agitation Or its any combinations is at least partly suspended in fluid phase.Various conditions can be implemented, so that what must fluidly be moved urges The fluid that agent particle will not be flowed through reactor is taken away from reactor.The reactor operated in these cases is properly termed as boiling A reactor is risen, partly because catalyst particle keeps in the reactor forming catalytic bed.It will be appreciated that this area is common Technical staff can select various conditions to realize fluidized bed reactor.For example, the catalyst of suitable concentration can be selected And/or catalyst size is to obtain desired reactor condition.

On the other hand, thus it is possible to vary these conditions, consolidate so as to obtain the catalyst particle fluidly moved with biomass Body flows through reactor together.The reactor operated in these cases is properly termed as slurry phase reactor.Needed in slurry phase reactor Sufficient catalyst distribution is wanted, to allow the soluble-carbohydrate formed during hydrothermal digestion to have an opportunity to show at it Write intercepted before degraded and change into more stable compound, even in the heat condition for promoting it to degrade otherwise Under.

If it is present, the second hydro-thermal reaction step can also be used not comprising the catalyst pellets fluidly moved The catalyst of son is carried out.For example, the second hydro-thermal reaction step can be in fixed bed known to persons of ordinary skill in the art Carried out in reactor or trickle bed reactor.For example, reaction is flowed through in fixed bed or trickle bed reactor operation and fluid During device, the situation when height of bed does not flow through reactor compared to fluid is not added to more than 10%.

If having the catalyst for not including the catalyst particle fluidly moved in the second hydro-thermal reaction step Reactor, then one is probably that cellulose fine particle in the first reaction product obtained by clearing up is blocked the problem of possible Bed.When disintegrating during cellulose biomass is being cleared up, less and less particulate can be produced, until being only left insoluble thing Matter.Before clearing up, cellulose fine particle can also be present in natural fiber cellulosic biomass.A kind of disposal cellulose fine particle Mode can use screen cloth in the fluid outlet of hydrothermal digestion unit, to help to maintain cellulose fines therein.May The periodicity backflow or " punching " of liquid or gas are needed to rinse out solid from this screen cloth, to maintain fluid to flow out.A certain Size, the reactor that cellulose fine particle can enter in second reaction zone by the screen cloth of hydrothermal digestion unit and at least.

Cellulose fine particle is solved, it is to gather around jointly to be particularly small enough to by the another way of the cellulose fine particle of screen cloth Some U. S. applications disclose the method and system disclosed in Reference Number 2013/0152456 (" ' 456 publication ").In general, ' 456 publication disclose a kind of solids separation unit, and the first reaction product can be directed in the solids separation unit with it At least a portion cellulose fine particle is removed before into the reactor in second reaction zone.Solids separation unit can comprising one or Multiple filters, wherein at least one filter can fall punching to remove cellulose fines therefrom, and one or more of the other Filter keeps connecting with the inlet fluid of the reactor in second reaction zone.

In some embodiments it is possible to the catalyst of anakmetomeres hydrogen can comprising individually or with such as Au, Ag, Cr, Zn, The metal of the accelerator such as Mn, Sn, Bi, B, O and its alloy or any combinations together, such as Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, Os and its alloy or any combinations.In certain embodiments, catalyst and accelerator can allow Such as hydrogenation and the various hydro-thermal reactions of hydrogenolysis while or carry out successively each other.In certain embodiments, such catalyst is also Can include containing transition metal (such as Cr, Mo, W, Re, Mn, Cu and Cd) or group VIII metal (such as Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir and Os) carbon containing pyropolymer.In certain embodiments, Above-mentioned catalytic agent can be with alkaline-earth metal oxide Thing combines or adhered to catalytic activity carrier.In some or other embodiments, being capable of the catalyst of anakmetomeres hydrogen can sink Product does not have in the catalyst carrier of catalytic activity in itself.

In certain embodiments, tolerance poison can be included for the catalyst in the first and/or second hydro-thermal reaction step The catalyst of thing.As used herein, term " catalyst of poison tolerant " refers to due to continuous operation at least about 12 hours Low catalytic activity is without regeneration or the catalyst for being capable of anakmetomeres hydrogen changed.When derived from cellulose biomass solid Not yet remove catalyst poison soluble-carbohydrate reaction when, using the catalyst of poison tolerant be especially in accordance with need Want.The catalyst for not tolerating poisonous substance can also be used to realize similar results, but it may need the catalyst than poison tolerant More frequently regenerate or change.

The catalyst of suitable poison tolerant can include such as sulphurized catalyst., can in some or other embodiments To use nitrided catalyst as the catalyst of poison tolerant.Jointly owned patent application publication case US2012/0317872 and It is suitable for the sulphurized catalyst of anakmetomeres hydrogen described in United States Patent (USP) 8,921,629.

Catalyst particle can have about 250 microns or smaller, about 100 microns or smaller or about 10 microns or smaller grain Degree.The minimum particle size of catalyst particle can be about 1 micron.Catalyst particle can include catalyst fines.As made herein With term " catalyst fines " refers to that nominal particle size is about 100 microns or smaller solid catalyst.Catalyst fines can be with By Catalyst Production technique, for example, produced during solid catalyst is extruded.Catalyst fines can also be larger by grinding Catalyst solid is produced during catalyst solid regenerates.It is used to make described in United States Patent (USP) 6,030,915 and 6,127,229 Make the appropriate methodology of catalyst fines.In some cases, catalyst fines can be intent to from solid catalyst production running Remove, because it is likely difficult to chelating in some Catalytic processes.Skill for removing catalyst fines from larger catalyst solid Art can include for example, screening or similarly sized separation method.It is former as described herein when carrying out situ catalytic reduction reaction method During the catalytic reduction reaction method of position, catalyst fines may be particularly suitable for, because its easy fluidisation and being distributed in the fiber cleared up In the void space of cellulosic biomass solid.

Not tolerating the catalyst of poisonous substance especially can also use with reference to technique described herein.Such catalyst can include Such as Ru on Ru, Pt, Pd for being placed on solid carrier or its compound, such as titanium dioxide or Ru on carbon.Although such Catalyst may not especially tolerate poisonous substance, but it for example can be regenerated by exposing the catalysts to water at high temperature, and it can With in subcritical state or supercriticality.

It can operate to produce molecular hydrogen with reference to the catalyst that approach described herein is used.For example, at some In embodiment, the catalyst (that is, APR catalyst) for being suitable for aqueous phase reforming can be used.Suitable APR catalyst can include For example, including Pt, Pd, Ru, Ni, Co or the other group VIII being modified with Re, Mo, Sn or other metal formation alloy or through it The catalyst of metal.Therefore, in certain embodiments described herein, it may not be necessary to which external hydrogen charging to reduce by being catalyzed Reaction effectively stabilizes soluble-carbohydrate.But, in other embodiments, external hydrogen can be used to feed, appointed Selection of land, the hydrogen produced with inside is combined.In other embodiments, required molecular hydrogen can be supplied externally to cellulose biomass In solid.Provided that external hydrogen, then molecular hydrogen can be supplied as the fluid stream being upwardly directed.There is described herein supply The benefit for the fluid stream being upwardly directed.

Clearing up solvent and can include organic solvent to the first reaction zone is provided.In various embodiments, clearing up solvent can To include organic solvent and water.Although at least partly any organic solvent miscible with water may be used to clear up in solvent, But particularly advantageous organic solvent is can be directly translated into blending of fuel thing and other materials and without being separated with alcohol component Organic solvent.That is, it proved especially advantageous that organic solvent be processed further in downstream reaction during can with it is produced The organic solvent processed altogether of alcohol component.In this regard, suitable organic solvent can include such as ethanol, second two Alcohol, propane diols, glycerine, phenols and its any combinations.Other suitable organic solvents can include such as sugar alcohol.

In certain embodiments, a small amount of monohydric alcohol can be additionally comprised by clearing up solvent.Clear up in solvent exist it is at least some Monohydric alcohol can advantageously improve clearing up and/or catalytic reduction reaction of wherein carrying out.For example, clearing up solvent is included about 1 weight % to about 5 weight % monohydric alcohols may be because surface cleaning is acted on and advantageously maintains catalyst activity.In higher unitary Under determining alcohol, bulk solvent effect may start to occupy an leading position.In certain embodiments, about 10 weights can be included by clearing up solvent % or less monohydric alcohol are measured, and clears up the remainder of solvent and includes water and another organic solvent.In certain embodiments, disappear Solve solvent can include 5 weight % or less monohydric alcohol, or about 4% or less monohydric alcohol, or about 3% or less unitary Alcohol, or about 2% or less monohydric alcohol, or about 1% or less monohydric alcohol.Being present in the monohydric alcohol cleared up in solvent can be with source From any source.In certain embodiments, monohydric alcohol can as the alcohol component formed by catalytic reduction reaction accessory substance Formed.In some or other embodiments, monohydric alcohol can by the subsequent catalysis reduction of initially manufactured alcohol component shape Into and be subsequently returned to cellulose biomass solid.In other embodiments again, monohydric alcohol can be derived from and cellulose raw The outside charging that material solid is in fluid communication.

In certain embodiments, the water that solvent may be embodied between about 1% and about 99%, wherein organic solvent structure are cleared up Into the remainder for clearing up solvent compositions.Although for environmental point of view, the water of higher percent may be more favourable, due to Organic solvent is more likely to dissolve carbohydrate and promotes the catalysis reduction of soluble-carbohydrate, therefore higher amount is organic Solvent can more effectively promote hydrothermal digestion.In certain embodiments, clearing up solvent can be comprising about 90 weight % or less Water.In other embodiments, about 80 weight % or less water can be included by clearing up solvent, or about 70 weight % or less Water, or about 60 weight % or less water, or about 50 weight % or less water, or about 40 weight % or less water, or about 30 weight % or less water, or about 20 weight % or less water, or about 10 weight % or less water, or about 5 weight % Or less water.

Being processed further area typically can be comprising the condensation reaction generally carried out in the presence of condensation catalyst, wherein alcohols Component or the product formed by it are condensed to form the compound of higher molecular weight, i.e. higher hydrocarbon with another molecule.Such as this paper institutes Use, term " condensation reaction " is coupled to be formed in higher molecular weight compound each other by two or more molecules are referred to The chemical transformation of carbon-carbon bond, generally entails the loss of such as water or alcohol small molecule.A kind of exemplary condensation reaction is this area skill Aldol reaction known to art personnel.

The a part of of the higher hydrocarbon products obtained by condensation reaction can provide each to obtain to Full distillation or multistage distillation Plant product frac.Optionally, before it is distilled, the water in higher hydrocarbon products can be removed.In one embodiment, from higher hydrocarbon The product frac of product stream can at least be included in the cut containing 4 carbon atoms to the cut containing 11 or 12 carbon atoms In the range of lighter fraction.It has the initial boiling point and about 200 DEG C of final boiling point of about 35 DEG C (95 ℉) under atmospheric pressure (395 ℉), can mainly be separated for gasoline application.Lighter fraction often (" is rich in aromatic compound rich in aromatic compound The logistics of thing " or " hydrocarbon for being rich in aromatic compound ").Hydrocarbon-fraction rich in aromatic compound, which can contain, has more than 10 weights %, preferably at least 25 weight %, the aromatic compound inclusion of more preferably at least 40 weight % aromatic compounds are measured, such as Benzene, toluene, dimethyl benzene, trimethylbenzene etc..In one embodiment, product frac from higher hydrocarbon products logistics can be down to It is few to include medium cut of the scope between 200 DEG C (392 ℉) and 350 DEG C (662 ℉) under atmospheric pressure, thus produce typical case Ground per molecule contains the mixture of the carbochain of the carbon atom between 8 and 21, can mainly separate for diesel fuel applications.In It is often relatively low (" low aromatic compound hydrocarbon ") Deng aromatic content in cut.In certain embodiments, low aromatic series The hydrocarbon-fraction of compounds content can contain at most 10 weight % aromatic content.Another medium cut, such as C7- C14, can be separated as kerosene, such as jet fuel application.Most heavy distillat may be used as lubricant or can be with cracking It is used for gasoline, kerosene and/or diesel oil distillate to produce other cuts.Such lighter fraction or any medium cut can be used as height At least a portion of level hydrocarbon products is used as extractant in the liquid-liquid extraction in Disengagement zone.Hydrocarbon rich in aromatic compound It can be particularly efficient liquid-liquid extraction solvent.

Reference picture 1-3 is further described into various exemplary embodiments.Exactly, Fig. 1-2 shows biomass processes system System 1, exactly, the exemplary embodiments of the system 1B in system 1A and Fig. 2 in Fig. 1.Fig. 3 shows aqueous Disengagement zone 25 Embodiment, the aqueous Disengagement zone can be used in the Disengagement zone in system or method processing the cellulose that the disclosure is provided The Disengagement zone 13 for the system 1 described in biomass, such as Fig. 1-2.

