CN104903425B - What the hydro-thermal hydrogenation catalyst for biomass processed can recirculation buffer agent - Google Patents

Abstract

Provide a kind of method that hydro-thermal hydrogenation catalyst processes biomass.In the presence of at least one in clearing up solvent, ammonia or ammonia source and the hydrogenolysis catalyst of load, lignocellulose biomass solid is provided to hydrothermal digestion unit, the hydrogenolysis catalyst of described load contains (a) sulfur in the suitable carrier of incorporation, (b) Mo or W, and (c) Co, Ni or their mixture.Heat lignocellulose biomass solid in the presence of at least one in hydrogen, the hydrogenolysis catalyst of load and ammonia or ammonia source and clear up solvent, thus being formed containing multiple oxidizing hydrocarbons and the reaction mixture of ammonia.At least some of of ammonia is separated and is recycled to hydrothermal digestion unit.

Description

What the hydro-thermal hydrogenation catalyst for biomass processed can recirculation buffer agent

This application claims the U.S. Provisional Patent Application system of the pending trial of December in 2012 submission on the 19th The rights and interests of row No.61/739354.

Technical field

The present invention relates to be applicable to transport fuel and the height of industrial chemistry material from biomass preparation The hydro-thermal hydrogenation catalyst of the biomass in level hydrocarbon processes.

Background technology

Widely pay close attention to exploitation and the new technique of energy is provided from non-fossil fuel resource.Biomass are aobvious It is shown as the resource of the prospect of Fossil fuel succedaneum.Being different from Fossil fuel, biomass are also Renewable.

Biomass can serve as recyclable fuel source.A kind of biomass are plant biomass.Due to Constituting the ligno-cellulosic materials of cell wall in higher plant, plant biomass is the richest Rich carbohydrate source.Plant cell wall is divided into two parts, primary cell wall and secondary Cell wall.Primary cell wall provides for expanding the structure of cell and by three kinds of main polysaccharide (cellulose, pectin and hemicellulose) and a class glycoprotein are constituted.Growth is stopped at cell The secondary cell wall of rear formation also comprises polysaccharide and by being covalently cross-linking to the polymerization of hemicellulose Lignin strengthens.Hemicellulose and pectin are generally abundant to be existed, but cellulose is main many Sugared and the abundantest carbohydrate source.But, prepare what fuel had difficulties from cellulose Technical problem.Some factors of this difficulty are the phsyical densities of lignocellulose (such as timber), Described phsyical density is so that be difficult to the biomass knot of chemical penetration lignocellulose Structure；With the chemical complexity of lignocellulose, described chemical complexity causes being difficult to cellulose Long chain polymeric STRUCTURE DECOMPOSITION become can be used for preparing the carbohydrate of fuel.Another of this difficulty Nitrogen compound that factor is contained within biomass and sulphur compound.The nitrogen being contained in biomass Compound and sulphur compound may make the catalyst poisoning used in subsequent treatment.

Major part haulage vehicle needs the high power provided by internal-combustion and/or propelling motor Density.These electromotors need the clean of normally liquid form or at least compressed gas form Fuel.Due to its high-energy-density and pumpability thereof, liquid fuel is more portable so that process Simpler.

At present, organism-based raw material such as biomass provide the most renewable of liquid transportation fuels to replace Dai Pin.Unfortunately, the process of the new technique that liquid biofuel is prepared in exploitation is being developed particularly The liquid feul aspect speed adapting to current infrastructure slows down.Although can be from biology Matter resource prepares a large amount of fuel, such as ethanol, methanol and vegetable oil, and gaseous fuel, such as Hydrogen and methane, these fuel requirements are adapted to new distribution technology and/or the burning skill of its feature Art.The preparation of some in these fuel also tends to costliness, and deposits in terms of its clean carbon saving In problem.Need directly to be processed into biomass liquid fuel.

Due to need directly in conjunction with biomass by hydrolyzation with the sugared and sugared catalytic hydrogenation/hydrogenolysis of release/ Hydrogenation deoxidation, to prevent from being decomposed into heavy end (caramel or tar), as the biology of charging The process of matter is challenging.Additionally, carry out nitrogen compound and the sulfuration of authigenic material charging Compound can make hydrogenation/hydrogenolysis/hydrogenation deoxidation catalyst (such as Pt/Re catalyst) be poisoned, and reduces The activity of catalyst.

Summary of the invention

Have been found advantageous that use following catalyst system carry out the catalytic hydrogenation/hydrogenolysis of biomass/ Hydrogenation deoxidation, described caltalyst ties up to tolerate in course of reaction nitrogen and sulfur, also keeps activity, And active metal minimal loss.

In one embodiment, a kind of method includes: in clearing up solvent, ammonia or ammonia source In the presence of the hydrogenolysis catalyst of at least one and load, lignocellulose biomass solid is provided To hydrothermal digestion unit, the hydrogenolysis catalyst of described load contains in the suitable carrier of incorporation (a) sulfur, (b) Mo or W, and (c) Co, Ni or their mixture；Hydrogen, Lignocellulose is heated in the presence of at least one in the hydrogenolysis catalyst of load and ammonia or ammonia source Biomass solid and clear up solvent, is consequently formed the reaction mixture containing multiple oxidizing hydrocarbons and ammonia； And ammonia is recycled to hydrothermal digestion unit at least partially.

In one embodiment, method includes: (i) provides lignocellulose biomass；(ii) Described biomass are made to contact with clearing up solvent, pre-to form the warp containing soluble-carbohydrate The biomass processed；(iii) at least one in ammonia or ammonia source and the hydrogenolysis catalyst of load In the presence of at 150 DEG C to making institute in the reactive mixture at a temperature in the range of less than 300 DEG C State pretreated biomass to contact with hydrogen, to be formed containing multiple oxidizing hydrocarbons and the product of ammonia Solution, the hydrogenolysis catalyst of described load contains (a) sulfur, (b) mixed in suitable carrier Mo or W, and (c) Co, Ni or their mixture；(iv) by least the one of ammonia Partial recirculation is to reactant mixture or pretreated biomass.

In another embodiment, a kind of compositions comprises:

(i) lignocellulose biomass；

(ii) containing (a) sulfur mixed in suitable carrier, (b) Mo or W, and (c) Co, Ni or the hydrogenolysis catalyst of their mixture；

(iii) water；With

(iv) at least one in ammonia or ammonia source.

The features and advantages of the present invention it will be apparent to those skilled in the art that.This Skilled person can make a large amount of amendment, and described amendment falls in the spirit of the present invention.

Accompanying drawing explanation

Described accompanying drawing shows some aspect of some embodiments of the present invention, and is not used in Limit or limit the present invention.

Fig. 1 is the square stream schematically shown of an embodiment of the process 100 of the present invention Cheng Tu.

Fig. 2 is the square stream schematically shown of the another embodiment of the process 200 of the present invention Cheng Tu.

Detailed description of the invention

The hydro-thermal hydrogenation catalyst that the present invention relates to use the biomass of catalyst system processes, described Caltalyst ties up to tolerate in course of reaction in the presence of the ammonia as pH buffer agent or ammonia source Nitrogen and sulfur, keep activity the most for a long time, and active metal in catalyst is (such as cobalt or other are non- Noble metal) loss reduction.Ammonia or ammonia source can be as ammonia recirculatioies, with at hydro-thermal hydrogenation catalyst Reaction mixture is formed ammonium buffers.Have been found that ammonia or ammonia source can be can as ammonia again Effective buffer agent that the hydro-thermal hydrogenation catalyst for biomass of circulation processes.

