CN103649044A - Process for preparing polyisocyanates from biomass - Google Patents

Process for preparing polyisocyanates from biomass Download PDF

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CN103649044A
CN103649044A CN201280034368.9A CN201280034368A CN103649044A CN 103649044 A CN103649044 A CN 103649044A CN 201280034368 A CN201280034368 A CN 201280034368A CN 103649044 A CN103649044 A CN 103649044A
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aromatic substance
enrichment
dealkylation
aromatic
cut
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E·史特约弗
O·马凯莫
S·毕特利希
R·普罗卡克
M·埃米卢思
E·庞都弗朗斯
J·莱辛斯基
D·克林勒
S·迪尔雷恩
S·雄克
J·亨克尔曼
D·史都泽尔
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
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Abstract

The present invention relates to a process for preparing polyisocyanates from natural raw material sources by starting from a biomass material and preparing a composition which comprises low molecular mass aromatics that contain per molecule at least one hydroxyl group or at least one alkoxy group (oxyaromatics), reacting these oxyaromatics to form the corresponding aromatic amines, and, optionally after condensation with formaldehyde, carrying out further reaction with phosgene to form compounds containing isocyanate groups.

Description

Method by biomass-making for polymeric polyisocyanate
Background of the present invention
The present invention relates to a kind of method of being prepared polymeric polyisocyanate by natural material source, wherein by biological material, prepare a kind of composition that contains low molecular weight aromatic compounds, described low molecular weight aromatic compounds per molecule contains at least one oh group or at least one alkoxy base (containing oxygen aromatic substance (oxyaromatics)), by these, containing oxygen aromatic compound conversion, be corresponding aromatic amine, and optionally with formaldehyde condensation after, further, with phosgene reaction, obtain the compound that contains isocyanate groups.
Prior art
Polymeric polyisocyanate (according to general custom, per molecule contains compound more than 2 NCO groups hereinafter sometimes also referred to as " vulcabond ") is the valuable raw material of preparing urethane.Urethane is the plastic type with widespread use.Therefore, the world market of polymeric polyisocyanate and urethane presents high growth speed always for many years.Most important polymeric polyisocyanate is MDI(methylene radical two (phenyl isocyanate)) and TDI(tolylene diisocyanate).
First, MDI sells as the mixture of oligopolymer and isomer, and this mixture is known as polymeric MDI (PMDI, polymethylene polyphenylene polymeric polyisocyanate).Secondly, MDI sells with the form of minimum oligopolymer (being 2-ring MDI), in the molecule of the oligopolymer that this is minimum, only comprise two aromatic rings and also referred to as monomer M DI(MMDI).MMDI both also sold with the form of mixtures of various isomer with pure isomer form.The oligopolymer of PMDI and isomer form by the embodiment of preparation method, its operational condition and described method to be determined.Therefore, PMDI be take the representative instance of the product that its preparation method is best features.MMDI can be separated by separating step by the crude product (thick MDI mixture) of the method.In technical scale, described separating step is generally distillation or crystallization.
Equally first the method for preparing TDI obtains mainly comprising TDI isomer and by the thick TDI mixture of urea and the crosslinked oligopolymer of vulcabond group.The composition of described oligopolymer is determined by preparation method equally.The mixture of pure isomer or specific isomer can be obtained by separation by thick TDI mixture, and described separation generally includes fractionation by distillation step.
As the intermediate of preparation MDI, corresponding MDA(methylene radical two (aniline)) can be by ordinary method and formaldehyde condensation under the existence of an acidic catalyst.Described method can be carried out (for example DD295628 and DD238042) continuously or in batches.In addition, known vulcabond can be prepared by corresponding amine photoreactive gas.This reaction---according to type of amine---is in gas phase or liquid phase, carry out in batches or continuously.Reaction continuous production organic diisocyanate by organic primary amine photoreactive gas is repeatedly recorded and is implemented in technical scale.
Above mention the modern industry of vulcabond synthetic be all almost to carry out continuously.Generally speaking, the continuous embodiment of the method comprises a plurality of stages.In the first stage of phosgenation, amine and phosgene reaction produce corresponding urea chloride and hydrogenchloride and amine hydrochlorate.Main reaction between amine and phosgene is very fast and heat release.For the by product and the solid that produce are minimized, amine photoreactive gas---is all optionally dissolved in organic solvent---and can for example mixes rapidly.The next stage of phosgenation had both comprised that urea chloride resolved into required vulcabond and also comprises that with hydrogenchloride amine hydrochlorate phosgenation becomes urea chloride.