Referring to Fig. 1-2, the hydrothermal digestion unit 2 in the first reaction zone 3 may also be referred to as clearing up area 3, containing including fiber Cellulosic biomass, the catalyst for being capable of anakmetomeres hydrogen, the first reaction contents for clearing up solvent and molecular hydrogen.Following article is further Discuss, being provided in parent material can be further comprising can conduct to the first reaction contents after hydrothermal digestion unit 2 Clear up the recycling phenolic moieties of a part for solvent.Although Fig. 1-2 shows the hydrothermal digestion unit 2 cleared up in area 3, It is to be understood that any suitable number of hydrothermal digestion list for being coupled to each other and (being such as in fluid communication with each other) can be included by clearing up area 3 Member, such as at least two, three, four, five, six or more hydrothermal digestion units.There is provided to the energy of hydrothermal digestion unit 2 The catalyst of enough anakmetomeres hydrogen preferably comprises the catalyst particle 10 fluidly moved.For example, hydrothermal digestion list Member 2 can be slurry phase reactor or fluidized bed reactor.For the sake of clarity, the cellulose in hydrothermal digestion unit 2 is not described Biomass, clear up solvent and molecular hydrogen.If reaction zone 3 has more than one hydrothermal digestion unit, then these units can be with It is any combinations of slurry phase reactor and/or fluidized bed reactor.

Reaction contents in heating hydrothermal digestion unit 2 are produced with forming the first reaction for including phenols and alcohol component Thing.Phenols is derived from the lignin in cellulose biomass, and alcohol component is by derived from the solvable of cellulose biomass Property carbohydrate is formed.Heat the first reaction contents realize situ catalytic reduce, wherein cellulose biomass clear up and The catalysis of soluble-carbohydrate is reduced to be carried out in same reactor.Reaction contents in hydrothermal digestion unit 2 are added Heat is to can be in the range of about 190 DEG C to 290 DEG C, such as in the range of about 200 DEG C to 275 DEG C, or such as at about 190 DEG C to about 260 DEG C In the range of temperature.For example, the reaction contents in hydrothermal digestion unit 2 can be heated to about 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C, 250 DEG C, 255 DEG C or 260 DEG C.

The heating of the first reaction contents in hydrothermal digestion unit 2 is preferably carried out under pressurised conditions.As made herein With term " pressurized state " refers to the pressure more than atmospheric pressure (1 bar (bar)).For example, hydrothermal digestion unit 2 can have There are at least about 30 bars, such as at least about 45 bars, at least about 60 bars, at least about 75 bars, at least about 90 bars, at least about 100 bars, at least about 110 bars, at least about 120 bars or at least about pressure of 130 bars.Hydrothermal digestion unit 2 can have at most about 450 bars, such as at most About 330 bars, at most about 200 bars, at most about 175 bars, at most about 150 bars or the at most about pressure of 130 bars.Therefore, hydrothermal digestion Unit 2 can have in the range of about 30 to 450 bars, such as in about 45 and 330 bar scopes or the pressure in the range of about 75 to 130 bars Power.It is preferred that adding hydrogen to realize the total head desired by hydrothermal digestion unit 2.For example, more than 5 bars, more than 10 bars or exceed The hydrogen dividing potential drop of 25 bars can provide to hydrothermal digestion unit 2 to realize desired total head.Extra pressure can be included by reaction The gasification of the water of thing and a part for volatile compound is produced.Clearing up in hydrothermal digestion unit 2 is heated under pressurised conditions Solvent can allow beyond the normal boiling point for clearing up various compounds in solvent, thus allow to maintain bulk fluid state, so that Hydrothermal digestion speed is allowed to increased relative to lower temperature digestion procedure.

Reaction contents in hydrothermal digestion unit 2 can be heated at least 30 minutes and at most 10 hours, most typically Between 120 minutes to 300 minutes.For example, clearing up can be carried out at least 30 minutes, at least 60 minutes, at least 120 points Clock, at least 180 minutes, at least 240 minutes, at least 300 minutes, at least 360 minutes, at least 420 minutes, at least 480 minutes, extremely It is few 540 minutes or at least 600 minutes.Clear up can be carried out within 600 minutes, at most 540 minutes, at most 480 minutes, at most 420 minutes, at most 360 minutes, at most 300 minutes, at most 240 minutes, at most 180 minutes, at most 120 minutes, at most 60 points Clock or at most 30 minutes.

Referring to Fig. 1-2, hydrothermal digestion unit 2 can load the desired amount of catalyst particles 10, while cellulose biomass Solid is added to wherein so that frequent speed is continuous or semi-continuous, thus allows hydrothermal digestion in a continuous manner.Can Periodically to take out catalyst solid and be replaced with fresh catalyst, with the catalyst degradation during compensating operation or via biomass Poison caused by component in charging.The water that cellulose biomass can be introduced into the first reaction zone via solid retraction mechanism 4 In hot cell unit 2.As used herein, finger is not made hydrothermal digestion list by term " continuous addition " and its grammer equivalents Cellulose biomass solid is added to the process in hydrothermal digestion unit in an uninterrupted manner under first decompression completely.As herein Used, term " semicontinuous addition " and its grammer equivalents will refer to fiber in the case where not making the decompression completely of hydrothermal digestion unit Cellulosic biomass solid is discontinuous but is added to as needed in hydrothermal digestion unit.That is, fresh fiber element is biological Matter solid can be added in hydrothermal digestion unit 2 to form soluble carbon water to supplement to have cleared up continuously or as needed The cellulose biomass solid of compound.

Solid retraction mechanism 4 can include mechanism loading 6 and pressure transition area 8, and pressure transition area can be with continuous or periodic Cellulose biomass is increased to the pressure of the operating pressure close to hydrothermal digestion unit 2 from atmospheric pressure, particularly when hydro-thermal disappears When solving unit 2 in pressurized state.Thus introduce continuous or semi-continuous in the case where not making the decompression completely of hydrothermal digestion unit 2 is allowed Cellulose biomass.That is, cellulose biomass solid can be added in hydrothermal digestion unit with continuous or semi-continuous, Hydrothermal digestion unit is in pressurized state simultaneously.Fresh fiber cellulosic biomass can not introduced to the hydrothermal digestion unit of pressurization In the case of, can occur the decompression and cooling of hydrothermal digestion unit during biomass is added, thus significantly reduce biomass and turn The energy and cost benefit of change process.

Pressure transition area 8 can include one or more suitable pressor areas, consolidate for pressurizeing and introducing cellulose biomass Body is into hydrothermal digestion unit 2.Such suitable pressor areas is described in greater detail in jointly owned U.S. Patent Application Publication In case 2013/0152457 and 2013/0152458.Another suitable example in exemplary pressure transition area is described in greater detail in altogether It is entitled for providing system and method for the feed-in material to compression system with what is submitted the 1 day October in 2014 possessed The U.S. of (SYSTEMS AND METHODS FOR PROVIDING FEED MATERIAL TO A PRESSURIZED SYSTEM) In state's number of patent application 62/058177.Suitable pressor areas described in it can be fed including such as pressure vessel, pressing screw Device, one or more it can extract solid and the pump of solid slurry etc..Multiple pressor areas can be connected in series to be stepped up fibre Tie up the pressure of cellulosic biomass solid.

In various embodiments, the soluble-carbohydrate produced by cellulose biomass solid can be by by can The catalytic reduction reaction of the catalyst mediation of anakmetomeres hydrogen changes into the reaction product comprising glycol.Such as jointly owned title " to be used for the method (Methods for manufacturing and processing the glycol reaction product obtained by hydrothermal digestion cellulose biomass solid for Production and Processing of a Glycol Reaction Product Obtained from Hydrothermal Digestion of Cellulosic Biomass Solids) " and " being used for will be by hydrothermal digestion fiber The glycol reaction product that cellulosic biomass solid is obtained changes into method (the Methods for of anhydrous monohydric alcohol charging Conversion of a Glycol Reaction Product Obtained from Hydrothermal Digestion Of Cellulosic Biomass Solids Into a Dried Monohydric Alcohol Feed) " United States Patent (USP) Apply for that some technological advantages can be presented in the manufacture of glycol, especially described in publication 20140121420 and 20140128639 It is in terms of being processed further reaction in downstream.In other side, the formation of monohydric alcohol may more cater to the need.

Referring to Fig. 1-2, catalyst particles 10 being capable of anakmetomeres hydrogen.At least a portion of catalyst particles 10 can be distributed In cellulose biomass, particularly in hydrothermal digestion unit 2.If carrying out situ catalytic reduction, then situ catalytic is also Original reaction needs catalyst particles 10 to be effectively distributed in whole cellulose biomass solid.This can be incited somebody to action by using fluid stream Realized in the void space that catalyst particles 10 are transported in cellulose biomass solid feedback material.It is as used herein, term " distribution (distribute/distribution) " and its version refer to so that catalyst particles are present in cellulose biology The situation of all height of matter feedback material.Distributed degrees are not implied especially using term " distribution " or its version.Catalyst Distribution can include substantial uniform distribution, the concentration of catalyst particles is presented all height of material in cellulose biomass It is substantially the same.Catalyst distribution can include uneven distribution, thus make to deposit in the various height that cellulose biomass presents material In the catalyst particles of various concentrations.When there is the uneven distribution of catalyst particles, the cellulose in hydrothermal digestion unit 2 The concentration of catalyst particles can from top to bottom increase or reduce from top to bottom in biomass solid.In certain embodiments, no Irregular concentration gradient can be included by being uniformly distributed.

Catalyst particles 10 can be transported in the cellulose biomass solid in hydrothermal digestion unit 2 is appointed with using to come from Where to fluid stream be distributed.Specifically, at least a portion catalyst particles 10 can be by the fluid that is upwardly directed Stream transports or at least existed the fluid stream being upwardly directed.For example, as shown in figs. 1-2, catalyst particles 10 can pass through Fluid inlet line 9 is supplied.Such fluid stream being upwardly directed can promote the extension of cellulose biomass solid and unfavorable The compacting for the gravity induction that Yu Qi occurs during adding and clearing up.In addition, when there is the fluid stream being upwardly directed, for profit Can with the sufficiently catalytic dose of demand for being distributed the mechanical agitation that may be needed or similar mechanical mixing techniques is obtained otherwise Can reduction.

It is suitable to make described in jointly owned Patent Application Publication 2014/0005445 and 2014/0005444 The technology of catalyst particles 10 is distributed in cellulose biomass solid with fluid stream.

As described therein, cellulose biomass solid can have to be used to retain transports catalyst particles 10 by fluid stream At least certain tropism, and at least a portion cellulose biomass solid can be set as advantageously promoting this guarantor with size Stay.In addition, forcing using fluid stream, the particularly fluid stream that is upwardly directed the active cycle of catalyst particles 10 by clearing up Cellulose biomass solid feedback material may insure sufficient catalyst distribution and advantageously reduce may during hydrothermal digestion The thermal gradient of appearance.As another advantage, the active cycle of catalyst particles 10 can be solved by cellulose biomass particulate Generation caused by the problem of because cellulose biomass particulate can be with catalyst particles common loop with hydrothermal digestion list What is carried out in member 2 continuously clears up.

The fluid stream being upwardly directed can include gas stream, liquid flow or its any combinations.In addition, the fluid being upwardly directed Stream can include a fluid stream being upwardly directed, or two fluid streams being upwardly directed, or three fluids being upwardly directed Logistics, or four fluid streams being upwardly directed, or five fluid streams being upwardly directed.

It is micro- that at least some in one or more of fluid streams being upwardly directed can contain catalyst at its source Grain.That is, fluid stream can include catalyst particles stream.One or more of fluid streams being upwardly directed can be transported Catalyst particles therein.Under other circumstances, one or more of fluid streams being upwardly directed may be at its source not Containing catalyst particles, but it still can will be located on or near the catalyst particles fluidisation of cellulose biomass solid.

One or more of fluid streams being upwardly directed can include gas stream.For example, for being upwardly directed The gas stream of fluid stream can include molecular hydrogen stream.Instead of molecular hydrogen stream or in addition to molecular hydrogen stream, can use such as steam or Inert gas, such as nitrogen.There may be at most about 40% steam in fluid stream.

One or more fluid streams being upwardly directed can include liquid flow, particularly for example fine when being not necessarily required to maintenance When catalyst particles and/or independent gas stream in dimension cellulosic biomass solid are not enough to distribution catalyst particles.Different from gas Stream, liquid flow can transport catalyst particles by cellulose biomass solid, be added to around cellulose biomass solid Liquid head, and finally overflow.Under other circumstances, catalyst flowization may be incomplete, and before liquid head spilling Liquid flow still can not may completely transport catalyst particles and pass through cellulose biomass solid.