The oxidizing hydrocarbons produced by described process can be used for being applicable to transport fuel from biomass preparation Higher hydrocarbon with industrial chemistry material.The higher hydrocarbon of preparation is used for forming transport fuel, such as, close Become gasoline, diesel oil and jet fuel, and industrial chemistry material.As used herein, Term " higher hydrocarbon " represents oxygen/carbon ratio example oxygen/carbon less than at least one component of biomass material The hydrocarbon of ratio.As used herein, term " hydrocarbon " expression mainly comprises hydrogen atom and carbon is former The organic compound of son, it is also unsubstituted hydrocarbon.In certain embodiments, the present invention Hydrocarbon also comprises hetero atom (i.e. oxygen, sulfur, phosphorus or nitrogen), and therefore term " hydrocarbon " can also wrap Containing substituted hydrocarbon.Term " soluble-carbohydrate " refers to dissolve in clears up solvent and permissible The oligosaccharide of raw material and monosaccharide (such as pentose and hexose) as hydrogenolysis.

Due to need directly in conjunction with biomass by hydrolyzation with the sugared and sugared catalytic hydrogenation/hydrogenolysis of release/ Hydrogenation deoxidation, to prevent from being decomposed into heavy end (caramel or tar), as the biology of charging The process of matter is challenging.The nitrogen compound and the sulphur compound that carry out authigenic material charging can Make hydrogenation/hydrogenolysis/hydrogenation deoxidation catalyst (such as Pt/Re catalyst) be poisoned, and reduce catalyst Activity.Reduction or the nitrogen compound of partial reduction or sulphur compound (as being present in biology In protein in matter charging and aminoacid visible those) for for activation for reduction reaction The possible poisonous substance of transition-metal catalyst of molecular hydrogen.Nitrate or the nitrogen of sulphate form Or the oxidised form of sulfur can not be used in hydrogen activation and many catalyst poisonings of reduction reaction.Raw Substance P hydrolysis starts on 120 DEG C, and continues through 200 DEG C.Sulphur compound and nitrogen compound Can by such as U.S. announce stable to 120 DEG C described in no.US2012/0152836 from Sub-exchange resin (acid) remove, but for complete N, S remove needed for basic resin without Method (weak base) or more than 60 DEG C (for strong alkali resin) more than 100 DEG C uses.From 60 DEG C Ion exchanges the temperature cycles of the reaction temperature between 120-275 DEG C and presents significant energy Loss of yield.Use during the course resistance to poisoned catalyst with can directly in conjunction with biomass by hydrolyzation and Catalytic hydrogenation/hydrogenolysis/the hydrogenation deoxidation of the sugar of gained is favourable for biomass fill process. The method of the present invention and system have the advantage that use resistance to poisoned catalyst for directly in conjunction with Catalytic hydrogenation/hydrogenolysis/the hydrogenation of the sugar of biomass by hydrolyzation and gained and other derivative intermediate takes off Oxygen, and the loss reduction that active metal is in time.

In some embodiments, at least in the oxidizing hydrocarbons produced in hydrogenolysis Divide recirculation in process and system, thus be at least a partially formed the solvent produced in situ, described Solvent is used for biomass digestion process.This recirculation can be used for carrying from biomass material in offer The solvent aspect taking nitrogen compound, sulphur compound and optional phosphorus compound is cost-effective.Additionally, By controlling the degraded of the carbohydrate in hydrogenolysis process, hydrogenation reaction can be with hydrogenolysis Carry out at a temperature of 150 DEG C to 300 DEG C together.Therefore, separate hydrogenation is optionally avoided Reaction section, and the fuel formation potentiality feeding the biomass material to process can be increased.This This process described in literary composition also produces capital cost saving and becomes this section with process operation with reaction process About.The advantage that specific embodiments is described in more detail.

In one embodiment, a kind of method includes: in clearing up solvent, ammonia or ammonia source In the presence of the hydrogenolysis catalyst of at least one and load, lignocellulose biomass solid is provided To hydrothermal digestion unit, the hydrogenolysis catalyst of described load contains in the suitable carrier of incorporation (a) sulfur, (b) Mo or W, and (c) Co, Ni or their mixture；Hydrogen, Lignocellulose is heated in the presence of at least one in the hydrogenolysis catalyst of load and ammonia or ammonia source Biomass solid and clear up solvent, is consequently formed the reaction mixture containing multiple oxidizing hydrocarbons and ammonia； And ammonia separated and is recycled to hydrothermal digestion unit at least partially.

In some embodiments, the present invention provides method, comprising: provide biomass material； Make described biomass material contact with clearing up solvent in digestion system, comprise solubility to be formed The intermediate stream of carbohydrate；In the hydrogenolysis catalyst loaded and ammonia or ammonia source at least one Make described intermediate stream contact with hydrogen in the presence of person, with formed multiple oxidizing hydrocarbons (or oxidation Intermediate) and ammonia, the hydrogenolysis catalyst of described load contains (a) sulfur and (b) Mo or W (c) Co and/or Ni, wherein the Part I of oxidizing hydrocarbons described in recirculation is to form solvent, And ammonia is recycled to reactant mixture or digestion system；And make the second of described oxidizing hydrocarbons Part contacts with catalyst, to form liquid fuel.

In another embodiment, a kind of method includes: (i) provides containing cellulose, half fibre Dimension element, lignin, nitrogen compound and the biomass of sulphur compound；(ii) described biomass are made Contact with clearing up solvent, to form the pretreated biomass containing carbohydrate；(iii) In the presence of at least one in ammonia or ammonia source and the hydrogenolysis catalyst of load, in reaction mixing Thing make described pretreated biomass directly contact with hydrogen, to form multiple oxidizing hydrocarbons, The hydrogenolysis catalyst of described load contains (a) sulfur and (b) Mo mixed in suitable carrier Or W and (c) Co and/or Ni.

Ammonia or ammonia source can continuously or semi-continuously or periodically or initially be added to reaction system (or anti- Answer mixture) in or produce in the reactive mixture so that active metal leach minimize And keep catalyst activity.Suitably ammonia source can be such as ammonium carbonate, propanoic acid ammonium, alcohol acid phosphate, Levulic acid ammonium, ammonium acetate, ammonium formate, butanoic acid ammonium, ammonium chloride and ammonium sulfate.Wish with foot The pH of reactant mixture is maintained at the amount of required pH by ammonia or the introducing reaction mixing of ammonia source In thing (or via pretreated biomass).In some reaction conditions, required pH can 3 to 10, preferably 4 to 8, in the range of more preferably 5 to 7.In other embodiments, Can wish to run reaction system under conditions of more alkaline.The amount in ammonia or ammonia source can correspondingly regulate.

Ammonia source can be ammonium salt (such as ammonium acetate) or the ammonium salt (such as ammonium sulfate) of strong acid of weak acid. Ammonia can be produced to the ammonium salt of strong acid by being added by highly basic (such as KOH or NaOH). This ammonia derivant (ammonia source) is the alkali that can be derived by ammonia.

Acetic acid is being neutralized under stress as the ammonia (or ammonia source) in the water of solvent.

NH₃+HOAc→NH₄ ⁺+OAc^-As in the water of solvent

When heated or when the pressure is reduced, reaction reverses.NH₃Gas is the most volatile group Point, therefore it orders about balance and returns to the left side, thus provides the NH of the alkali as recirculation₃Gas.