Liquid phase phosgene turns to and is for example described in EP-A-1616857, WO2004/056756, WO2006/130405, EP-A-1509496, EP-A-1270544 and DE-A-19961973.
For fear of the intermediate that forms undesirable amine hydrochlorate, phosgenation also can at high temperature be carried out as gas phase phosgenation.This method is described in, for example, and EP-A-593334, WO2003/045900, WO2008/086922 and the phosgenation of WO2008006775(aerosol).
In addition, phosgenation can be carried out (WO2008/049783) in supercritical solvent.Also can use isocyanic ester itself (EP-A-1401802, US6,683,204) or ionic liquid (WO06048141, WO2006048171) as solvent.
A major issue to be solved is cheap and supplies chronically suitable amine, and the availability that amine accounts for 40 to 80% and described amine of polymeric polyisocyanate production cost is limited in the international market.Described problem is for the supply particularly important of aromatic amine.
In the prior art, aromatic amine is also prepared nitryl group hydrogenation by denitrification step subsequently by corresponding aromatic substance (as benzene or toluene) conventionally to generate corresponding amine.For the preparation of nitro-aromatics, known a large amount of batch process and continuous processing.Nitrating agent is generally the mixture of nitric acid and sulfuric acid or independent nitric acid.Aromatic substance is by after nitrated and functionalized, and it answers hydrogenation to obtain corresponding amine.Hydrogenation is carried out conventionally under the existence of catalyzer, obtains the water as by product simultaneously.Industrial, its can various industrial implementation modes as fluidized-bed or fixed bed or implement in liquid phase or gas phase.
Therefore, according to prior art, prepare polymeric polyisocyanate and there is following technological deficiency:
-denitrification step and step of hydrogenation all produce needs the special waste water of processing.
-because nitro-compound is high energy (energy-rich) material with high resolution (>1000J/g), so the method must be taked complicated security measures.
-aromatic group molecule functionalized---to be provided for preparing the amine of TDI or the MDI---multi-stage method that needs are complicated.
Therefore, need to be provided for preparing the alternative method of the suitable amine of polymeric polyisocyanate.
So far, the biomass of a large amount of natural continuous productions are only usingd not half with acting on as material use or for the renewable raw materials of power generation.In order to preserve raw material resources, be necessary to have and make to substitute fossil feedstock with biomass material and become possible method.In order to realize high-level efficiency, seek to utilize completely provided biological material is Utopian.
Knownly the material stream that comes from the various digestion methods of the material that comprises xylogen and lignocellulose can be processed to obtain valuable material.
US2,057,117 have described a kind of method of preparing Vanillin, wherein, the raw material that is selected from lignocellulose, rugose wood extract and lignosulfonic acid is heated with alkali metal hydroxide aqueous solution under superatmospheric pressure, thereby and the reaction mixture obtaining is mixed with sulfuric acid and organic composition precipitated and make Vanillin be converted into soluble form.
WO99/10450 has described a kind of method that is hydrocarbon fuel by lignin conversion.In this document, xylogen is carried out to base catalysis solution coalescence and carry out subsequently hydrotreatment.Described hydrotreatment comprises hydrogenation deoxidation and mild hydrocracking.Mild hydrocracking occurs to carry out under partially hydrogenated condition at aromatic ring.
WO2008/027699A2 has described a kind of method, wherein after removing water soluble component, will originate in xylogen decarboxylation and the hydrogenation deoxidation of biomass pyrolytic and subsequently the organic product that comes from the method step be carried out to hydrocracking.
WO2010/026244 has described a kind of integral method of preparing Mierocrystalline cellulose and at least one valuable low molecular weight material, wherein
A) provide the raw material of lignocellulose-containing and this raw material digested by treatment media,
B) cut of enrichment cellulosic is separated from the material through digestion with the cellulosic cut of at least one meager set, wherein Mierocrystalline cellulose depleted fraction comprises at least a portion from step treatment media a),
C) Mierocrystalline cellulose depleted fraction is processed to obtain at least one valuable low molecular weight material, and
D) by valuable material from step c) separated in the processing product that obtains.
WO2009/108601 has described a kind of preparation method of raw material, and described raw material is for preparing the biorefinery method of biofuel from containing the raw material of xylogen.In this document, by the xylogen from pulping method black liquor or black liquor this in hydrogen-containing gas be carried under the existence of the catalyzer on amorphous oxidation carrier or crystallization oxidation carrier and carry out hydrotreatment.