Therefore, in some cases, at least a portion liquid head can cycle through cellulose biomass solid.Altogether With describing being adapted to of being arranged to that feed flow mutually circulates through in the Patent Application Publication 2014/0004015 that possesses The hydrothermal digestion unit 2 described in hydrothermal digestion unit, such as Fig. 1-2.Exactly, hydrothermal digestion unit 2 can include fluid Circulation loop, liquid phase and optionally catalyst particles 10 cycle through this loop, to be distributed in cellulose biomass solid.

The another way of distribution catalyst particles 10 is to transport at least a portion comprising phenols in hydrothermal digestion unit 2 Point above at least a portion of cellulose biomass solid simultaneously discharges this part.In the presence phenols, particularly in phenols In the case that aggregation forms the liquid phase rich in phenols containing most of phenols in unit 2, catalyst particles 10 can be inclined to In accumulating and be agglomerated into larger particle.The formation of liquid phase rich in phenols is by being rich in containing most of catalyst in unit 2 The cut of catalyst is provided above the cellulose biomass solid into hydrothermal digestion unit 2, and this can be used for release catalyst micro- Grain is to penetrate through downwards cellulose biomass solid.Jointly owned entitled " for slurry catalyst to be distributed in into fibre Tie up method and system (the Methods and Systems for Distributing a Slurry in cellulosic biomass solid Catalyst in Cellulosic Biomass Solids) " Patent Application Publication number 2014/0117276 and U.S. State's patent discloses the technology for describing and being permeated downwards for catalyst particles and phenols in Reference Number 2014/0174432.

In Fig. 1 in the embodiment of shown system 1, the first reaction product from hydrothermal digestion unit 2 can be provided Into Disengagement zone 13.Fig. 2 show system 1 another embodiment-system 1B, wherein the first reaction product via pipeline 12 provide to Phenolic compound conversion unit 16 in second reaction zone, i.e. region 17.Although Fig. 2 shows a phenol generalization in reaction zone 17 Compound conversion unit 16, it will be appreciated that reaction zone 17 can include it is any it is suitable number of be coupled to each other (for example each other fluid connect It is logical) reactor, such as at least two, three, four, five, six or more phenolic compound conversion units.Phenols chemical combination Thing conversion unit 16 produces the second reaction product, and second reaction product is provided to Disengagement zone 13.Clear up and deposited in product 12 A part of dihydric alcohol and glycol desired single oxygen intermediate can also be changed into via conversion unit 16.

As shown in Figure 2, the first reaction product is optionally to provide to the second reaction of phenolic compound conversion unit 16 A part for inclusion.Second reaction contents are further comprising the catalyst and molecular hydrogen for being capable of anakmetomeres hydrogen.Following article It is discussed further, being provided in original material can also be further to the second reaction contents after phenolic compound conversion unit 16 Include phenolic compound part.The second reaction contents are heated in phenolic compound conversion unit 16 to be formed comprising unconverted Phenolic compound, the second reaction product of the hydrocarbon converted by phenolic compound.Optionally, the second reaction product also can include by The monohydric alcohol of triol in alcohol component and glycol conversion in first reaction product.

Referring to Fig. 2, the second reaction contents in phenolic compound conversion unit 16 are heated with the first reaction product Compound hydrotreating, the compound can hydrotreating but the not yet hydrotreating in hydrothermal digestion unit 2.Specifically Say, the second reaction contents of heating cause at least a portion phenolic compound in phenolic compound conversion unit 16 to change into Hydrocarbon, and optionally, at least a portion triol and glycol is changed into monohydric alcohol.Reaction in phenolic compound conversion unit 16 Inclusion is heated in the range of about 210 DEG C to 300 DEG C, such as the temperature in the range of 270 DEG C to 290 DEG C or at least 270 DEG C. For example, the reaction contents in phenolic compound conversion unit can be heated to about 210,215,220,225,230, 235th, 240,245,250,255,260,265,270,275,280,285,290,295 or 300 DEG C.In a specific embodiment In, exceed going out in hydrothermal digestion unit 2 in the temperature of second reaction product in the exit of phenolic compound conversion unit 16 The temperature of the first reaction product at mouthful.The second reaction contents hydrotreating in phenolic compound conversion unit 16 also may be used Regenerate the catalyst particles (if present) accumulated in the first reaction product.

In fig. 2, phenolic compound conversion unit 16 is preferably at pressurized state.For example, phenolic compound turns At least about 30 bars, such as at least about 45 bars, at least about 60 bars, at least about 75 bars, at least about 90 bars, at least can be had by changing unit 16 About 100 bars, at least about 110 bars, at least about 120 bars or at least about pressure of 130 bars.Phenolic compound conversion unit 16 can have There are at most about 450 bars, such as at most about 330 bars, at most about 200 bars, at most about 175 bars, at most about 150 bars or at most about 130 bars Pressure.Therefore, phenolic compound conversion unit 16 can have in the range of about 30 to 450 bars, such as from about 45 and 330 bar scopes Or the pressure in the range of about 75 to 130 bars.Preferably use the total head needed for hydrogen acquisition phenolic compound conversion unit 16.Lift For example, can provide more than 5 bars, more than 10 bars or more than 25 bars hydrogen dividing potential drop to phenolic compound conversion unit 16 with acquisition Required total head.

Referring to Fig. 2, the reaction contents in phenolic compound conversion unit 16 can be heated at least 30 minutes and at most 10 hours, such as 120 minutes to 300 minutes.For example, clear up can carry out at least 30 minutes, at least 60 minutes, at least 120 Minute, at least at least 180 minutes, at least 240 minutes, at least 300 minutes, at least 360 minutes, at least 420 minutes, 480 minutes, At least 540 minutes or at least 600 minutes.Clear up can be carried out within 600 minutes, at most 540 minutes, at most 480 minutes, at most 420 minutes, at most 360 minutes, at most 300 minutes, at most 240 minutes, at most 180 minutes, at most 120 minutes, at most 60 points Clock or at most 30 minutes.

The hydro-thermal reaction carried out in phenolic compound conversion unit 16 can turn phenolic compound derived from lignin The desired hydrocarbon that can be used in such as gasoline blending of fuel thing of chemical conversion.Exemplary non-limiting hydrocarbon compound includes being adapted to use Alkane, alkene, cycloalkane and its alkyl substituent or derivative in the fuel composition such as gasoline or diesel oil, Yi Jihuan Alkene and its alkyl substituent or derivative.For example, exemplary hydrocarbon compound can include but is not limited to following any： It is hexamethylene, cyclohexene, propyl group pentamethylene, propyl group cyclopentene, propyl cyclohexane, cyclohexyl alkene, methyl phenyl ethers anisole, propylbenzene, oxygen-containing Hydrocarbon ring hexanone or methyl cyclohexanone, and methyl-propyl benzene.Hydrocarbon may be endless needed for phenolic compound derived from lignin is changed into Entirely so that unconverted phenolic compound may be remained in the second reaction product.Optionally, converted in phenolic compound The hydro-thermal reaction carried out in unit 16 can also realize hydrodeoxygenation, and triol and glycol wherein in alcohol component change into unitary Alcohol.Hydrodeoxygenation may be not exclusively so that triol and glycol may be remained in the second reaction product.Therefore, second is anti- Product is answered to include at least a portion of unconverted phenolic compound, the hydrocarbon converted by phenolic compound, and alcohol component.

In phenolic compound conversion unit 16, phenols can also be converted to cyclic alcohol, including alkyl cyclohexanol and alkane At least one of basic ring amylalcohol, the cyclic alcohol can similarly serve as a part for extractant.Phenol generalization can be selected The operating condition of compound conversion unit 16 is to produce cyclic alcohol derived from relatively large number of some phenols, so that less phenol Class is stayed in the second reaction contents in unit 16.At least one of cyclohexanol and cyclopentanol can also activated point By the carbohydrate in hydro-thermal unit unit 2 and phenolic compound conversion unit 16 (if deposited in the presence of the catalyst of sub- hydrogen If) formed via hydrodeoxygenation reaction.

As mentioned, it was found that in reaction zone 17, second such as carried out in Fig. 2 phenolic compound conversion unit 16 The yield of hydro-thermal reaction step hydrocarbon under low phenolic compound concentration is higher than the yield of hydrocarbon under high concentration phenolic compound.Unit 16 The concentration of middle phenolic compound includes at most 50 weight %'s with the gross weight meter of the inclusion of phenolic compound conversion unit 16 Concentration.The non-limiting exemplary phenolic compound concentration of the reaction contents of unit 16 can be in about 0.1 weight % to 50 weights Measure in the range of %, and can be any amount between the two, including in terms of total weight of inclusions of the second hydro-thermal reaction step Less than 45 weight %, less than 40 weight %, less than 35 weight %, less than 30 weight %, less than 25 weight %, less than 20 weights Measure %, less than 15 weight %, less than 10 weight % or less than 5 weight %.

In addition, as mentioned, if realizing conversion in the presence of water, then conversion of the lignin to phenols can be improved And/or phenolic compound is to the conversion of hydrocarbon compound.Referring to Fig. 2, it can be realized at least partially by water with inclusion in unit 16 Weight meter 50% or less unit 16 in phenolic compound concentration.For example, in phenolic compound conversion unit 16 The concentration of water can be at least 10 weight % with the gross weight meter of the inclusion of unit 16.It is anti-in phenolic compound conversion unit 16 The non-limiting exemplary water concentration for answering inclusion can be at least 10 in terms of total weight of inclusions of the second hydro-thermal reaction step Weight %, at least 15 weight %, at least 20 weight %, at least 25 weight %, at least 30 weight %, at least 35 weight % or at least 40 weight %.

Fig. 1-2 shows gas separator unit 18, and it is optional.In Fig. 1, the first reaction product is carried via pipeline 19 It is supplied to gas separator unit 18.In fig. 2, the second reaction product is provided to gas separator unit 18 via pipeline 19.Depending on Need or if necessary, gas separator unit 18 allows to remove the excessive gas in reaction product.As discussed above, from water Heat clears up the first reaction product of unit 2 and the second reaction product from phenolic compound conversion unit 16 is provided under stress Into gas separator unit 18, because unit 2 out of the ordinary and unit 16 are to operate under pressurised conditions.It therefore, it can by inciting somebody to action Gas separator unit 18 is maintained at pressure that is identical with the hydrothermal digestion unit of the system 1A in Fig. 1 or reducing by comparison Under, or from anti-under pressure that is identical with the phenolic compound conversion unit 16 of the system 1B in Fig. 2 or reducing by comparison Product is answered to discharge excessive gas.As shown in figs. 1-2, excessive gas can be provided via pipeline 23 to being processed further area 22. Most excessive gas is less than 100 DEG C of other compounds, including methane, carbon dioxide, an oxygen comprising hydrogen and normal boiling point Change carbon and water.Other compounds, such as lightweight list oxygen compound, especially less than C4 compound may reside in excessive gas In, wherein this logistics can provide additional materials and be used to change into fuel Products in area 22 is processed further.Gas separator The pressure of unit 18 can be based on considering in Disengagement zone 13 needed for liquid-liquid extraction unit 20 or selected operating pressure and/or enter one Needed for step processing district 58 or selected operating pressure is selected.For example, the reaction in gas separator unit 18 is not produced It is to need to be intended for being processed further being produced by Disengagement zone 13 for area 58 that thing, which is depressurized to less than an a certain amount of Consideration, Raw product pressurizes again.It is therefore to be understood that the pressure of gas separator unit 18 can be depending on other in system 1A or 1B Unit and/or the pressure in area.The non-limiting illustrative example of the pressure of gas separator unit 18 can be in about 5 to 50 bars In the range of, including 10 bars, 15 bars, 20 bars, 25 bars, 30 bars, 35 bars, 40 bars or 45 bars.

As mentioned, gas separator unit 18 is optional, therefore the first reaction product or the second reaction product can be with There is provided respectively from hydrothermal digestion unit 2 or phenolic compound conversion unit 16 to Disengagement zone 13, do not pass through gas separator unit 18.Referring to Fig. 1-2, Disengagement zone 13 includes liquid-liquid extraction unit 20, aqueous Disengagement zone 25, non-aqueous distillation unit 27 and optionally Ground lignin depolymerization unit 29.In liquid-liquid extraction unit 20, the reaction product provided via pipeline 26, which is divided into, is depicted as pipeline 28 aqueous streams and the non-aqueous logistics for being depicted as pipeline 24.Aqueous streams in pipeline 28 are provided to aqueous Disengagement zone 25.Non-aqueous logistics in pipeline 24 is provided to non-aqueous distillation unit 27.Optionally, exist in lignin depolymerization unit 29 Under, the non-aqueous logistics of the lignin containing depolymerization can be provided via pipeline 30 to lignin deposit area 62.