In some embodiments, can add before hydrothermal digestion unit, particularly at water Heat clears up unit when being pressurized state, can by by continuous or semi-continuous interpolation to hydrothermal digestion list Lignocellulose biomass (solid) pressurization in unit.Cellulose biomass solid is being added Before hydrothermal digestion unit, cellulose biomass solid is forced into pressurized state by atmospheric pressure Can carry out in one or more pressor areas.Can be used for pressurization lignocellulose biomass and by it Introduce the suitable pressor areas in pressurized hydrothermal digestion unit and be described in greater detail in common institute In some U.S. Patent Application Publication 20130152457 and 20130152458.Described herein Suitably pressor areas can include such as pressure vessel, pressing screw feeder etc..Implement at some In scheme, multiple pressor areas can be connected in series, thus it is biological to increase cellulose in stepwise fashion The pressure of matter solid.

With reference to Fig. 1, in an embodiment of the process 100 of the present invention, by biomass 2 There is provided to can have one or more unit and clear up unit 6, described in clear up unit 6 containing negative The hydrogenolysis catalyst that carries, clear up solvent 10 (can be from process recirculation), and in ammonia or ammonia precursor At least one, thus when together with molecular hydrogen 21 heating time produce oxidizing hydrocarbons, described load Hydrogenolysis catalyst contain (a) sulfur and (b) Mo or W and (c) Co and/or Ni or it Mixture.Oxidizing hydrocarbons, and ammonia is contained from the effluent product stream clearing up unit 28 Or at least one in ammonia precursor.Can be recycled to clear up by separating to separate from product stream 30 The ammonia of unit 6, can be by heating in separative element 36 (such as tower top stream 25) or fall Low-pressure and promote described separation.In one embodiment, digestion device-reactor can be as to draw The co-pending U. S. application no. that the 31 days October in 2012 being expressly incorporated herein by mode submits to Construct disclosed in 61/720757.

With reference to Fig. 2, in an embodiment of the process 200 of the present invention, by biomass 102 There is provided to can have one or more digestion device and clear up district 106, thus make biomass and clear up Solvent 110 contacts.Treated biological chylema 120 containing soluble-carbohydrate and contains There are the sulphur compound of authigenic material and other intermediate of nitrogen compound.Sulfur and nitrogen content are desirable The most different in biomass sources 102.At least some of of treated biomass 120 is loading Hydrogenolysis catalyst and by containing ammonium halide precursor stream supply ammonia source or ammonia at least In the presence of one in hydro-thermal hydrogenation catalyst treatment region 126 with hydrogen 121 catalytic reaction, with produce Raw containing multiple oxidizing hydrocarbons and the product stream 128 in ammonia and/or ammonia source, the hydrogenolysis of described load is urged Agent contains (a) sulfur and (b) Mo or W and (c) Co and/or Ni；From product stream (its Can be the overhead 125 containing ammonia) and product stream 130 in separation of ammonia.By containing ammonia stream The reactant mixture (such as Fig. 2) being recycled at least partially in 126, or via stream 120 (not shown) is recycled to pretreated biomass.Oxidation intermediates can be processed further At least some of to produce higher hydrocarbon, thus form liquid fuel.Clear up district 106 and hydro-thermal adds Hydrogen catalysis treatment region 126 can be carried out in same reactor or in reactor respectively.Can appoint Selection of land is washed treated before contacting in hydrogenolysis district (or hydro-thermal hydrogenation catalyst treatment region) 126 Biomass 120.If washing, the most most commonly use water as cleaning solvent.

(not shown) in another embodiment, ammonium hydroxide or ammonium halide precursor can with disappear Solution solvent, biomass, catalyst are concomitantly introduced into or introduce respectively, if ammonium hydroxide or hydrogen-oxygen Change ammonium precursor to exist in hydrogenolysis district together with the hydrogenolysis catalyst of load.

The wood fibre of any suitable (the most cheap and/or be readily obtained) type can be used Cellulosic biomass.Suitably lignocellulose biomass can be selected from but be not limited to forestry residue, Agriculture residues, herbaceous material, MSW, waste paper and recycled writing paper, pulp mill's residue and Paper mill residue and combinations thereof.Therefore, in some embodiments, biomass can include such as Corn straw, Caulis et Folium Oryzae, bagasse, Miscanthus, Sorghum vulgare Pers. slag, switchgrass, bamboo, Herba Eichhorniae, Hardwood, hardwood sheet, hard wood pulp, cork, cork sheet, soft wood pulp and/or the combination of these raw materials. Biomass can consider to select, such as but not limited to cellulose and/or hemicellulose based on following Content, content of lignin, growth time/season, growth place/cost of transportation, growth cost, Harvesting cost etc..

With clearing up before solvent processes, washable undressed biomass and/or reduced Size (such as shred, crush or peeling) is to contributing to movement biomass or mixing and dipping From clearing up the convenient size of chemical substance of solvent and certain quality.Therefore, real at some Execute in scheme, it is provided that biomass can include the plant gathering in lignocellulose-containing, such as palohierror Or softwood trees.Tree can stand peeling, be chopped into the wood chip of desired thickness, and washs to remove Any residual soil, dirt etc..

According to accreditation, it is desirable to washing with water to rinse and removing such as before clearing up solvent process Nitrate, sulfate and phosphatic simple salt, the most described simple salt will exist, and lead Cause the measurement concentration of the nitrogen compound, sulphur compound and the phosphorus compound that exist.This washing is being less than Complete at a temperature of 60 degrees Celsius, and do not occur to significantly including the hydrolysis cleared up Degree.Other nitrogen compounds, sulphur compound and phosphorus compound are bound to biomass and are more difficult to Remove, and need biomass clear up and react with realize removal.These compounds can derive Other structures in protein, aminoacid, phospholipid and biomass, and can be powerful Catalyst poison.Resistance to poisoned catalyst described herein allows some in these to be more difficult to remove It is present in the nitrogen compound in process subsequently and sulphur compound.

In clearing up district, reduced size of biomass with wherein clear up reaction clear up solvent Contact.Clear up solvent and must effectively clear up lignin.

At an aspect of described embodiment, clearing up solvent can be to comprise following Kraft class Clear up solvent: (i) is to clear up in terms of solvent at least 0.5wt%, preferably at least 4wt% at most 20wt%, more preferably to 10wt% selected from sodium hydroxide, sodium carbonate, sodium sulfide, hydrogen-oxygen Change potassium, potassium carbonate, ammonium hydroxide and at least one alkali of mixture thereof, (ii) optional with Clear up the anthraquinone of solvent meter 0 to 3%, sodium borate and/or polysulfide；(iii) water (is made For clearing up the remainder of solvent).In some embodiments, clear up solvent and can have 0.5% Active alkali between 25%, between more preferably 10 to 20%.As used herein, the term " active alkali " (AA) is the percentage ratio of the alkali cpd of combination, and it is expressed as with low water content The sodium oxide of the weight meter of biomass (drying solid biomass).Clear up generally 2 to 6, Carry out under steaming and decocting liquid in the range of preferably 3 to 5/biomass ratio.Clear up reaction from 60 DEG C, At a temperature of preferably in the range of 100 DEG C to 270 DEG C and time of staying of 0.25h to 24h Under carry out.Reaction is carried out under the following conditions: described condition effectively provides pretreated biology Mass flow and chemical liquid stream, described pretreated biological mass flow contains pretreated biomass, Described pretreated biomass have 20% less than the amount in feeding in untreated biomass Content of lignin, described chemical liquid stream contains the lignin of alkali cpd and dissolving and half fine Dimension cellulosic material.