WO2009/108599 discloses the content similar to WO2009/108601, focuses on paper product.
At Angew.Chem.2008, in 120,9340 – 9351, M. described the biomass catalyzing of enrichment lignocellulose transformed to obtain BTL(bio-oil (biomass-to-liquid) in biorefinery) fuel.
US2009/0227823 has described a kind of method of being prepared at least one liquid hydrocarbon product by solid hydrocarbons raw material (as ligno-cellulosic materials), wherein described raw material is carried out to catalyse pyrolysis and makes subsequently catalyse pyrolysis product carry out catalyzed reaction to obtain liquid product.
At Chem.Rev.2006, in 106,4044 – 4098, G.W.Huber etc. have described the method by biomass synthetic fuel.According to the document, ligno-cellulosic materials can be converted into liquid fuel through three different paths of initial step in principle: gasification is to produce synthetic gas, and pyrolysis is to produce bio oil, and hydrolysis is to produce sugar and xylogen.Subsequently, the bio oil obtaining in pyrolysis can be carried out under the existence of hydrogen to hydrogenation deoxidation or steam reformation.
Undocumented european patent application 10162255.3,10162256.1 and 10162259.5 has been described by the raw material digestion of lignocellulose-containing and has been prepared valuable organic materials.Undocumented european patent application 10171278.4 has been described a kind of composition, it contains the catalyzer in composition described in xylogen and at least one dispersion liquid, has also described a kind of preparation method of this composition containing catalyzer and xylogen and for the preparation of the purposes of aromatic composition.
Document about biorefinery mentioned above do not have one piece provide any by biomass material for combined the suggestion of preparing aromatic polyisocyanate and other valuable products by corresponding aromatic amine.
The problem that is provided for preparing the suitable amine of polymeric polyisocyanate unexpectedly can be by utilizing the aftertreatment by product of biological basis product to obtain valuable product and then to provide aromatic amine to solve.Particularly the material of processing lignocellulose-containing as timber or bagasse in as the reaction of the xylogen that obtains in slurrying, can obtain for preparing the particularly advantageous aromatic amine of polymeric polyisocyanate by the inventive method thus.
An importance of the present invention is to improve aromatic amine is provided economically with in ecology by utilizing the functionalized of the natural aromatic substance obtaining.
Summary of the invention
Now have been surprisingly found that, it is possible by biomass material, advantageously preparing the polymeric polyisocyanate with aromatic ring.
Therefore, first the present invention provides a kind of method of preparing polymeric polyisocyanate, wherein uses biomass material to prepare C 14with C 12isotopic ratio be 0.5x10 -12to 5x10 -12aromatic amine composition and the composition of described aromatic amine is carried out to phosgenation.
About the suitable and preferred embodiment of phosgenation, below for step g) information that provides all includes this specification sheets by reference in.
Biomass material for the preparation of the composition of aromatic amine preferably carries out at least one reaction, described reaction comprises the aromatic composition (" containing oxygen aromatic substance composition ") of decomposing to obtain containing aromatic substance, described aromatic substance per molecule contains at least one oh group and/or at least one alkoxy base, and containing oxygen aromatic substance composition, carries out amination by described.
Containing oxygen aromatic substance composition, preferably contain at least 75 % by weight based on gross weight meter, particularly preferably at least 90 % by weight, the especially monocyclic aromatics of at least 95 % by weight.
The present invention also provides a kind of method of preparing polymeric polyisocyanate, wherein
-biomass material is comprised to the reaction of decomposition, with the aromatic substance composition (" containing oxygen aromatic substance composition ") that obtains containing aromatic substance, described aromatic substance per molecule contains at least one oh group and/or at least one alkoxy base
-will be containing the amination of oxygen aromatic substance composition,
-optionally by aminate and formaldehyde source condensation,
-by aminate or by the condensation product phosgenation of (if aminate and formaldehyde source condensation) aminate and formaldehyde source.
Suitable and the preferred embodiment of decomposing about biomass material, below for step b) information that provides all includes this specification sheets by reference in.
Other reactions and/or the treatment step that about (through digestion) biomass material, can carry out, below for step c) and the information that d) provides all include by reference this specification sheets in.
About the suitable and preferred embodiment of amination, below for step e) information that provides all includes this specification sheets by reference in.Ammonia is preferred for amination.