Liquid-liquid phase separation unit or liquid-liquid extraction unit 20 allow to utilize aqueous phase separation of the extractant from reaction product And/or extract various compounds.This can by using have compound to be extracted dissolubility ratio wherein in aqueous phase it is high Extractant realize.At least a portion of the extractant comes from reaction product, and the reaction product can be high Level hydrocarbon products (reaction product can also be its cut, be referred to as " higher hydrocarbon products ") 49, the centre from distillation unit Cut or the tower bottom distillate of non-aqueous logistics flash vessel (not shown) even as described in this article.As shown in figs. 1-2, Extractant can be provided via pipeline 45.As indicated, before liquid-liquid extraction unit 20 is entered, solvent in pipeline 45 can be with Optionally combined via pipeline 45A with the reaction product in pipeline 26.Besides or furthermore, the solvent in pipeline 45 can be via pipe Line 45B is provided to unit 20, is mixed with the reaction product with the pipeline 26 in unit 20.

As shown in figs. 1-2, the senior hydrocarbon stream for lignin deposit can be come from by pipeline 53 is processed further Area 58.Additionally, optionally at least a portion of extractant described in pipeline 45 can be come from by pipeline 49 and is processed further Area 58.At least a portion for lignin deposit and the senior hydrocarbon stream for being optionally used for extractant can also be by further adding Work order member 22 is provided by optional distillation unit 50.Lignin deposit and optionally liquid-liquid extraction degree can depend on following again Ring is optimized on demand to the cut 51 of respective areas.In one embodiment, such senior hydrocarbon-fraction 51 can be rich in The hydrocarbon-fraction of aromatic compound.In another embodiment, senior hydrocarbon-fraction 51 can be that aromatic content is relatively low Hydrocarbon-fraction.In another embodiment, it can be such logistics or from the another of the higher hydrocarbon products for being processed further unit The combination of any cut 51.If 51 be light fraction, then 52 be optional senior hydrocarbon-fraction, such as medium cut, or if 51 It is medium cut, then 52 be light fraction.54 be most heavy distillat.

If necessary, at least a portion wood can be removed or isolated in lignin separation unit 60 as described above Quality.Then, such treated logistics is provided into distillation unit 27 by separation or without isolation via pipeline 31. If the not separating lignin from lignin separation unit 60, then lignin can divide more easily in distillation unit 27 From.

If it is present, the extractant in the pipeline 45 provided can be in than 9 parts pipes of the solvent in 1 part of pipeline 45 Reaction product in line 26 is to the solvent in 9 parts of pipelines 45 than the ratio in the range of the reaction product in 1 part of pipeline 26.It is unrestricted Property illustrate sex rate include than 9 parts reaction products (1 of 1 part of solvent:9), than 8 parts reaction products (1 of 1 part of solvent:8), 1 part of solvent ratio 7 parts of reaction products (1:7), than 6 parts reaction products (1 of 1 part of solvent:6), than 5 parts reaction products (1 of 1 part of solvent:5), 1 part of solvent Than 4 parts reaction products (1:4), than 3 parts reaction products (1 of 1 part of solvent:3), than 2 parts reaction products (1 of 1 part of solvent:2), 1 part it is molten Than 1 part reaction product (1 of agent:1), than 1 part reaction product (2 of 2 parts of solvents:1), than 1 part reaction product (3 of 3 parts of solvents:1), 4 parts Than 1 part reaction product (4 of solvent:1), than 1 part reaction product (5 of 5 parts of phenols:1), than 1 part reaction product (6 of 6 parts of solvents:1)、7 Part than 1 part reaction product (7 of solvent:1), than 1 part reaction product (8 of 8 parts of solvents:1), than 1 part reaction product (9 of 9 parts of solvents:1)、 Than 1 part reaction product (10 of 10 parts of solvents:And its any combinations 1).

The reaction product produced by the phenolic compound conversion unit 16 in the hydrothermal digestion groove 2 or Fig. 2 in Fig. 1 is aqueous phase With the mixture of at least one nonaqueous phase, therefore its typically often have than other compound higher amounts water emulsion. When the amount of extractant in liquid-liquid extraction unit 20 is in lower end, liquid-liquid extraction process may behave much like liquid-liquid phase point From, wherein extractant by increasing the concentration of nonaqueous phase, make its ratio with aqueous phase closer to 1:1 come help reaction product breast Liquid is divided into each layer and/or each phase.In lower end, the level extracted from aqueous phase during each group assigns to solvent is minimum.Material in pipeline 45 It is considered as extractant, because its composition is different from the non-aqueous liquid phase separated from the reaction product in pipeline 26.With addition To the amount increase of the extractant of liquid-liquid extraction unit 20, the extraction levels or degree of some compounds also increase.It can select The condition of liquid-liquid extraction unit 20 is so that extraction levels reach maximum.

Referring to Fig. 1-2, can use can be distributed into reaction product aqueous streams and any of non-aqueous logistics is adapted to Liquid-liquid extraction method and system.These methods can be by batch mode, half point batch mode, continuous mode or its any combinations Operation.

In general, blender-settler equipment available for liquid-liquid extraction unit 20 includes the mixing with agitator Reaction product of the container to mix the solvent provided by pipeline 45 Yu be provided by pipeline 26.The inclusion of mixing can be provided It is each wherein mutually to coalesce and separate into subsider, therefore aqueous streams can be discharged via pipeline 28 and can be via Pipeline 24 discharges non-aqueous logistics.

In general, centrifuge contactor is the high speed rotating machine being characterized with the relatively low residence time.In centrifugal device Number of stages be typically one, but it is also possible to using with multiple stages centrifuge contactor.Centrifuge contactor utilizes machine Tool device stirs mixture to increase interface zone and reduce resistance to mass tranfer.The equally applicable different types of differential for making unit 20 Extractor (also known as " continuously contacting extractor ") includes but is not limited to, centrifuge contactor and contact tower, such as plate column, injection Tower, packed column, rotary-disk contactor and pulse-column.

Contact tower is suitable for various liquid-liquid extraction operations.Filler, tower tray, spraying or the mechanism of other formation droplets or its Its equipment be used to increase the surface area that two liquid phases (that is, solvent phase and hydrocarbon phase) contact, and also increase effective length of flow path Degree.In the type and/or concrete configuration of slective extraction device, material or construction and packing material type and feature (that is, average grain Degree, shape, density, surface area etc.) when, it is also contemplated that flow and the change of physical characteristic along extractor length.Citing For, the extractant in pipeline 45 can be provided relative to the flowing of the reaction product in pipeline 26 with the flow direction of adverse current In unit 20.

Specifically, liquid-liquid separation unit 20 can include plate column, and the wherein reaction product in pipeline 26 is provided to tower Bottom and extractant be provided in top of tower or near.In addition, the tower can be had known to those of ordinary skill The multi-stage countercurrent contactor of multiple tower trays and related down-comer.

The another type unit operation for being suitable for liquid-liquid extraction unit 20 is packed bed tower, and it typically comprises suitable Packing material, including but not limited to Paar ring (Pall ring), Raschig ring (Raschig ring), Ka Sike rings (Kascade Ring), English Teller saddle packing (Intalox saddle), Bai Er saddle packings (Berl saddle), super English Teller saddle type Filler, super Bai Er saddle packings, demisting pad, demister, carbon graphite random packing elements, other type saddle packings etc., including this One or more combinations in a little filler materials.Packing material provides larger interface zone for being in contact, and thus causes drop Coalescence and restructuring.

Being suitable for other type equipments of liquid-liquid extraction includes rotary-disk contactor.Rotary-disk contactor is the inverse of mechanical agitation Flow extractor.Stirring is provided by rotating disk mechanism.

The another type equipment for being suitable for extracting aromatic compound in the system and method for the present invention is pulse-column, its Filler or sieve plate with multiple shortage down-comers.Hole in sieve plate is typically less than the hole of non-pulse tower.Produce pulse Device, such as reciprocating pump imposes pulse with frequently time interval to the inclusion of tower.The fast reciprocating fortune of relatively small amplitude Fold is added in the usual flowing of liquid phase.Pulsation causes the contact between each phase, thus influence extraction.

Liquid-liquid extraction process can also relate to allow or promote the equipment of each phase coalescence, including horizontal subsider, one or Multiple fishgarths, centrifuge or hydraulic cyclone type device, fibre conglomerates pad or packed bed coalescer.As mentioned, liquid-liquid extraction Unit 20 provides the non-aqueous logistics in aqueous streams and pipeline 24 in pipeline 28.

Aqueous streams include most of water present in the reaction product in liquid-liquid extraction unit 20.For example, it is aqueous Logistics comprises more than 50 weight %, including 55 weight % or bigger, 60 weight % or bigger, 70 weight % or bigger, 75 weights Measure % or bigger, 80 weight % or bigger, 85 weight % or bigger, 90 weight % or bigger and 95 weight % or bigger unit The water in reaction product in 20.Accordingly, non-aqueous logistics is included in the reaction product out of the ordinary in liquid-liquid extraction unit 20 Small part water.For example, non-aqueous logistics includes at most 50 weight %, be included in 0.1 weight % and at most 50 weight %, At most 45 weight %, at most 40 weight %, at most 35 weight %, at most 30 weight %, at most 25 weight %, at most 20 weights Measure in the reaction product in the unit 20 of the amount in the range of %, at most 15 weight %, at most 10 weight % or at most 5 weight % Water.Non-aqueous logistics includes the reaction product of the remainder not in aqueous streams.For example, non-aqueous logistics can have Have more than a phase.

If the relative quantity of extractant used is relatively low, such as when extractant is with relative to the reaction product in pipeline 26 When being provided less than 50 weight %, then extraction degree may be minimum, therefore in addition to water soluble salt and ash content, aqueous streams can be with Comprising at least partly can be miscible with the water in reaction product pipeline 26 and providing to the majority of compounds of unit 20, including lightweight Compound, intermediate boiling compounds, heavy compounds.Light compounds include the compound that normal boiling point is less than 150 DEG C.Lightweight The non-limiting illustrative example of compound includes monohydric alcohol, aldehyde, ketone, acid and its any combinations.In present in aqueous streams Between boiling-point compound include compound normal boiling point in the range of 150 to 350 DEG C or higher boiling point, it can include glycol And phenols.Heavy compounds include compound normal boiling point more than 350 DEG C.

If the relative quantity of extractant used is higher, such as when extractant is with relative to the reaction product in pipeline 26 When being provided more than 50 weight %, then aqueous streams, which can substantially lack, light compounds to be extracted, including single oxidation At least one of compound (such as C1-C4), some dihydric alcohols and free acid (such as acetic acid or higher level).That is, at these Under situation, aqueous streams can be containing having to be extracted and provide to the micro part of unit 20 in the reaction product in pipeline 26 Light compounds, wherein these light compounds include single oxygen compound (such as C1-C4), some dihydric alcohols and free acid (such as second At least one of acid or higher level).In these cases, aqueous streams still can include glycol, including ethylene glycol and third Glycol, and a certain amount of extractant.Aqueous streams also contain water soluble salt, including hydrochlorate and ash content.

Referring to Fig. 1-2, aqueous streams can be provided via pipeline 28 to aqueous Disengagement zone 25.After liquid-liquid extraction process, If aqueous streams contain the light compounds that those of ordinary skill thinks recyclable threshold quantity, such as when extraction levels are under During end, then light compounds can be reclaimed in aqueous Disengagement zone 25.Aqueous streams can undergo flash distillation, and reduce steam vapour Influence is proposed, because compared with the reaction product with multiple liquid phases, aqueous streams contain less amount of phenols so that in flash distillation step The phase rich in phenolic compound of separation can be minimized during rapid.Flash distillation aqueous streams are recovered to various light compounds, These light compounds can be further processed into fuel Products.Light compounds can include normal boiling point and be less than 150 DEG C Compound, including but not limited to monohydric alcohol, aldehyde, ketone, acid and its any combinations.