Clearing up can be in the suitable appearance of the pressure vessel of such as carbon steel or stainless steel or similar alloy Device is carried out.Clear up district to carry out in same containers or separate container.Steaming and decocting can be with even Continuous or batch mode is carried out.Suitably pressure vessel includes but not limited to " PANDIA^TM Digester " (Voest-Alpine Industrienlagenbau GmbH, Lin Ci, Austria), " DEFIBRATOR Digester " (Sunds Defibrator AB Corporation, Si De Ge Ermo, Sweden), M&D (Messing Durkee) digester (Bauer Brothers Company, Springfield, Ohio, the U.S.) and KAMYR Digester (Andritz Inc., Glen Falls, New York, the U.S.).Depend on active alkali AA's Concentration, clears up solvent and has 10 to 14, the pH of preferably from about 12 to 13.Content can be at 100 DEG C In the range of 230 DEG C, at a temperature in the range of 130 DEG C to 180 DEG C, more preferably keep one The section time.The described time can be 0.25 to 24.0 hour, preferably 0.5 to 2 hour, heel row Go out the pretreated content in digestion device.In order to fully permeate, need the liquid of q.s Wetted to guarantee all biological surface.Supply enough liquid with provide specify clear up molten Agent/biomass ratio.The effect of bigger dilution is to reduce the concentration of active chemistry and therefore drop Low reaction speed.

Similar with those used in Kraft slurry and paper-making process solvent is cleared up using In the system of (as Kraft class clears up solvent), chemical liquid can with Kraft slurry and The mode of paper chemical regeneration similar process regenerates.

In another embodiment, there is part aqueous, preferably greater than 2 weights in water Amount %, the organic solvent that at least part of water soluble mixes can be used as clearing up solvent, to contribute to clearing up Lignin, nitrogen compound and sulphur compound.In a this embodiment, clearing up solvent is There is the water-ORGANIC SOLVENT MIXTURES of optional mineral acid accelerator (such as HCl or sulphuric acid). Demonstrate that the most water miscible oxidation solvent is for preferably clearing up solvent.In this process In, organic clear up solvent mixture can be such as methanol, ethanol, acetone, ethylene glycol, the third two Alcohol, triethylene glycol and tetrahydrofurfuryl alcohol.During at least partially soluble mixed organic solvent, all As acetic acid, oxalic acid, aspirin and salicylic organic acid also be used as catalyst (as Acid accelerator).Temperature for clearing up can be 130 to 270 DEG C, preferably 140 to 220 DEG C, Time of contact is 0.25 to 24 hour, preferably 1 to 4 hour.Preferably, tie up in systems Hold 2 to 100 bars, the most commonly pressure of 5 to 50 bars, with avoid the boiling of solvent or flash distillation from Open.

Optionally, depend on embodiment, pretreated biology can be washed before hydrogenolysis district Mass flow.In washing system, pretreated biological mass flow can be washed before hydrogenolysis to remove One or more of non-fiber cellulosic material and non-cellulosic materials.Pretreated biomass Stream washs to remove in pretreated biological mass flow with current the most under certain condition Lignin, hemicellulosic materials and salt at least some of.Such as, pretreated biomass Stream available water washing is to remove the material dissolved, including that degrade but the most accessible cellulose Compound, the lignin of dissolving and/or for steaming and decocting or during steaming and decocting (or pretreatment) produce The alkaline chemical (such as sodium compound) of any residual.By as described below further Processing (such as mechanical dehydration), scrubbed pretreated biological mass flow can be containing higher solid Body burden.

In a preferred embodiment, the pretreated biological mass flow of countercurrent washing.Washing can Carry out in digestion device at least in part and/or use separate scrubber to carry out in outside.At this In one embodiment of invention process, washing system includes more than a washing step, such as Washing for the first time, second time washing, washing for the third time etc., it produces from washing for the first time Scrubbed pretreated biological mass flow, scrubbed preprocessed from second time washing Biological mass flow etc., described biological mass flow and watery vomiting flow operation, then as scrubbed through pre- The biological mass flow processed is sent to process subsequently.Water passes through the first recirculation scrub stream and second Recirculation scrub stream recirculation, is then recycled to the 3rd recirculation scrub stream.By concentration it is The water that chemically liquid of uniting flows back to receive can be recycled to washing system as washings.It should be understood that Washing step can be carried out with any amount of step, scrubbed the locating through pre-needed for obtaining The biological mass flow of reason.It addition, washing can will be used for the pH regulator of later step to being used for hydro-thermal The required pH that hydrogenation catalyst processes.Can the most optionally add ammonium hydroxide or hydroxide Ammonium precursor, with by pH regulator to the required pH being used for the process of hydro-thermal hydrogenation catalyst.

In an embodiment of process of the present invention, biomass 102 are provided to having one Individual or multiple clear up district and/or digestion container clear up district 106, thus biomass with clear up solvent Contact.Optionally, clear up at least some of of solvent to follow again from hydrogenolysis as recirculation flow Ring.Hydrogenolysis recirculation flow can comprise a large amount of component, and including the solvent produced in situ, it can be down to Small part or be fully used as clearing up solvent.Represent whole " in situ " as the term is employed herein The component produced in process；It is not limited to use in preparation or use particular reactor, therefore with During produce component synonym.The solvent produced in situ can comprise oxidation intermediates.In order to The digestion process removing nitrogen compound and sulphur compound can change in reaction medium so that temperature Degree gradient exists in reaction medium, thus allows carrying under cellulose lower temperature than extracting Take nitrogen compound and sulphur compound.Such as, reaction sequence can include increasing from biomass material 102 The thermograde added.The most extractible solid can be removed from reaction as outlet stream.Through place The biological mass flow 120 of reason is intermediate stream, and described intermediate stream can comprise at least partially carbon The treated biomass of hydrate form.The composition of treated biological mass flow 120 is variable Change, and the most different compounds can be comprised.Preferably, the carbohydrate tool comprised There are 2 to 12 carbon atoms, even more preferably 2 to 6 carbon atoms.Carbohydrate also can have There is the oxygen/carbon ratio of 0.5:1 to 1:1.2.Also can exist containing the oligomeric carbon having more than 12 carbon atoms Hydrate.In one embodiment, in the presence of at least one in ammonia or ammonia source Containing (a) sulfur and the hydrogenolysis catalyst of the load of (b) molybdenum and/or tungsten and (c) cobalt and/or nickel In the presence of make to clear up at least some of of slurry and contact with hydrogen, to produce multiple oxidizing hydrocarbons.? In another embodiment, clearing up solvent and containing in the presence of at least one in ammonia or ammonia source There is the hydrogenolysis catalyst of the load of (a) sulfur and (b) molybdenum and/or tungsten and (c) cobalt and/or nickel In the presence of make lignocellulose biomass contact with hydrogen, to produce multiple oxidizing hydrocarbons.It is present in Ammonia in product stream or ammonia source and oxidizing hydrocarbons can divide in Disengagement zone or unit 136 or 36 From, to produce oxidizing hydrocarbons stream and the ammonia (or oxidation intermediates stream) of 126 or 6 can be recycled to. Part I from the oxidizing hydrocarbons (or oxidation intermediates stream) of product stream 130 or 30 can divide It is not recycled to clear up district 106 or hydrothermal digestion unit 6.Process oxidizing hydrocarbons (or in oxidation Mesosome stream) Part II, form liquid fuel to produce higher hydrocarbon.

Charging to step (iv) with prepare higher level hydrocarbon fuel before, use for step (ii) allow independent of oxidation intermediates to single oxide with the processing region of difference of (iii) The optimization that converts and clearing up and hydrogenating or the condition of hydrogenolysis is carried out the biomass components through clearing up Optimize.By initially carrying out at low temperatures hydrogenating and hydrogenolysis step, in step (iii) more Low reaction temperature can be conducive to the formation making heavy distillat by-product to minimize.Have been observed that But this produces rich in dihydroxylic alcohols and polyhydric alcohol is substantially free of the intermediate stream of unhydrogenated monosaccharide, The most described unhydrogenated monosaccharide will serve as heavy distillat precursor.The intermediate that major part is dissolved is subsequently Conversion can the most effectively carry out, wherein the time of staying is minimized, with The successive reaction of less desirable single oxide is avoided to form alkane or olefin by-products.With this Mode, can improve required single oxide by carrying out converting in two or more stages Overall production rate.