About the suitable and preferred embodiment with formaldehyde source condensation, below for step f) information that provides all includes this specification sheets by reference in.
About the suitable and preferred embodiment of phosgenation, below for step g) information that provides all includes this specification sheets by reference in.
The present invention also provides a kind of method of preparing polymeric polyisocyanate, wherein
A) provide biomass material,
B) biomass material is decomposed,
C) material through decomposing obtaining step b) is optionally separated into the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one poor aromatic substance),
D) from step b) degradation production or from step c) the cut C1 of enrichment aromatic substance) be optionally dosed to dealkylation district and react under the existence of hydrogen and/or water vapour,
From dealkylation district, take out ejecta, and
In the future the ejecta of autospasy alkylation zone is optionally separated to obtain at least material stream D1 of one enrichment dealkylation aromatic substance) and at least one enrichment more the material of volatile components flow D2),
E) will be from step b) degradation production or from step c) the cut C1 of enrichment aromatic substance) or from steps d) in the ejecta in dealkylation district or the material of enrichment dealkylation aromatic substance stream D1) amination by the reaction of Yu An amination district
F) make from step e) aminate optionally with formaldehyde source condensation,
G) make from step e) aminate or described aminate with from f) in formaldehyde source
Condensation product phosgenation.
The present invention also provides a kind of polyisocyanate composition, wherein C 14with C 12the ratio of isotropic substance is 0.4x10 -12to 4.5x10 -12.
The present invention also provides a kind of polyisocyanate composition, and it can obtain by method as described above and below.
Polyisocyanate composition of the present invention has at least 30 nco value.
Embodiment
For the object of present patent application, term " biomass " refers to non-fossil origin vegetable material.Biomass comprise plant and the plant parts of dead, such as withered tree, straw, leaf etc.Term biomass also comprise that non-fossil origin vegetable material has wherein passed through the product of chemistry and/or physical treatment.Described product specifically comprises from lignocellulose as the product of lignin digestion and fractionation.Biomass do not comprise coal, oil, Sweet natural gas, peat and upgrading products thereof especially, as coke.
For object of the present invention, statement " containing oxygen aromatic substance " refers to the aromatic substance that per molecule contains at least one oh group and/or at least one alkoxy base.Therefore, " containing oxygen aromatic substance composition " is for containing the composition containing oxygen aromatic substance.Preferred is monocyclic aromatics or the composition with high monocyclic aromatics content containing oxygen aromatic substance.That in the inventive method, uses preferably comprises at least 75 % by weight based on gross weight meter, preferably 90 % by weight, the especially monocyclic aromatics of at least 95 % by weight containing oxygen aromatic substance composition.
Described monocycle is preferably selected from the compound of general formula (I) containing oxygen aromatic substance
Figure BDA0000455479010000071
Wherein
Radicals R 1be hydrogen or C separately independently of one another 1-C 6alkyl,
Radicals R 2independently selected from C 1-C 6alkyl, C 1-C 6hydroxyalkyl, C 1-C 6alkoxy-C 1-C 6alkyl, formyl radical, C 2-C 6acyl group, C 1-C 6alkoxy carbonyl and C 1-C 6alkyl-carbonyl oxygen base,
M is 1,2 or 3,
N be 0,1,2,3 or 4 and
M and n's and be 1 to 6 integer.
Especially, the inventive method make to provide contain monomer containing oxygen aromatic substance become possibility containing oxygen aromatic substance composition, described monomer is selected from phenol, phenol ether, cresols, xylenol, methyl catechol, verasine, Resorcinol, pyrocatechol, Resorcinol and composition thereof containing oxygen aromatic substance.
In a specific embodiment, method of the present invention comprise the monocyclic aromatics content that provides from biomass material high containing oxygen aromatic substance composition.For object of the present invention, monocyclic aromatics also refers to " monomer aromatic substance ".The polynuclear aromatic compound that contains 2 to 15 aromatic rings is also referred to as " oligomeric aromatic substance ".
In the method for the invention, if biomass material is at least decomposed once in order to prepare aromatic amine composition, obtain the aromatic substance composition as main degradation production, it contains at least 1 % by weight based on gross weight meter, particularly preferably the monocycle of at least 2 % by weight is containing oxygen aromatic substance.The ratio of monocyclic aromatics can significantly improve by other reactions and/or treatment step hereinafter described.Other components that herein obtain can advantageously be recycled in method of the present invention or process to obtain other valuable products or for generation of energy.