Referring to Fig. 1-2, most of light compounds in aqueous streams are reclaimed in aqueous Disengagement zone 25.For example, More than 50 weight % in aqueous streams in region 25, especially at least 75 weight %, at least 80 weight %, at least 85 weights The compound that amount %, at least 90 weight % or at least 95 weight % normal boiling point are less than 150 DEG C is recovered.These lightweight chemical combination Thing can be provided via pipeline 32 to being processed further area 58, be processed further its in area described and can be further processed into institute Product is needed, as further discussed below.As shown in figs. 1-2, before area 58 is processed further, water is come from via pipeline 32 The light compounds of property Disengagement zone 25 can with it is many in the pipeline 23 from gas separator unit 18 (if present) Remaining combination of gases.Besides or furthermore, it can be divided into region 58.In some cases, heavier compound, such as normal boiling point It is the compound of 150 DEG C or higher boiling point, including phenols and glycol, can also reclaims in aqueous Disengagement zone 25.If These heavier compounds are reclaimed in region 25, then it can be provided via pipeline 33 to clearing up area 3 and/or reaction zone 17 In, as shown in figs. 1-2.Specifically, Fig. 1 shows the pipeline 33 between hydrothermal digestion unit 2 and aqueous Disengagement zone 25, and Fig. 2 shows the pipeline 33 between phenolic compound conversion unit 16 and region 25.It will be appreciated that pipeline 33 is extended in Fig. 2 Hydrothermal digestion unit 2, even if not shown.As mentioned, glycol and/or phenols may be used as clearing up a part for solvent.It is dirty Thing is contaminated, such as salt, ash content, caramel and tar residual can be disposed as discarded object via pipeline 34.

If the relative quantity for being fed to the extractant of unit 20 is higher, than 2 parts pipelines 26 of such as more than 1 part extractant In reaction product, then may not be needed or wish the light compounds in the aqueous streams in recovery line 28.Therefore, water Property logistics may and be processed not as described in aqueous Disengagement zone 25, hence in so that region 25 is optional.Besides or furthermore, The disposal of aqueous streams in region 25 can be configured to provide for the heavier compound of such as phenols and glycol and replace lighting Compound, so that pipeline 32 is optional.

Aqueous Disengagement zone 25 can become known for separating appointing for these light compounds comprising those of ordinary skill in the art What appropriate methodology.For example, region 25 can include one or more flash vessels.Under a kind of situation (not shown), region 25 can include a flash vessel, to be flashed aqueous streams to reclaim light compounds in overhead fraction, and contain The tower bottom distillate for having water soluble salt and ash content can be abandoned as discarded object.But, obtained tower bottom distillate is flashed by single Other valuable heavier compounds, such as phenols and glycol can also be contained.Fig. 3 is shown for reclaiming these valuable heavierization One selection scheme of the aqueous Disengagement zone 25 of compound, wherein region 25 include more than one flash vessel：Flash vessel 35 and flash distillation Device 36.In figure 3, light compounds are reclaimed in the overhead fraction of flash vessel 35, its provided via pipeline 32 to further plus Work area 58.The tower bottom distillate of flash vessel 35 is provided to flash vessel 36 via pipeline 37.In flash vessel 36, including phenols and glycol Valuable heavier compound inside is recovered in overhead fraction, and it can be provided via pipeline 33 to clearing up area 3 and/or anti- Answer area 17.Pollutant leaves as discarded object via pipeline 34.Other suitable separation method bags available for aqueous Disengagement zone 25 Include and be separated from water organic matter and salt using film.

Referring to Fig. 1-2, as mentioned, before non-aqueous distillation unit 27 is entered, from the non-aqueous of liquid-liquid extraction unit 20 Property logistics can be provided to optional lignin depolymerization unit 29.If it is present, non-aqueous logistics can be via pipeline 24 Into unit 29.Lignin depolymerization unit 29 can reduce viscosity to improve by using the reaction of one or more lignin depolymerizations The product separation of non-aqueous logistics.Lignin depolymerization unit 29 can include any suitable lignin depolymerization reaction.

Suitable lignin depolymerization reaction is as known in the art.Non-limiting exemplary lignin depolymerization reaction includes Thermal response, the reaction can be carried out with or without under catalyst.In general, the hot lignin solution carried out under without catalyst Poly- reaction is typically carried out at a temperature of more than 300 DEG C.Catalyst and hydrogen can be added reaction is fallen below into 300 ℃.Any suitable catalyst in solid or liquid form, including acid or base catalyst can be used.For example, exist U. S. application discloses the side described in Reference Number 2012/0302796 on the lignin depolymerization catalyst using solid catalyst Method.Include U.S. Application No. 6,100,385 and 7,964 on other disclosures using catalyst in lignin depolymerization, 761.Make lignin depolymerization in non-aqueous logistics other methods include pyrolysis (thermal decomposition), gasification, hydrogenolysis, chemical oxidation and Hydrolyze at supercritical conditions.Additional detail on these methods is found in Pandey and Kim,《Lignin depolymerization and conversion： Commentary (the Lignin Depolymerization and Conversion of thermochemical method:A Review of Thermochemical Methods)》,《Chemical Engineering and Technology (Chem.Eng.Technol.)》, the 2011, the 1st phase, 29- 41.If be still present in lignin before pressure decatizing evaporates in non-aqueous logistics, then it can precipitate and form lignin slurries. In this case, it is optionally possible in non-aqueous logistics is caught before pressure decatizing evaporates using lignin removal mechanism this lignin At least partially.Any suitable lignin removal mechanism can be used.Nonrestrictive suitable lignin removal mechanism includes Filter, forcing press, hydrocyclone plant or its any combinations.The lignin caught by lignin removal mechanism can be provided To lignin depolymerization unit 29, with further depolymerization or any other depolymehzation step of progress.

Referring to Fig. 1-2, the non-aqueous logistics of the lignin with optional depolymerization is provided to non-aqueous distillation unit 27, institute Any suitable Distallation systm or method, including multistage distillation can be included by stating non-aqueous distillation unit.As indicated, non-aqueous In distillation unit 27, distill non-aqueous logistics and obtain various product fracs, including overhead fraction, one or more midbarrels, And tower bottom distillate.

Being depicted as the overhead fraction from non-aqueous flow separation of pipeline 38 includes providing single to distilling via pipeline 30 Most of light compounds in the non-aqueous logistics of member 27.For example, exist in the non-aqueous logistics in distillation unit 27 Normal boiling point be less than in 150 DEG C of compound more than 50 weight %, especially at least 75 weight %, at least 80 weight %, extremely During few 85 weight %, at least 90 weight % or at least 95 weight % are the overhead fraction in pipeline 38.

Midbarrel can include the compound than light compounds weight, and particularly normal boiling point is 150 DEG C or more height boiling The compound of point.Distillation unit 27 can be operated to exceed a kind of midbarrel to provide.For example, distillation can be operated to carry It is about 150 DEG C to 250 DEG C of the first midbarrel for normal boiling point, is depicted as pipeline 39, it typically catches phenolic compound； And the second midbarrel with 200 DEG C to 350 DEG C of higher standard boiling point, pipeline 40 is depicted as, it typically catches wooden Plain oligomer.Distillation can also be operated to provide the midbarrel that normal boiling point is about 150 DEG C to 350 DEG C.As mentioned above, Exist overlapping in the normal boiling point of midbarrel, this is at least attributed to the distribution of compound during still-process.Therefore, pipeline 39 In the first midbarrel can include compound normal boiling point in the range of about 150 DEG C to 300 DEG C.It is depicted as pipeline 40 Second midbarrel can include the compound that normal boiling point is 200 DEG C to 350 DEG C, and it typically catches lignin oligomer. Being depicted as the bottom fraction of pipeline 41 has compound of the normal boiling point more than 350 DEG C, and it, which typically catches, is considered as discarded object Or the most heavy compound of accessory substance, such as caramel and/or tar.Although the first midbarrel can be referred to as phenols cut and Two midbarrels can be referred to as lignin oligomeric fraction, it is to be understood that phenols cut can contain lignin oligomer, and And lignin oligomer can contain phenols.It will be appreciated that it can be that phenols evaporates to distill obtained midbarrel by non-aqueous logistics Point, lignin oligomeric fraction or its combination.As described by, Disengagement zone 13 provides one or more midbarrels, the centre Cut, which contains, is provided with most of phenolic compound into the reaction product of Disengagement zone 13.

Referring to Fig. 1-2, the overhead fraction from distillation unit 27 can be provided via pipeline 38 to being processed further area 58. As indicated, before unit 22 is processed further, material in pipeline 38 can be with reclaiming in pipeline 32 from aqueous streams The excessive gas group reclaimed in other light compounds and/or pipeline 23 from gas separator unit 18 (if present) Close.Besides or furthermore, the material in pipeline 38 can be provided separately to being processed further area 58.

Referring to Fig. 1-2, at least a portion of one or more midbarrels from distillation unit 27 can be recycled to Each position in system 1.For the sake of simplicity, do not show and the midbarrel from distillation unit 27 is connected in system 1 The pipeline of other positions.In fact, the import and part there is provided pipeline are described.It will be appreciated that these pipelines can be as described It is connected to each other, even if not providing complete picture.Referring to Fig. 1-2, one or more midbarrels can also provide to clear up area 2, In at least one of reaction zone 17 and lignin depolymerization unit 29.In Fig. 1-2, the first midbarrel in pipeline 39 can be with There is provided via the pipeline 39 for being connected to import 44 into hydrothermal digestion unit 2 for use as the part for clearing up solvent.Or it is or another Outside, although be not preferred, the second midbarrel but in pipeline 40 can be provided via the pipeline 40 for being connected to import 44 to Hydrothermal digestion unit.Can also be via pipeline 39A and 40A by second in the first midbarrel in pipeline 39 and pipeline 40 Between cut combine, wherein the mixture of both can be provided to hydrothermal digestion unit 2 via the pipeline 46 for being connected to import 44. Single midbarrel comprising the first midbarrel and the second midbarrel can also be provided to hydrothermal digestion unit 2.Pipeline 39, The amount provided in 40 or 46 to the material of hydrothermal digestion unit 2 can as discussed above, by providing to hydrothermal digestion unit 2 The amount of lignin determine.

Besides or furthermore, in fig. 2, at least one midbarrel from distillation unit 27 also via pipeline 42 provide to Phenolic compound conversion unit 16.In fig. 2, the first midbarrel in pipeline 39 is carried via the pipeline 39 for being connected to pipeline 42 It is supplied to unit 16.Besides or furthermore, the second midbarrel in pipeline 40 is provided to list via the pipeline 40 for being connected to pipeline 42 Member 16.Besides or furthermore, the first midbarrel in pipeline 39 can be with the second midbarrel in pipeline 40 via pipeline 39A With 40A combinations, wherein the mixture of both may be used as a part for extractant and via the pipeline being connected with pipeline 42 46 provide.Single midbarrel comprising the first midbarrel and the second midbarrel can also be provided to phenolic compound and converted Unit 16.Phenols at least one of these cuts can be further converted into hydrocarbon in unit 16, as described herein. Lignin at least one of these cuts can be further converted into phenols in unit 16, as described herein.

Referring to Fig. 2 unit is influenceed there is provided the amount by distilling the midbarrel that non-aqueous logistics is obtained to conversion unit 16 The amount of phenolic compound concentration in 16.As mentioned, it is preferable that phenolic compound conversion unit 16 includes lignin oligomer Amount including phenolic compound concentration maintain 50 weight % or lower.If going to phenols from hydrothermal digestion unit 2 First reaction product of compound conversion unit 16 contains certain phenolic compound concentration, then to consider whether from non- The part of midbarrel for aqueous streams distillation is added to unit 16, so as to can be as needed or desired in maintenance unit 16 Phenolic compound concentration.For example, cut from least one of pipeline 39 and pipeline 40 can with pipeline 12 First reaction product is provided to phenolic compound conversion unit 16 in certain ratio or percentage.Specifically, non-limiting example The amount that illustrative example includes the material from least one of pipeline 39 and pipeline 40 is the first reaction product in pipeline 12 Amount or flow velocity be no more than 50wt%.In this case, relative to portion from least one of pipeline 39 and pipeline 40 Material, the amount of the first reaction product is at least two parts.

As shown in figs. 1-2, the material from least one of pipeline 39 and pipeline 40 can also be carried via pipeline 43 It is supplied to lignin depolymerization unit 29 (if present).At least from the material of at least one of pipeline 39 and pipeline 40 Lignin can further depolymerization, thus improve distillation unit 27 in distillation efficiency because further reduction via pipeline 30 The viscosity of the material of offer.

Some or all of at least one of pipeline 39 and pipeline 40 material can be provided to lignin depolymerization unit 29.For example, by distilling at least 10wt% in the midbarrel that non-aqueous logistics is obtained, exactly, at least 20 weights Measure %, at least 30 weight %, at least 40 weight %, at least 50 weight %, at least 60 weight %, at least 70 weight %, at least 80 Weight % or at least 90 weight % material are provided to lignin depolymerization unit 29.It can be passed through by those of ordinary skill in the art Balance different factors to select the amount, the factor, which is included in liquid-liquid extraction unit 20, hydrothermal digestion unit 2, uses phenol Class further converts and changed into hydrocarbon as lignin in solvent and phenolic compound conversion unit 16.More material is followed again Ring causes less material to be recycled to other positions to a position.During startup or as needed, external solvent is (i.e., not again The solvent of circulation) it can provide into system 1, particularly hydrothermal digestion unit 2.