The organic acid (such as carboxylic acid) formed by the Partial digestion of carbohydrate ingredient is assisted The dissolving and the hydrolysis that help become complete at a temperature of about 210 DEG C.Some lignins can be Dissolve before hemicellulose, and other lignins can tolerate higher temperature.One can be comprised The Organic substance of partial oxidation intermediate (including but not limited to light alcohols and polyhydric alcohol) produces in situ Solvent can assist dissolving and the extraction of lignin and other components.

At a temperature of more than 120 DEG C, carbohydrate can be by the contracting certainly of series of complex Closing reaction degraded and form caramelan, described caramelan is considered as to be difficult to change into fuel Products Catabolite.Generally, apply temperature time in aqueous reaction conditions under can expect that some are degraded Reaction, premise is that water not exclusively suppresses oligomeric and polyreaction.

In certain embodiments, hydrolysis can temperature and 1 between 20 DEG C to 270 DEG C Carry out under pressure between atm to 100atm.Enzyme can be used to be used for water under low temperature and low pressure Solve.In comprising the embodiment of strong acid and enzymatic hydrolysis, hydrolysis can be at as little as environment At a temperature of temperature and 1 bar (100kPa) is to the pressure between 100 bars (10,100kPa) Under carry out.In some embodiments, hydrolysis can comprise hydrolyst (such as metal Or acid catalyst), to assist hydrolysis.Catalyst can be to affect appointing of hydrolysis What catalyst.Such as, suitable catalyst may include but be not limited to acid catalyst, base catalyst, Metallic catalyst and their combination in any.Acid catalyst can include organic acid such as acetic acid, first Acid, levulic acid and their combination in any.In one embodiment, acid catalyst can be Hydrogenolysis produces, and constitutes the component of oxidation intermediates stream.

In some embodiments, clearing up solvent can be containing the solvent produced in situ.Produce in situ Solvent generally comprise some can dissolved in the sulphur compound of biomass material and nitrogen compound At least one alcohol, ketone or polyhydric alcohol.Such as, alcohol can be used for dissolved nitrogen compound, sulfuration is closed Thing and optional phosphorus compound, and dissolve from used in the process of the lignin of biomass material. The solvent produced in situ may also comprise one or more organic acid.In some embodiments, exist Removing in nitrogen compound and sulphur compound by some hydrolysis of biomass material, organic acid can Serve as catalyst.Every kind of solvent composition produced in situ can pass through external source supply, in mistake Produce in journey, and be recycled to hydrolysis area, or their combination in any.Such as, anti-in hydrogenolysis A part for the oxidation intermediates produced in should can separate, for use as hydrolysis in cyclone stage The solvent that reaction situ produces.The solvent in one embodiment, produced in situ is separable, Store and be selectively implanted recirculation flow, the concentration needed for keeping in recirculation flow.

Each reactor vessel preferably includes entrance and is suitable to remove product from container or reactor The outlet of stream.In some embodiments, the container wherein occurring at least some to clear up can include Extra outlet, to allow the part of removal reaction logistics.In some embodiments, wherein The container occurring at least some to clear up can include extra entrance, to provide extra solvent or to add Add agent.

Clear up and can occur in any catalyst being suitable to solid-liquid contact.Clear up and can such as exist Single or multiple containers are carried out, wherein biomass solid be completely immersed in liquid clear up in solvent or Person contacts with solvent with trickle bed or heap Degradation Models.As another example, clearing up step can be Such as United States Patent (USP) No.7285179 (Snekkenes et al., " Continuous Digester for Cellulose Pulp including Method and Recirculation System for such Digester ") described in continuous multizone catalyst in carry out.Or, clearing up can be at tool There is the fluid bed of suspended solid or stir generation in catalyst.Clear up can for pre-washing, after It is conducted batch-wise in the same containers of washing and/or reactions steps subsequently.

In treated biological mass flow, the impact of composition relatively of various carbohydrate ingredients is at hydrogen Solve the formation of less desirable by-product (such as tar or heavy distillat) in reaction.Especially, at warp The carbon water of the low concentration existed as reducing sugar in the biological mass flow processed or contain free aldehyde radical Compound can make the formation of undesirable by-product reach minimum.In preferred embodiments, uncommon Hope have in treated biomass with total level meter concentration less than 5wt% can be easy to fall The carbohydrate of the monomeric form solved or heavy distillat precursor, cleared up district by use and urged simultaneously Change working in coordination with instead between reaction zone (its carbohydrate-modifying one-tenth oxidation intermediates that will dissolve) Should or quick liquid recirculation, thus keep total organic intermediate concentration the highest, described Organic intermediate can comprise oxidation intermediates derived from carbohydrate (such as single oxide, Dihydroxylic alcohols and/or polyhydric alcohol).

For any person in structure, the solvent from clearing up step is used to remove the big of lignin Part.In one constructs, remaining lignin (if present) can be when cooling or from hydrogen Remove when hydrolysis products stream is partially separated oxide, thus constitute the efflux of solids of precipitation.Optionally, The efflux of solids that the efflux of solids of the precipitation containing lignin can be cleared up by cooling before hydrogenolysis And formed.In another constructs, do not use and clear up lignin entrance step (iv) that solvent is removed, Wherein during processing to produce senior hydrocarbon stream, lignin can produce in evaporation or separation hydrogenolysis Precipitate during logistics.

Treated biological mass flow 120 can comprise C5 and the C6 carbon that can react in hydrogenolysis Hydrate.For including the embodiment of hydrogenolysis, oxidation intermediates is (such as sugar alcohol, polynary sugar Alcohol, carboxylic acid, ketone and/or furan) fuel can be changed into further processing in reaction.Hydrogenolysis Reaction comprises hydrogen and hydrogenolysis catalyst, to assist reaction to carry out.Various reactions can result in One or more oxidizing hydrocarbons (or oxidation intermediates stream) 130.

It is included in for carrying out a kind of suitably method of the hydrogenolysis of the biomass of carbohydrate containing In hydrogenolysis under conditions of being effectively formed the product comprising less molecule or polyhydric alcohol, Make carbohydrate or stablize hydrogen and the hydrogenolysis that hydroxy intermediate with hydrogen or mixes with applicable gas Catalyst contacts.Most generally, hydrogen is dissolved in the liquid mixture of carbohydrate, institute State liquid mixture to contact with catalyst under conditions of catalytic reaction is provided.Carbohydrate enters At least some of of material directly contacts with hydrogen in the presence of hydrogenolysis catalyst." straight by term Connect ", react carbohydrate at least some of on carry out, and without first will All carbohydrate-modifying for stable hydroxy intermediate." less as the term is employed herein Molecule or polyhydric alcohol " include any molecule with more low-molecular-weight, it can include compared with beginning carbon The lesser amount of carbon atom of hydrate or oxygen atom.In one embodiment, product Comprising less molecule, described less molecule includes polyhydric alcohol and alcohol.This aspect of hydrogenolysis need carbon- The fracture of carbon bond, wherein supply hydrogen is to meet the bonding requirement of the less molecule of gained, as such as Shown in lower example:

RC(H)₂-C(H)₂R'+H₂→RCH₃+H₃CR'

Wherein R and R' is any organic moiety.