Referring to Fig. 1-2, any suitable number of reactor that unit 22 can include being coupled to each other is processed further, for example At least one, two, three, four, five or six be processed further unit.The reaction occurred in area 58 is processed further Alcohol component can be changed into required hydrocarbon compound.Although not showing, turn from the phenolic compound in the second reaction product The hydrocarbon of change be sent to be processed further area 58 before can be separated with the second reaction product, or can be retained in second anti-for the hydrocarbon Answer in product and by being processed further area 58, as described herein.In addition, before remaining cut is processed further can remove or Dehydrogenation and vapor are not gone.

Referring to Fig. 1-2, being processed further area 58 typically can be comprising the condensation generally carried out in the presence of condensation catalyst Reaction, wherein alcohol component or the product formed by it are condensed to form the compound of higher molecular weight with another molecule.Such as this Text is used, and term " condensation reaction " will refer to two or more molecules and be coupled to be formed in higher molecular weight compound each other Carbon-carbon bond chemical transformation, generally entail the loss of such as water or alcohol small molecule.A kind of exemplary condensation reaction is this area Aldol reaction known to technical staff.

Although a variety of different types of catalyst can be used to mediate condensation reaction, in this regard, zeolite is urged Agent is also likely to be particularly advantageous.A kind of zeolite catalyst for being particularly suitable for adjusting the condensation reaction of alcohol is ZSM-5 (Zeolite Socony Mobil 5), this catalyst is that have composition NanAlnSi96-nO19216H2O (0<n<27) Five sial silicate zeolites, can by alcohol charging be transformed into condensation product.Other suitable zeolite catalysts can include example Such as ZSM-12, ZSM-22, ZSM-23, SAPO-11 and SAPO-41.

In various embodiments, condensation reaction can between about 275 DEG C with about 450 DEG C at a temperature of enter OK.Condensation reaction can be carried out in condensation phase (such as liquid phase) or in the gas phase.It is anti-for the condensation that carries out in the gas phase Should, temperature can be between about 300 DEG C with about 400 DEG C, such as 350 DEG C or higher.Condensation reaction can be arrived in about 5 bars 50 bars, such as 10 bars are carried out to 30 bars, including under pressure in the range of about 15 bars to 20 bars.

Compared with other conventional methanol conversion process, alcohol component, particularly when it includes methanol and oxygenatedchemicals When (such as at least one of ketone, aldehyde, furans and ether), methanol can be improved and changed into such as fuel compounds such as gasoline or diesel oil Conversion ratio.Such one example of conventional methanol reforming technique is the technique that methanol changes into gasoline.

The higher molecular weight compound produced by condensation reaction can be included>C4 hydrocarbon, such as C4-C30 hydrocarbon, C4-C24 hydrocarbon, C4-C18 hydrocarbon or C4-C12 hydrocarbon；Or>C6 hydrocarbon, such as C6-C30 hydrocarbon, C6-C24 hydrocarbon, C6-C18 hydrocarbon or C6-C12 hydrocarbon.As made herein With term " hydrocarbon " refers to the compound containing carbon and hydrogen, and other elements that may be present are not referred to.Therefore, replace through hetero atom Compound also described herein by term " hydrocarbon ".The specific composition of the higher molecular weight compound produced by condensation reaction can To change depending on the catalyst and temperature for catalytic reduction reaction and condensation reaction and such as pressure other parameters.

Single catalyst can mediate alcohol component be transformed into be suitable for carry out condensation reaction and mediate condensation reaction sheet The form of body.Zeolite catalyst is suitable in this way being directly translated into alcohol one class catalyst of condensation product.With regard to this For point, particularly suitable zeolite catalyst can be ZSM-5, but other zeolite catalysts may also be adapted to.

On the other hand, the first catalyst can be used to mediate alcohol component to be transformed into the shape for being suitable for carrying out condensation reaction Formula, and the second catalyst can be used for mediation condensation reaction.Unless otherwise indicated, otherwise it will be appreciated that reference is made to be condensed Reaction and condensation catalyst refer to any type of condensation course.The following is the further open interior of suitable condensation catalyst Hold.Zeolite catalyst may be used as the first catalyst or the second catalyst.In addition, in this regard, particularly suitable zeolite Catalyst can be ZSM-5, but other zeolite catalysts may also be adapted to.

Various catalysis process can be used, higher molecular weight compound is formed by condensation reaction.In some embodiments In, for mediating the catalyst of condensation reaction to include basic site or acidic site and basic site.Simultaneously comprising acidity The catalyst of site and basic site will be referred to herein as multifunctional catalyst.In some or other embodiments, for being situated between One or more metallic atoms can be included by leading the catalyst of condensation reaction.If necessary, any condensation catalyst can also be optional Ground is placed on solid carrier.That is submitted on October 30th, 2013 is jointly owned entitled for solid in cellulose biomass Method and system (the Methods and Systems for Processing of lignin are processed during body hydrothermal digestion Lignin During Hydrothermal Digestion of Cellulosic Biomass Solids) United States Patent (USP) The additional detail on being adapted to catalyst is described in application 14/067330.

For example, condensation catalyst can also include zeolite and contain group ia compound (such as Li, Na, K, Cs and Rb) Other porous carriers.Preferably, the amount of group ia material is smaller than neutralizing the amount required for the acidity of carrier.Metal official Can roll into a ball can also be provided by adding group viii b metal, or Cu, Ga, In, Zn or Sn.In certain embodiments, it is condensed Catalyst can form hydrotalcite material derived from MgO and Al2O3 combination.Another condensation catalyst can comprising MgO with ZrO2 combination, or ZnO and Al2O3 combination.These materials can also each contain by copper or such as Ni, Pd, Pt VIIIB Race's metal, or the additional metal functional group that foregoing combination is provided.

The condensation reaction mediated by condensation catalyst can be carried out in any reactor for being adapted to design, the reactor Including continuous flowing type, batch-type, semi-batch or multisystem reactor, in terms of design, size, geometry, flow velocity It is unrestricted.The reactor assembly can also use fluid catalytic bed system, swing bed system, fixed bed system, moving bed The combination of each thing of system or more.In certain embodiments, can use two-phase (such as liquid-liquid) and three-phase (for example liquid-liquid- Solid) reactor progress condensation reaction.

In certain embodiments there is provided a kind of system, the system includes：The first reaction zone including reactor, it is described Reactor is arranged to heating cellulose biomass solid, molecular hydrogen, the catalyst for being catalyzed hydrogen and clears up solvent to form the One reaction product；Optional gas Disengagement zone, it includes separator unit, and the separator unit has and the described first reaction The import that area is in fluid communication, wherein the gas separator unit is arranged to remove the first reaction product Plays boiling Point is at least a portion of 100 DEG C or lower boiling volatile compound, wherein the first of the gas separator unit goes out Mouthful with liquid-liquid phase separation unit or liquid-liquid extraction unit fluid communication with by the institute of the volatile compound without the removal Reaction product is stated to provide into the liquid-liquid phase separation unit or liquid-liquid extraction unit and the light fraction separator list The second outlet of member is in fluid communication so that the volatile compound is provided to described further with the unit that is processed further Machining cell；Disengagement zone, the Disengagement zone includes：Liquid-liquid phase separation unit or liquid-liquid extraction unit, it has and described the The communication of reactor described in one reaction zone is to receive the import of first reaction product, wherein the liquid-liquid Separation units or liquid-liquid extraction unit are configured to provide for aqueous streams and non-aqueous logistics, wherein the aqueous phase is included Most of water in the part of first reaction product；For by the lightweight chemical combination at least a portion of the aqueous phase Thing is recovered in the aqueous streams Disengagement zone in overhead fraction, wherein the overhead fraction includes the part of the aqueous streams Plays boiling point is less than 150 DEG C of majority of compounds, and the aqueous streams Disengagement zone has and the liquid-liquid phase separation unit Or the communication of liquid-liquid extraction unit is to receive the import of the aqueous streams；The overhead fraction is with further adding Work area is in fluid communication；Lignin deposit unit, the lignin deposit unit and the liquid-liquid phase separation unit or the liquid- The communication of liquid extraction cells is to receive at least a portion of the non-aqueous logistics and be processed further with described The communication in area is to receive at least a portion of the hydrocarbon products；And distillation unit, the distillation unit have with The communication of the lignin deposit unit is to receive the import of lignin deposit unit outlet streams, wherein described steam Evaporate unit and be configured to provide at least overhead cut, middle distillate cut and the bottomsstream cut；And enter One step processing district, it includes being processed further unit, and the unit that is processed further has and at least one following fluid communication Import：(i) Disengagement zone, at least a portion to receive the overhead fraction from the distillation unit；(ii) The aqueous Disengagement zone, at least a portion to receive first overhead fraction from the aqueous Disengagement zone；And (iii) the gas separator unit, at least a portion of the volatile compound to receive the removal, wherein it is described enter One step processing district is configured to provide for higher hydrocarbon products.

In certain embodiments there is provided a kind of system, the system includes：The first reaction zone including reactor, it is described Reactor is arranged to heating cellulose biomass solid, molecular hydrogen, the catalyst for being catalyzed hydrogen and clears up solvent to form the One reaction product；Second reaction zone including reactor, the reactor goes out with reactor described in first reaction zone Mouth is in fluid communication to receive first reaction product, wherein the reactor in the second reaction zone is arranged to add Second reaction contents of the heat comprising first reaction product, molecular hydrogen and the catalyst for being catalyzed hydrogen are produced with forming the second reaction Thing；Optional gas Disengagement zone, it includes separator unit, the separator unit with first reaction zone and/or The import that the second reaction zone is in fluid communication, wherein the gas separator unit be arranged to remove described first and/ Or second reaction product Plays boiling point be 100 DEG C or lower boiling volatile compound at least a portion, wherein described The first outlet of light fraction separator unit is in fluid communication that will be free of with liquid-liquid phase separation unit or liquid-liquid extraction unit The reaction product of the volatile compound of the removal is provided to the liquid-liquid phase separation unit or liquid-liquid extraction unit And the second outlet of the light fraction separator unit and it is processed further unit and is in fluid communication with by the volatility Compound provides to described and is processed further unit；Disengagement zone, the Disengagement zone includes：Liquid-liquid phase separation unit or liquid-liquid extraction Unit, it has with the communication of reactor described in the second reaction zone to receive second reaction product Import, wherein the liquid-liquid phase separation unit or the liquid-liquid extraction unit are configured to provide for aqueous streams and non-aqueous Logistics, wherein most of water in the part of the aqueous phase comprising first reaction product；For by the aqueous phase Light compounds at least a portion are recovered in the aqueous streams Disengagement zone in overhead fraction, wherein the overhead fraction is included The part Plays boiling point of the aqueous streams is less than 150 DEG C of majority of compounds, the aqueous streams Disengagement zone tool There is the communication with the liquid-liquid phase separation unit or liquid-liquid extraction unit to receive the import of the aqueous streams； The overhead fraction is with being processed further area's fluid communication；Lignin deposit unit, the lignin deposit unit and the liquid- The communication of liquid phase separation unit or the liquid-liquid extraction unit is to receive at least a portion of the non-aqueous logistics And with the communication for being processed further area to receive at least a portion of the hydrocarbon products；And distillation is single Member, the distillation unit has with the communication of the lignin deposit unit to receive the outlet of lignin deposit unit The import of logistics, wherein the distillation unit be configured to provide at least overhead cut, middle distillate cut and The bottomsstream cut；And be processed further area, it includes being processed further unit, it is described be processed further unit have with At least one import being in fluid communication below：(i) Disengagement zone, evaporates to receive the tower top from the distillation unit At least a portion divided；(ii) the aqueous Disengagement zone, evaporates to receive first tower top from the aqueous Disengagement zone At least a portion divided；And (iii) described gas separator unit, to receive the volatile compound of the removal at least A part, wherein the area that is processed further is configured to provide for higher hydrocarbon products.

Any of system described above can be comprised additionally in：Lignin depolymerization unit in Disengagement zone, it is described Lignin depolymerization unit has described to receive with the communication of the liquid-liquid separation unit or liquid-liquid extraction unit At least one of import of non-aqueous logistics, wherein the lignin depolymerization unit is arranged to make the non-aqueous logistics In lignin at least partly depolymerize, wherein the outlet of the lignin depolymerization unit and the precipitation unit be in fluid communication with The non-aqueous logistics that at least part lignin depolymerization is closed is provided.The Disengagement zone can include liquid-liquid extraction unit.It is described enter one Step machining cell can be connected with the inlet fluid of liquid-liquid extraction unit at least a portion to provide higher hydrocarbon products and/or At least a portion of midbarrel.

In any of the above-described system, aqueous Disengagement zone includes：It is arranged to the first overhead fraction of manufacture and the first bottom of towe First flash vessel of cut, wherein the part Plays boiling point of first overhead fraction comprising the aqueous streams is less than 150 DEG C of majority of compounds, and wherein described second overhead fraction includes the change that normal boiling point is 150 DEG C or higher boiling point Compound；Wherein described first flash vessel includes connecting with the inlet fluid of the second flash vessel providing first tower bottom distillate To the outlet of second flash vessel.

Those skilled in the art will be apparent that, although reference feature illustrates with the one or more particular combinations measured The present invention, but these features and having in measuring many functionally independently of further feature and measure so that its can on an equal basis or Similarly it is applied independently in other embodiments or combination.

For ease of more fully understanding the present invention, there is provided the following instance of preferred embodiment.Following instance is never understood that To limit or limiting the scope of the present invention.

Illustrative example

Example 1：The distillation of total reactor inclusion

To load in 450ml Paars reactor (Parr reactor) 20.02 grams of 2- methoxyl group -4- propylphenols (MPP), Cobalt molybdate catalyst (the DC- that 190.01 grams of deionized waters, 0.4192 gram of potassium hydroxide buffer solution and 7.2522 grams of nickel oxide promote 2534, containing the 1-10% cobalt oxides being loaded on aluminum oxide and molybdenum trioxide (at most 30 weight %), and less than 2% nickel), it is described Catalyst is obtained from Criterion Catalyst＆Technologies L.P. and by US2010/0236988 examples 5 Described method is vulcanized.

Then pine broom (the southern that 14.02 grams of sizes are 3 × 5 × 5mm of nominal size is loaded into reactor Pine) small pieces (10% moisture), then uses 52 bar pressurized with hydrogen, and is heated to 190 DEG C, and holding 1 hour is then to slowly warm up to 245 DEG C, kept for 2.5 hours.

After reaction, cool down reactor and depressurize.Nominal 14 grams of wood chips are added, then with 52 bar H2 repressurizations, and phase are used Second reaction cycle is carried out with heating kenel.Described program is proceeded, it is necessary to add by the timber addition of 8 circulations 100.8 grams of seasoned woods.

After the response procedures of 8 circulations, reactor is heated overnight (15 hours) so as to be cleared up by timber at 270 DEG C The intermediate of formation is further hydrogenated and hydrodeoxygenation.

It is isolated by filtration after catalyst, short path Vigreux stills (about 4 grades) is used in 500ml 3 neck flasks Reactor content is distilled, there is the still vacuum adapter to isolate for taking out sample.

Under N2 layers of protectiveness, 230.5 grams of initial fractions are produced via distillation under atmospheric pressure, wherein distillation and bottoms Temperature is all 100+/- 1 DEG C, shows a large amount of aqueous distillate evaporations and is condensed.However, the initial fraction of overheads stream is divided while hot Into two-phase, 16.74 grams of upper stratas or top layer and 217.65 grams of lower floors are obtained.When removing distillation, apply true under nominal 100 support Sky, and continue distillation, while making bottom pot temperature slowly be warming up to 325 DEG C.18.03 grams of overheads streams are produced again.Finally Overhead product is 28.75 grams, reaches 95.98% mass balance.

By gas chromatography, 60m × 0.32mm ID and the DB-5 posts of 1 micron of thickness, 50 are used:1 split ratio, 2ml/min helium flow amounts, and chromatogram column oven keeps for 8 minutes at 40 DEG C, is then to slowly warm up to 285 with 10 DEG C/min DEG C, and 53.5 minute retention time, carry out analytical distillation product.Injector temperature setting is at 250 DEG C, and detector temperature is set Put at 300 DEG C.It was observed that a series of alkane, ketone and aldehyde list oxygen compound and residual diol intermediate, including ethylene glycol (EG), 1,2-PD (PG) and glycerine, and the initial feedback material from solvent phenolic component and the phenols group that is formed in the reaction Point.

Overhead product analysis indicates there are 31.9 weight % propylphenols (being derived from MPP) in the upper strata from overhead fraction #1 With methoxy-propyl phenol (MPP), 5.35 grams of phenols are constituted.Only 0.051 weight % is observed in the aqueous cut in bottom, is constituted Only 0.11 gram of phenolic compound.For cut #1, propylphenol and MPP summation are 16.01wt%, account for 2.89 grams.

Total tower top distillation phenols present in initial fraction #1 is collected under 100 DEG C of boilings and condensation temp 64%, but the normal boiling point of these components is more than 200 DEG C.This exception can be explained by following：Formed during distilling Second liquid phase not miscible with water and rich in phenols so that the evaporation of water evaporates these component " steam stripping " to tower tops Go out in thing.

Thus overhead produces 5.47 grams of phenols, and 3.82 grams of lightweight list oxygen compounds (ethanol, 1- propyl alcohol), and The other intermediates obtained by timber hydrodeoxygenation.

Tower bottom product forms solid tar phase in cooling, and can not be melted or topple over again when being again heated to 200 DEG C.

This example show that, the reactor product obtained by timber hydrothermal digestion is directly distilled so that heavy component largely steams Vapour is stripped in overhead product, thus makes the inefficient or invalid of the separation based on boiling point progress.

Example 2：By extract and separate, each phase is then distilled

Using 5.0035 grams of RaneyTM Co catalysts (WR Grace 2724), and comprising 21.1 grams of 2,6- xylenols Solvent repeats example 1 as phenol solvent, and 2, the 6- xylenols is dissolved into 7.00 grams of methyl isobutyl carbinols first, and It is added to together with 182.01 grams of deionized waters in 450ml reactors.Reaction cycle is carried out 1 hour at 160 DEG C, is then existed Carry out 1 hour, then carried out 3 hours at 240 DEG C at 190 DEG C.The timber addition of six circulations is carried out, then under 52 bar H2 It is heated overnight at 270 DEG C, so that intermediate completes conversion.

At the end of response procedures, 87.03 grams of toluene (the aromatic compound gasoline product of simulation) are added to reaction In device, and at 150 DEG C stirred reactor 2 hours to realize extraction.Then stop stirring, and cool down reactor.It is decanted off 127.39 grams of tops are rich in the phase of toluene, are then decanted off the phase that 220.65 grams of bottoms are rich in water.Catalyst stays in reactor bottom Portion.

At the end of separable programming, in aqueous bottoms also clearly visible flocculence or SOLID ORGANIC phase.In addition toluene In the sample obtained before, this is not mutually obvious.

Table 1 shows the distribution of reaction intermediates and solvent between top organic phase and lower aqueous.Phenolic compound two Cresols and methoxy-propyl phenol (MPP) are particularly conducive to the phase that top is rich in organic matter.Some reaction intermediates can also It is extracted in so far phase.

Table 1：The distribution coefficient of toluene extraction

Upper layer is distilled in the 250ml 3 neck flasks of short path Vigreux stills and suction vacuum adapter are equipped with. Via under N2 layers, distillation produces 79.71 grams of initial fraction # under atmospheric pressure and tower top temperature in the range of 105-120 DEG C 1.This cut contains about 89% toluene, but only containing 0.14% xylenols and undetectable methoxy-propyl phenol (in reaction Period is formed).In the presence of 2.45 weight % lightweight list oxidation products.

Second is obtained after applying nominal 100 support vacuum and continuing to distill between about 120 DEG C to 205 DEG C of column bottom temperature to evaporate Point.Cut #2 accounts for 10.01 grams.The concentration of xylenols is only 0.04 weight %, and lightweight list oxygen compound is only 0.159 weight Measure %.Estimate that toluene is 87%, and fail to detect MPP.It was observed that boiling point exceedes n-butyl alcohol but many less than xylenols Plant oxygen-containing intermediate and be used as reaction intermediates.

Under nominal 100 support vacuum, as column bottom temperature further increases, continue to distill, in the range of 205 to 340 DEG C Column bottom temperature under produce the 3rd cut comprising 22.33 grams of products.The concentration for analyzing xylenols in this cut is 47.9 weights Measure %, and via timber clear up and react formed propylphenol plus MPP accounts for 10.1 weight %.(volatility is small for light fraction In n-butyl alcohol) it is less than 0.1 weight %, and toluene is less than 7 weight %.Produced in this final high-temperature fraction more than 98% The xylenols and phenols produced in product of distillation.

Only 12.09 grams of the tower bottom product obtained by distillation, and only contain 0.42 weight % xylenols.Thus exist Tower top distillation obtains the most of xylenols recycled as solvent, is present in cut #3.Final bottoms keeps fluid Form and it can be poured out when being again heated to 200 DEG C from flask.

Obtained aqueous cut is reacted in identical equipment to 217.84 grams via independent distillation to distill.Distillation 194.2 grams of overhead products are under atmospheric pressure in the aqueous distillate of 100 DEG C of boilings.Xylenols content is only 0.118 weight %. Under 100 support vacuum, continue to distill in the case where column bottom temperature increases to 200 DEG C, produce 9.33 grams of cut #2, and in column bottom temperature Generation accounts for 5.76 grams of cut #3 when increasing to 325 DEG C.6.86 grams of final tower bottom product is dim solid, and when reheating It can not be melted again during to 200 DEG C.

Xylenols and MPP can not be detected in cut #1 and cut #2, but account in cut #3 1.00% and 0.417%.Mutually distilled relative to bottom of towe, be collected into 99.5% xylenols in upper layer (toluene phase) distillation, reflect Phenolic compound is preferentially distributed into toluene during extraction.

This result shows that phenolic compound is mainly extracted into the phase that top is rich in aromatic compound via liquid extraction In.Using extraction and separation before phase of the distillation rich in organic matter and rich in water respectively, it is included in precipitation and separation before distillation Heavy organic solid, cause efficiently separating for the component based on boiling point.It is entirely almost in the high boiling fraction being distilled to recover Higher boiling phenolic compound (more than 99%), but according to example 1, due to being distilled together with immiscible liquid phase, and be not distributed in In the cut of all generations.

In addition, separating the mobility phase that produced double distilled split-phase shows by the solid of toluene distillation extract and autoprecipitation For being made moderate progress as total distillation in example 1 or the cut produced by aqueous distillation.This flowable phase is easily entered as fuel Expect into recovery boiler, or as pitch byproduct.

Example 3：The miscible solvent of addition

Load 3.01 grams of xylenols (2,6- xylenols) into 75 milliliters of reactors of Paar 5000 and 21.07 grams are gone Ionized water, 0.107 gram of potassium carbonate buffer and the catalyst of 0.301 Cray Buddhist nun cobalt 2724 (WR Grace).What 2.0 grams of loading was ground Southern pine (nominal 10% moisture).Reactor is forced into 52 bars with hydrogen, and is heated to 190 DEG C, is kept for 1 hour, It is subsequently heated to 240 DEG C, is kept for 4 hours.

Nominal 2.0 grams of timber addition of three circulations is completed again, and last subsequent circulation is needed with pressurized with hydrogen to 35 Bar, and it is heated to 270 DEG C, 15 hours degree to expand hydrodeoxygenation reaction conversion of holding.

At the end of conversion cycles, cool down reactor and depressurize.44.3 grams of acetone of addition are included with dissolving all reactors Thing.As confirmed by magnetic attachment, the catalyst of 0.3 gram of recovery is filtrated to get, wherein in the absence of visible organic solid, and The deposit-free in sidewall of reactor or inside.The GC of the product liquid diluted for acetone, which is analyzed, to be indicated, forms the mono- oxygen of C1-C3 Compound ethylene glycol and propane diols, tetrahydrofurfuryl alcohol, the phenols (including methoxy-propyl phenol) in addition to xylenols solvent, and one Serial dihydric alcohol and single oxygen compound, including carbon number the alcohol and some ketone between 3 and 6.

This example show that at the end of biomass is cleared up with catalytic hydrogenation deoxygenation, when addition miscible solvent acetone When, form the homogeneous liquid of the only catalyst solid containing suspension.

Example 4：Add precipitating solvent

By after 270 DEG C of conversion reactions, 10 grams of toluene of addition and under agitation, the reheating under nominal 15 bar hydrogen To 150 DEG C, kept for repeat example 3 within 5 hours.Reactor is cooled down in the case where not stirring, to be separated into top phase and bottom phase.