In one embodiment, carbohydrate (the carbon hydrate of such as 5 and/or 6 carbon Thing molecule) hydrogenolysis can be used in the presence of hydrogenolysis catalyst and change into comprise propylene glycol, Ethylene glycol and the stable hydroxy intermediate of glycerol.

Hydrogenolysis catalyst can comprise the carrier material having mixed wherein or being loaded with metal component, institute Stating metal component is the active metallic compound of the catalytic hydrogenolysis to soluble-carbohydrate Or the metal compound that the catalytic hydrogenolysis to soluble-carbohydrate is active can be converted into Thing.Carrier material can include any suitable nothing being generally used for carrying catalytically-active metals component Machine oxide material.The example of the inorganic oxide material that may can use includes aluminium oxide, oxidation Silicon, silica-alumina, magnesium oxide, zirconium oxide, boron oxide, titanium oxide and this inorganic oxygen Two or more mixture any in compound.For forming the most inorganic of carrier material Oxide is aluminium oxide, silicon oxide, silica-alumina and their mixture.But, Preferential oxidation aluminum.

In the preparation of hydrogenolysis catalyst, the metal component of carbon monoxide-olefin polymeric can be by any conjunction Suitable method or apparatus mixes in carrier material, and described method or apparatus provides and is mounted with activity gold Belonging to the carrier material of precursor, therefore, compositions comprises carrier material and metal component.By metal A kind of method that component mixes in carrier material includes such as being co-mulled and made into carrier material and active metal Or metal precursor, to generate the mixture being co-mulled and made into of two kinds of components.Or, other method bag Include co-precipitation carrier material and metal component, to form the co-precipitation of carrier material and metal component Mixture.Or, in a method for optimizing, use any person's (example in known infusion process Such as incipient wetness) use metal component impregnated support material, metal component to be mixed carrier material In material.

When using infusion process to be mixed in carrier material by metal component, preferably by carrier material Material is shaped to comprise the forming particles of inorganic oxide material, the most preferably by with slaine Forming particles described in aqueous impregnation and load active metal precursor.In, with provide containing slaine molten The carrier material of the metal of liquid.In order to form forming particles, inorganic by preferably powder type Oxide material and water and (be it desired to or if necessary) peptizer and/or binding agent mix, To form the mixture that can be configured to agglomerate.Wish that mixture is for being suitable to be extruded as extrudate grain The form of the extrudable paste of son, described extrudate particle can have such as cylinder, trilobal Deng various shape and such as 1/16 ", 1/8 ", 3/16 " etc. nominal size.Therefore, this The carrier material of bright compositions preferably comprises the forming particles of inorganic oxide material.

Forming particles through calcining can have at 1m²/ g to 500m²Surface area in/g range (by using N₂BET method, ASTM Test Method D 3037 measures).

In one embodiment, use one or more containing at least one slaine water-soluble Liquid metal component impregnates the forming particles through calcining in one or more impregnation steps, wherein The metallic compound of metal salt solution is active metal or active metal precursor.In.Metallic element is (a) Molybdenum (Mo) and (b) cobalt (Co) and/or nickel (Ni).Phosphorus (P) is alternatively required group Point.For Co and Ni, slaine includes metal acetate, metal formate, metal Fructus Citri Limoniae Hydrochlorate, metal-oxide, metal hydroxides, metal carbonate, metal nitrate, metal Sulfate, and two or more in them.Preferably slaine is metal nitrate, example Such as nickel or the nitrate of cobalt, or above-mentioned both.For Mo, slaine includes metal-oxide Or metal sulfide.Preferably comprise the salt of Mo and ammonium ion, such as ammonium heptamolybdate and ammonium dimolybdate.

Phosphorus is to mix the additive in these catalyst.The phosphorus dissolubility with increase molybdenum can be added, And allow to form cobalt and/or the nickel stable solution with molybdenum for dipping.It is not intended to be limited to reason Opinion, it is believed that phosphorus also can promote hydrogenation and hydrodenitrogeneration (HDN).The ability of promotion HDN is Important ability, because the known inhibitor that nitrogen compound is HDS reaction.Phosphorus is added to this A little catalyst can increase HDN activity, owing to going to denitrogenate inhibitor, therefore from reaction medium Increase HDS activity.Phosphorus also promotes that the ability of hydrogenation is also beneficial to HDS, because the position of difficulty Some of resistance sulfur molecule are mainly via indirect mechanism approach desulfurization, and described indirect mechanism approach experiences The initial hydrogenation of the aromatic ring in these molecules.The hydrogenation activity of these catalyst is promoted to increase by phosphorus Add the desulfurization of the sulfur-containing molecules of these types.The phosphorus content of final catalyst generally 0.1 to In the range of 5.0wt%.

The pore volume of the carrier material that consideration aqueous solution is to be impregnated, selects the metal in dipping solution The concentration of compound, to provide required tenor in the final composition of hydrogenolysis catalyst. Generally, the concentration of the metallic compound in dipping solution is in the range of 0.01 to 100 mol/L.

Cobalt, nickel or combinations thereof can be with 0.5wt% to 20wt%, and preferably 1wt% is extremely Amount in the range of 15wt%, most preferably 1wt% to 12wt% be present in have incorporation wherein Metal component carrier material in, using the metal component (b) as metal oxide form (c) meter；Molybdenum can be with 1wt% to 50wt%, preferably 2wt% to 40wt%, Amount in the range of most preferably 2wt% to 30wt% be present in have incorporation metal component therein Carrier material in, using in terms of the metal component (b) of metal oxide form and (c). The above-mentioned percentage by weight of metal component is based on dry carrier material and (to incite somebody to action " first as element Element " change to " metal oxide form ") metal component, regardless of whether the reality of metal component Border form how.

The catalyst that metal loads can cure before it loads to reactor vessel or system For use as hydrogenolysis catalyst, or can vulcanize in gas phase or liquid phase activation procedure situ.One In individual embodiment, lipid soluble carbohydrate can be made under the contact conditions of the present invention former Material contacts with sulfur-containing compound, and described sulfur-containing compound can be hydrogen sulfide or be decomposed into hydrogen sulfide Compound.The example of this decomposable compound includes mercaptan, CS₂, thiophene, diformazan Base thioether (DMS), dimethyl sulfoxide (DMSO), NaHS and dimethyl disulfide (DMDS).It is further preferred that by making at hydrogen under the conditions of suitable vulcanizing treatment The compositions of reason contacts with the suitably charging source containing certain density sulphur compound.Hydro carbons is former Material sulphur compound can be organosulfur compound, particularly biomass derived raw material or other contain The organosulfur compound of sulfur aminoacid (such as cysteine).

Suitably vulcanizing treatment condition is for providing the active metal component of precursor hydrogenolysis catalyst to it Those conditions of conversion of sulfur form.Generally, precursor hydrogenolysis catalyst and sulphur compound Contact curing temperature at 150 DEG C to 450 DEG C, preferably 175 DEG C to 425 DEG C, most preferably 200 DEG C In the range of 400 DEG C.

When the soluble-carbohydrate raw material of the stand-by catalyst treatment of use is to vulcanize, sulfuration Condition can be identical with the process condition carrying out hydrogenolysis.Sulfide stress generally can at 1 bar to 70 bars, Preferably 1.5 bars are to 55 bars, in the range of most preferably 2 bars to 35 bars.Gained active catalyst It is generally of and with 0.1wt% to 40wt%, preferably 1wt% to 30wt%, most preferably 3wt% Amount to 24wt% mixes sulfur content therein, using the metal component as metal oxide form B () and (c) counts.