After reactor is opened, it was observed that there is a large amount of organogenous sediments in addition to catalyst solid.These deposit stucks In in sidewall of reactor (" stickiness "), and remaining can be separated by filtering from product liquid.

This example show that biomass clear up and catalytic hydrogenation deoxygenation at the end of, by adding immiscible low pole Property and low-dielectric toluene solvant makes organic double distilled fractional precipitation.It is observable on GC to be dissolved in top phase and bottom phase Reaction product with observed in example 3 those are substantially consistent.This result shows that organogenous sediment is heavy distillat, these Cut can not be vaporized or detected by GC in GC injectors, it can not be processed into liquid via subsequent sour condensation step Body bio-fuel.

Therefore, instant invention is especially suited for the purpose and benefit that realization is previously mentioned, and wherein intrinsic those purposes and benefit Place.Specific embodiment disclosed above is exemplary, because the present invention can be aobvious and easy by those skilled in the art See that the different but equivalent modes with this paper teachings benefits are changed and put into practice.In addition, it is undesirable to structure shown in this article Make or design details is construed as limiting, unless be described in appended claims., it will thus be apparent that disclosed above Particular exemplary embodiment can be modified, combine or change, and it is all it is such change be considered as the present invention model Enclose with spirit.The exemplary disclosed present invention preferably without any key element not specifically disclosed herein and/or is being disclosed herein herein Any optional key element in the presence of put into practice.Although on " include (comprising) ", " containing (containing) " or " including (including) " various components or step describe composition and method, but these compositions and method can also " mainly by Various component or step compositions " or " being made from it ".All numerals and scope disclosed above can have a certain amount of change. When disclosing the number range with lower and upper limit, disclose particularly in the scope any digital and any is included Scope.Exactly, each value scope disclosed herein (" about a to about b " or equally, " about a to b " or equally, " about a-b " form) it is interpreted as being set forth in each numeral and scope covered in the range of wide value.In addition, unless Patentee separately explicitly and clearly defines, and otherwise the term in claims has its common accustomed meanings.In addition, Indefinite article " one (kind) (a/an) " used in claims, which is defined herein as referring to the indefinite article, to be drawn One (kind) or more than one (kind) in the key element gone out.If the usage of a word or term in this manual with drawing herein There is any contradiction in one or more patents or other documents, then should be using the definition for meeting this specification.

Claims

1. a kind of method, methods described includes：

Heating cellulose biomass solid in reactor in the first reaction zone, molecular hydrogen, the catalyst for being catalyzed hydrogen and clear up Solvent is to produce the first reaction product；

Before providing to Disengagement zone, optionally at least a portion of first reaction product is provided to gas separator unit In, include the vapor fraction that normal boiling point is 100 DEG C or lower boiling compound to reclaim；

At least a portion of first reaction product is provided to including liquid-liquid phase separation unit or liquid-liquid extraction unit To reclaim aqueous streams and non-aqueous logistics in Disengagement zone, wherein the aqueous streams are described comprising first reaction product Most of water in part；

The aqueous streams are provided to aqueous streams Disengagement zone with by the light compounds at least a portion of the aqueous phase It is recovered in overhead fraction, wherein the part Plays boiling point of the overhead fraction comprising the aqueous streams is less than 150 DEG C majority of compounds；

A part for the vapor fraction, at least a portion of the aqueous phase overhead fraction and/or the distillate tower top are evaporated At least one of at least a portion divided is provided to area is processed further, to provide higher hydrocarbon products；

There is provided to before distillation unit, by least a portion of the higher hydrocarbon products provide into the non-aqueous logistics with Precipitate at least a portion of lignin in the logistics, so as to provide slurry stream；And

At least a portion of the slurry stream is provided into distillation unit to reclaim distillate overhead fraction, in the middle of distillate Cut and distillate tower bottom distillate.

2. a kind of method, methods described includes：

At least a portion, molecular hydrogen and the catalysis hydrogen of first reaction product are heated in reactor in second reaction zone Catalyst is to produce the second reaction product；

Before providing to Disengagement zone, optionally by least one of first reaction product and second reaction product extremely A few part is provided to gas separator unit, and the steaming that normal boiling point is 100 DEG C or lower boiling compound is included to reclaim Gas cut；

At least a portion of second reaction product is provided to including liquid-liquid phase separation unit or liquid-liquid extraction unit To reclaim aqueous streams and at least one non-aqueous logistics in Disengagement zone, wherein the aqueous streams include the described second reaction production Most of water in the part of thing；

3. the method according to any preceding claims, methods described is comprised additionally in：

Before the higher hydrocarbon products are provided, by the way that at least a portion of the non-aqueous logistics is provided to lignin depolymerization Unit is so that the lignin in the non-aqueous logistics at least partly depolymerizes.

4. the method according to any preceding claims, methods described is comprised additionally in：

Extractant, which is provided to described, includes the Disengagement zone of liquid-liquid extraction unit.

5. method according to claim 4, evaporates wherein the extractant is the centre from the distillation unit At least a portion divided.

6. method according to claim 4, wherein the extractant is at least a portion of the higher hydrocarbon products.

At least a portion of the non-aqueous logistics is entered 7. according to the method described in claim 1, methods described is comprised additionally in Row flash distillation is to reclaim the overhead fraction comprising light compounds and the tower bottom distillate comprising alkyl cyclohexanol, wherein by the flash distillation The part Plays boiling point of the obtained overhead fraction comprising the non-aqueous logistics is less than 150 DEG C of most of chemical combination Thing, and the tower bottom distillate wherein obtained by flash distillation includes the compound that normal boiling point is 150 DEG C or higher boiling point；

The Part I of the tower bottom distillate obtained by flash distillation is provided into the liquid-liquid extraction unit；And

The Part II of the tower bottom distillate obtained by flash distillation is provided into the distillation unit.

8. the method according to any preceding claims, wherein described be processed further including condensation reaction.

9. method according to claim 8, wherein it is described be processed further including by the condensation reaction products provide to In after-fractionating unit.

10. the method according to any preceding claims, wherein the aqueous Disengagement zone include at least one flash vessel with Reclaim the overhead fraction.

11. method according to claim 10, wherein the aqueous Disengagement zone includes the first flash vessel and the second flash vessel, Wherein methods described is comprised additionally in：

The aqueous streams are provided to first flash vessel to reclaim the first overhead fraction and the first tower bottom distillate；

First tower bottom distillate is provided to second flash vessel and evaporated so that intermediate boiling compounds are recovered in into the second tower top Point and the second tower bottom distillate in,

The part Plays boiling point of wherein described first overhead fraction comprising the aqueous streams is less than 150 DEG C of major part Compound, and

Wherein described second overhead fraction includes the compound that normal boiling point is 150 DEG C or higher boiling point.

12. the method according to any preceding claims, methods described is comprised additionally in：

At least a portion of the middle distillate cut from the distillation unit is provided to the lignin depolymerization list Member.

13. the method according to any preceding claims, methods described is comprised additionally in：

At least a portion of the middle distillate cut from the distillation unit is provided into first reaction zone The reactor and the second reaction zone at least one of the reactor in.

14. the method according to any preceding claims, methods described is comprised additionally in：

At least a portion of the lignin of the precipitation is removed by filtering or by hydrocyclone.

15. the method according to any preceding claims, methods described is comprised additionally in：

Before providing to the distillation unit, at least a portion of lignin in the non-aqueous logistics is removed；And

At least a portion of the lignin of the removal is provided to the lignin depolymerization unit.

16. the method according to any preceding claims, wherein providing at least a portion of the hydrocarbon products to described Two distillation units are rich in the hydrocarbon-fraction of aromatic compound to reclaim, preferably by the hydrocarbon-fraction rich in aromatic compound At least a portion provided as the higher hydrocarbon products to the non-aqueous logistics.

17. the method according to any preceding claims, wherein at least a portion of the hydrocarbon products is provided to second Distillation unit is preferably relatively low by the aromatic content to reclaim the hydrocarbon-fraction that aromatic content is relatively low At least a portion of hydrocarbon-fraction is provided to the non-aqueous logistics as the higher hydrocarbon products.

18. according to the method described in claim 1, wherein Disengagement zone includes liquid-liquid extraction unit.

19. a kind of system, the system includes：

The first reaction zone including reactor, the reactor is arranged to heating cellulose biomass solid, molecular hydrogen, urged Change the catalyst of hydrogen and clear up solvent to form the first reaction product；

Optional gas Disengagement zone, it includes separator unit, and the separator unit has and the first reaction zone fluid The import of connection, wherein the gas separator unit be arranged to remove the first reaction product Plays boiling point be 100 DEG C or at least a portion of lower boiling volatile compound, wherein the first outlet of the gas separator unit with Liquid-liquid phase separation unit or liquid-liquid extraction unit are in fluid communication with by the described anti-of the volatile compound without the removal Product is answered to provide into the liquid-liquid phase separation unit or liquid-liquid extraction unit and the light fraction separator unit Second outlet is processed further with the unit fluid communication that is processed further so that the volatile compound is provided to described Unit；

Disengagement zone, the Disengagement zone includes：

Liquid-liquid phase separation unit or liquid-liquid extraction unit, it has the outlet stream with reactor described in first reaction zone Body connection to receive the import of first reaction product, wherein the liquid-liquid phase separation unit or liquid-liquid extraction unit by with Put for providing aqueous streams and non-aqueous logistics, wherein in the part of the aqueous phase comprising first reaction product Most of water；

For the aqueous streams Disengagement zone being recovered in the light compounds at least a portion of the aqueous phase in overhead fraction, The part Plays boiling point of the wherein described overhead fraction comprising the aqueous streams is less than 150 DEG C of majority of compounds, The aqueous streams Disengagement zone has the communication with the liquid-liquid phase separation unit or the liquid-liquid extraction unit To receive the import of the aqueous streams；The overhead fraction is with being processed further area's fluid communication；

Lignin deposit unit, the lignin deposit unit and the liquid-liquid phase separation unit or the liquid-liquid extraction unit Communication with receive the non-aqueous logistics at least a portion and with the outlet stream for being processed further area Body connects to receive at least a portion of the hydrocarbon products；And

Distillation unit, the distillation unit has is sunk with the communication of the lignin deposit unit with receiving lignin The import of shallow lake unit outlet streams, evaporates wherein the distillation unit is configured to provide at least overhead cut, centre Go out thing cut and the bottomsstream cut；And

Area is processed further, it includes being processed further unit, and the unit that is processed further has and at least one following stream The import of body connection：(i) Disengagement zone, at least one to receive the overhead fraction from the distillation unit Point；(ii) the aqueous Disengagement zone, at least one to receive first overhead fraction from the aqueous Disengagement zone Point；And (iii) described gas separator unit, at least a portion of the volatile compound to receive the removal, wherein The area that is processed further is configured to provide for higher hydrocarbon products.

20. a kind of system, the system includes：

Second reaction zone including reactor, the outlet fluid of the reactor and reactor described in first reaction zone connects Receiving first reaction product is passed to, wherein the reactor in the second reaction zone, which is arranged to heating, includes institute State the first reaction product, molecular hydrogen and be catalyzed the second reaction contents of the catalyst of hydrogen to form the second reaction product；

Optional gas Disengagement zone, it includes separator unit, the separator unit with first reaction zone and/or The import that the second reaction zone is in fluid communication, wherein the gas separator unit be arranged to remove described first and/ Or second reaction product Plays boiling point be 100 DEG C or lower boiling volatile compound at least a portion, wherein described The first outlet of light fraction separator unit is in fluid communication that will be free of with liquid-liquid phase separation unit or liquid-liquid extraction unit The reaction product of the volatile compound of the removal is provided to the liquid-liquid phase separation unit or liquid-liquid extraction unit And the second outlet of the light fraction separator unit and it is processed further unit and is in fluid communication with by the volatility Compound provides to described and is processed further unit；

Disengagement zone, the Disengagement zone includes：

Liquid-liquid phase separation unit or liquid-liquid extraction unit, it has the outlet stream with reactor described in the second reaction zone Body connection is to receive the import of second reaction product, wherein the liquid-liquid phase separation unit or the liquid-liquid extraction unit Aqueous streams and non-aqueous logistics are configured to provide for, wherein the aqueous phase includes the part of first reaction product In most of water；

For the aqueous streams Disengagement zone being recovered in the light compounds at least a portion of the aqueous phase in overhead fraction, The part Plays boiling point of the wherein described overhead fraction comprising the aqueous streams is less than 150 DEG C of majority of compounds, The aqueous streams Disengagement zone has with the communication of the liquid-liquid phase separation unit or liquid-liquid extraction unit to connect By the import of the aqueous streams；The overhead fraction is with being processed further area's fluid communication；