Carry out the condition of hydrogenolysis by type based on biomass parent material and required product (such as gasoline or diesel oil) and change.Those skilled in the art in benefit of this disclosure will know For carrying out the felicity condition reacted.Generally, hydrogenolysis can be excellent at 110 DEG C to 300 DEG C Select 170 DEG C to less than 300 DEG C, carry out at a temperature in the range of most preferably 180 DEG C to 290 DEG C.

Urge it has been found that buffer agent supply can be extended to hydrogenolysis mixture in course of reaction The agent life-span.

In one embodiment, hydrogenolysis is at 0.2 to 200 bar (20 to 20,000kPa) In the range of, in the range of preferably 20 to 140 bars (2000kPa to 14000kPa), even more Preferably carry out under the pressure in the range of 50 to 110 bars (5000 to 11000kPa).

Hydrogen used in the hydrogenolysis of the present invention can include external hydrogen, recycle hydrogen, in situ The hydrogen produced and their combination in any.

In one embodiment, compared to the reaction causing reactant to be reformed, use hydrogenolysis anti- Less carbon dioxide and more substantial polyhydric alcohol should be produced.Such as, reformation can be by from mountain Pears alcohol forms isopropanol (i.e. IPA or 2-propanol) and represents:

C₆H₁₄O₆+H₂O→4H₂+3CO₂+C₃H₈O；DHR=-40J/g-mol (equation 1)

Or, in the presence of the hydrogen, polyhydric alcohol and single oxide (such as IPA) can pass through hydrogenolysis Formed, wherein consume rather than produce hydrogen:

C₆H₁₄O₆+3H₂→2H₂O+2C₃H₈O₂；DHR=+81J/gmol (equation 2)

C₆H₁₄O₆+5H₂→4H₂O+2C₃H₈O；DHR=-339J/gmol (equation 3)

Due to the difference (existence of such as hydrogen) of reaction condition, the product of hydrogenolysis can comprise More than 25 moles of %, or the polyhydric alcohol more than 30 moles of %, this can react with post processing The conversion ratio that middle generation is bigger.It addition, use hydrogenolysis rather than carry out under the condition of reorganization Reaction may result in less than 20 moles of %, or the carbon dioxide less than 30 moles of % produces. " oxidation intermediates " is often referred to have one or more carbon atom and 1 to 3 as used herein The hydrocarbon compound (being referred to herein as C1+O1-3 hydro carbons) of the oxygen atom between individual, as many Unit's alcohol and less molecule (such as one or more polyhydric alcohol, alcohol, ketone or there is at least one Any other hydro carbons of oxygen atom).

In one embodiment, hydrogenolysis is carried out as required under neutrality or acid condition, with Hydrolysis is also accelerated in addition to hydrogenolysis.The hydrolysis of oligomeric carbohydrate can be with hydrogenation group Close, to produce the sugar alcohol that can experience hydrogenolysis.

The second aspect of hydrogenolysis needs the fracture of-OH key, such as:

RC(H)₂-OH+H₂→RCH₃+H₂O

This reaction also referred to as " hydrogenation deoxidation ", and can be carried out with C-C bond fission hydrogenolysis simultaneously. Dihydroxylic alcohols can change into single oxide via this reaction.Along with by increase temperature or with catalysis Time of contact of agent and increase reaction severe degree, due to this reaction, relative to single oxide, The concentration of polyhydric alcohol and dihydroxylic alcohols reduces.Will compared to the selectivity of C-OH key hydrogenolysis to C-C Change with catalyst type and formula.Can also occur complete deoxidation formed alkane, but such as Fruit is intended to preparation can be condensed or oligomerized into the fuel of higher molecular weight in post-processing step Single oxide or dihydroxylic alcohols and polyhydric alcohol, then completely deoxidation to form alkane the most less desirable. General it is desired that only list oxide or dihydroxylic alcohols are sent to post-processing step, because Higher Alcohol may cause being formed too much coke on condensation catalyst or oligomerisation catalyst, and alkyl Do not react in basis, and can not be combined and produce the fuel of higher molecular weight.

Therefore, in the reaction region, reactant mixture can contain:

(i) lignocellulose biomass；

(ii) containing (a) sulfur mixed in suitable carrier, (b) Mo or W, and (c) Co, Ni or the hydrogenolysis catalyst of their mixture；

(iii) water；With

(iv) at least one in ammonia or ammonia source.

In some embodiments, compositions also can comprise (v) and clears up organic solvent.At another In embodiment, catalyst also can comprise (d) phosphorus.

In one embodiment of the invention, except optional hydrogenation is (as jointly treated The hydrogen described in patent application publication no.US20110154721 and US20110282115 examined Change reaction) outside, the pretreated biomass containing carbohydrate can be in suitably reaction Container is changed into the stable hydroxy intermediate comprising corresponding 01 derivatives by hydrogenolysis.

Oxidation intermediates stream 130 can be subsequently from hydrogenolysis system is sent to further processing stage.One In a little embodiments, optional separation phase includes allowing oxidizing hydrocarbons is separated into different component Element.In some embodiments of the present invention, separation phase can receive from hydrogenolysis Oxidation intermediates stream 130, and various components are divided into two or more stream.Such as, close Suitable separator may include but be not limited to phase separator, stripper, extractor, filter or steaming Evaporate tower.In some embodiments, separator was installed before processing reaction, with by from oxygen Change and intermediate separates higher polyol and is conducive to producing higher hydrocarbon.In such an implementation, Higher polyol can be recycled back to hydrogenolysis, and other oxidation intermediates are sent to process reaction. It addition, when being recycled to digestion device 106, from separation phase containing oxidation intermediates What the outlet stream of a part may act as producing in situ clears up solvent.In one embodiment, also Separation phase can be used to remove some or all lignins from oxidation intermediates stream.Lignin Such as separation phase can be left as outlet stream as separating stream.

In one embodiment, process reaction and can include that condensation reaction is to produce fuel blends. In one embodiment, higher hydrocarbon may function as transporting the part of the fuel blends of fuel. In such an implementation, the condensation of oxidation intermediates can form the catalyst of higher hydrocarbon In the presence of carry out.Although being not intended to be limited to theory, it is believed that the preparation of higher hydrocarbon by include carbon- Carbon bond formed progressively additive reaction and carry out.Gained product includes any number of chemical combination Thing, as being described in more below.

With reference to Fig. 1, in some embodiments, comprise at least one of of oxidation intermediates Outlet stream 130 can be sent to one or more process and react.Suitably process reaction can include for One or more oxidation intermediates are condensed into the multiple catalysts of higher hydrocarbon, described higher hydrocarbon quilt It is defined as the hydro carbons containing carbon more more than oxidation intermediates precursor.Higher hydrocarbon may be constructed fuel Product.The fuel Products reacted by process and produce represent at senior hydrocarbon stream from totally The product stream of process.In one embodiment, the higher hydrocarbon reacted by process and produce Oxygen/carbon ratio is less than 0.5, or less than 0.4, or preferably smaller than 0.3.

Reaction can process oxidation intermediates, to produce fuel blends one or more process. In one embodiment, condensation reaction can be used to produce fuel blends together with other reactions, And condensation reaction can by comprise acid functional site or alkalescence functional site or the two urge Agent is catalyzed.Generally, it is not only restricted to any particular theory, it is believed that alkaline condensation reaction is logical Often by including that following series of steps forms: the dehydrogenation reaction that (1) is optional；(2) optional The dehydration being catalyzed by acids；(3) aldol reaction；(4) optional ketonization Reaction；(5) optional furan ring-opening reaction；(6) the hydrogenation condensation product of gained thus shape Become C4+ hydrocarbon；(7) their combination in any.Acid catalyzed condensation can need to appoint similarly The hydrogenation of choosing or dehydrogenation reaction, dehydration and oligomerization.Extra refining reaction can also be used (polishing reaction), so that product meets specific fuel standard, is included in hydrogen and hydrogen Change and carry out from final fuel Products, remove the reaction of functional group in the presence of catalyst.Can make With comprising alkalescence functional site, acid and alkaline functional site and optionally comprising metal official's energy Catalyst carry out condensation reaction.

In one embodiment, can use aldol reaction with produce meet diesel fuel or The fuel blends of the requirement of jet fuel.In one embodiment of the invention, current mistake The fuel productivity of journey can be more than other biological based raw material conversion process.It is not intended to be limited to theory, It is believed that ammonium hydroxide or ammonium halide precursor and used in the process of tolerance nitrogen or the catalyst of sulfur Existence extend the life-span of this catalyst by preventing the leaching of the active metal of such as cobalt.

For the ease of being more fully understood that the present invention, it is provided that in terms of some of some embodiments as Lower embodiment.Below embodiment is not to be read as limiting or limiting the gamut of the present invention.

Embodiment

Embodiment 1: ammonia buffer agent

75 milliliters of Parr5000 reactors load the 50wt% third in the deionized water of 30.21 grams Triol, the ammonium carbonate buffer agent of 0.202 gram, and the catalyst of 0.304 gram (DC-2534 contains There are 1-10% cobalt oxide on alumina and molybdenum trioxide (at most 30wt%), and are less than The nickel of 2%), described catalyst available from Criterion Catalyst & Technologies L.P., And vulcanized by the method being described in US2010/0236988 embodiment 5.

Use hydrogen that reactor is forced into 53 bars, and reactor is heated to 250 DEG C reaches 5 Hour.Obtain 5.6 final pH, show to acetic acid and as byproduct of reaction formed other Effective buffering of acid.

By using the gas chromatography analysis reactor of 60mx0.32mm ID DB-5 post to produce Thing, described post has 1 μ m thick, 50:1 split ratio, 2mL/min helium stream, and column temperature Case is maintained at 40 DEG C and reaches 8 minutes, rises to 285 DEG C with 10 DEG C/min afterwards, the retention time It it is 53.5 minutes.Injector temperature is set as 250 DEG C, and detector temperature is set as 300 ℃.GC analyzes and shows 26% conversion ratio of glycerol, is formed as the 1 of primary product, 2-the third two Alcohol, and the ethanol of a little percentage by weight and propanol.

Embodiment 2: distill with ammonia buffer agent

Reactor content the most under atmospheric pressure short-path distillation from embodiment 1. Distillation continues under the column bottom temperature of 142.5 to 245 DEG C, to generate the 50.1% of initial charge Overhead product.The pH average out to 7.5 of distillation, and comprise the final of the 8% of initial charge Distillation sample obtains the pH of 8.6.The pH of residue tower bottom distillate is 6.6.

This embodiment illustrates and distill the ammonia buffer agent ability as alkali at tower top, described ammonia buffers Agent can recirculation to neutralize the acidity in reaction cycle subsequently.

Embodiment 3 and 4: buffer agent recirculation

Two 75 milliliters of Parr5000 reactors equipped with 10 grams of deionized waters as solvent, 0.25 Gram from the DC-2534 catalyst of embodiment 1, and 2.7 grams of Southern Pine small pieces (39% moisture). The combination overheads from embodiment 2 of 10 grams (pH 8.6) are added to embodiment 3 In reactor.For embodiment 4, add 10 grams of deionized waters.

Use hydrogen that two reactors are forced into 52 bars, and be heated to 190 DEG C and reach 1 hour, It is heated to 250 DEG C afterwards to reach 4 hours, stirring.After clearing up and reacting, by two reactions Device cooling and decompression, then open, and reactor content is via Whatman GF/F filter paper mistake Filter, with the percentage ratio of the assessment wood solid through clearing up.For two reactors, clear up almost Completely.But, compared to the pH of 2.8 during interpolation deionized water replacement distillation, have and add The pH of the embodiment 3 of the overhead added is 3.5 at the end of reaction.

GC analyzes and shows, compared to embodiment 4, have the mesh of the embodiment 3 of the distillation of interpolation The concentration of the twice of the single oxide of mark and dihydroxylic alcohols intermediate.

The explanation of this result is via from embodiment 1 and 2 (wherein ammonium carbonate is used as buffer agent) The recirculation of overhead also distills subsequently, it is possible to buffer matter digestion device reactor is to obtain Get Geng Gao pH.

Claims (14)

1. a hydro-thermal hydrogenation catalyst processing method for biomass, comprising: (i) clear up molten By wood fibre in the presence of at least one in agent, ammonia or ammonia source and the hydrogenolysis catalyst of load Cellulosic biomass solid provides to hydrothermal digestion unit, and the hydrogenolysis catalyst of described load contains to be mixed Enter (a) sulfur in suitable carrier, (b) Mo or W, and (c) Co, Ni or they Mixture；(ii) at least one in hydrogen, the hydrogenolysis catalyst of load and ammonia or ammonia source In the presence of heat lignocellulose biomass solid and clear up solvent, be consequently formed containing multiple Oxidizing hydrocarbons and the reaction mixture of ammonia；And ammonia is recycled to water by (iii) at least partially Heat clears up unit.

2. a hydro-thermal hydrogenation catalyst processing method for biomass, comprising: (i) provides wooden Cellulose biomass；(ii) making described biomass contact with clearing up solvent, containing with formation can The pretreated biomass of soluble carbohydrate；(iii) at least in ammonia or ammonia source At 150 DEG C to the temperature in the range of less than 300 DEG C in the presence of the hydrogenolysis catalyst of person and load Under make described pretreated biomass contact with hydrogen in the reactive mixture, to be formed containing many Planting oxidizing hydrocarbons and the reaction mixture of ammonia, the hydrogenolysis catalyst of described load contains incorporation suitably (a) sulfur in carrier, (b) Mo or W, and (c) Co, Ni or their mixture； (iv) ammonia is recycled to reactant mixture or pretreated biomass at least partially.

Method the most according to claim 1 and 2, wherein said ammonia source is ammonium salt.

Method the most according to claim 3, wherein said ammonium salt is selected from ammonium carbonate, propanoic acid Ammonium, alcohol acid phosphate, levulic acid ammonium, ammonium acetate, ammonium formate, butanoic acid ammonium, ammonium chloride and sulfur Acid ammonium.

Method the most according to claim 1 and 2, wherein provides ammonia to reactant mixture.

Method the most according to claim 1 and 2, wherein ammonia produces outside reactant mixture Raw.

Method the most according to claim 1 and 2, wherein by adding highly basic to strong acid Ammonium salt in and described ammonia source is provided.

Method the most according to claim 7, wherein said highly basic is KOH or NaOH, Described ammonium salt is ammonium sulfate.

Method the most according to claim 1 and 2, wherein oxidizing hydrocarbons described in recirculation Part I, is formed with part and clears up solvent.

Method the most according to claim 2, wherein of oxidizing hydrocarbons described in recirculation A part, with the solvent in part forming step (ii).

11. according to the method described in claim 2 or 10, wherein ammonia and described oxidizing hydrocarbons Part I recirculation together.

12. according to the method described in claim 2 or 10, and wherein ammonia is turned up the soil as ammonia flow point again It is recycled to reactant mixture or pretreated biomass.

13. methods according to claim 1 and 2, the sulfur content of wherein said catalyst In the range of 0.1wt% to 40wt%, using as metal oxide form component (b) and C () counts.

14. methods according to claim 1 and 2, the Co of wherein said catalyst and/ Or Ni content is in the range of 0.5wt% to 20wt%, using the group as metal oxide form (b) and (c) is divided to count.