In a specific embodiment, provide the reaction containing the biomass material of oxygen aromatic substance composition to comprise at least one step dealkylation.The content of the monocycle dealkylation aromatic substance of the dealkylation product obtaining is by this way apparently higher than the content of the monocycle dealkylation aromatic substance of initial aromatic substance composition.This is particularly advantageous containing oxygen aromatic substance composition for being further converted to polymeric polyisocyanate.
For object of the present invention, term " dealkylation " refers to that the replacement and/or the polynuclear aromatic compound that are contained in aromatic substance composition react under the existence of hydrogen and/or water vapour, wherein these transform at least partly in this way, the compound that the compound cracking that makes substituting group be replaced and/or contain a plurality of aromatic rings by hydrogen contains lesser amt ring with formation.The substituting group being replaced by hydrogen is selected from alkyl group, oh group, alkoxy base, aryloxy group etc.For object of the present invention, term " dealkylation " also comprises the reaction that other are relevant to decrease in molecular weight, for example dehydroxylation, de-alkoxylate or aromatic substance cracking.In this article, term aromatic compound cracking refers to that the number of per molecule aromatic ring significantly reduces and the not destroyed reaction of aromatic ring itself.Yet according to the present invention, the oxygen aromatic substance per molecule that contains of the dealkylation obtaining by dealkylation has at least one oh group and/or at least one alkoxy base conventionally.
biomass material (step a) is provided
The step of the inventive method a) in, containing the material of xylogen, preferably as biomass material, provide.
The suitable raw material containing xylogen is Vinsol and the composition that contains xylogen.Herein, the content of lignin of composition is not crucial in wide region; Just when content of lignin is too low, the method is moved no longer economically.
Containing the xylogen that the raw material of xylogen preferably contains at least 10 % by weight of the dry mass meter based on material, preferably the step of at least 15 % by weight provides in a).Containing the composition of xylogen, preferably contain 10 to 100 % by weight of the dry mass meter based on material, the preferred xylogen of 15 to 95 % by weight.For object of the present invention, term dry mass is used with the meaning of standard ISO 11465.
The raw material containing xylogen that provides the inventive method used is also provided the material of lignocellulose-containing.Lignocellulose forms the structural framework of plant cell wall, and comprises xylogen, hemicellulose and the Mierocrystalline cellulose as main component.The material of other compositions of plant cell wall and the lignocellulose-containing obtaining is thus, for example silicate, can extract low molecular weight organic compound (being called extractable content, as terpenes, resin, fat), polymkeric substance as protein, nucleic acid and vegetable jelly (being called exudate) etc.
Xylogen is the biological polymer that elementary cell is mainly phenylpropyl alcohol alkane, and according to natural source, described phenylpropyl alcohol alkane can have hydroxyl by one or more methoxy substitutions and on propyl group unit on phenyl ring.Therefore, the typical structure unit of xylogen is by ehter bond and C-C para hydroxybenzene propane connected to one another, guaiacyl propane and Syringa oblata Lindl. base propane (syringylpropane).
It is no matter without further chemical treatment and the material of the lignocellulose-containing using as timber or straw with its natural composition, or as the preparation method's from xylogen (pulping process) the stream of the material containing xylogen, it is all suitable as the biomass material for the inventive method from the lignocellulose course of processing.
The spendable ligno-cellulosic materials of the present invention can for example be obtained by the timber as raw material and vegetable fibre.Preferred ligno-cellulosic materials be by timber and from wood-processing industry form with resistates those.It comprises, for example, various timber, from deciduous tree as the timber of maple, beech, pear tree, Oak Tree, alder, Chinese ash, eucalyptus, Fagus sylvatica, cherry tree, lime, nutwood, poplar tree, willow etc. and from softwood tree as the timber of Pseudotsuga menziesii (Mirbel) Franco, dragon spruce, Japanese yew, Chinese hemlock spruce, pine tree, tamarack, fir, cdear etc.Timber not only can be divided into deciduous tree timber and wood of coniferous tree also can be divided into " hardwood " and " cork ", its not respectively with term deciduous tree timber and wood of coniferous tree synonym.Contrary with hardwood, term cork refers to that lighter timber (is that kiln drying (kiln-dried) density is less than 0.55g/cm 3timber, for example willow, poplar tree, lime and nearly all wood of coniferous tree).All hardwood and all corks are all applicable to method of the present invention in principle.Timber for the inventive method can also exist by form processing, with particle form, exists.From the suitable resistates of wood-processing industry, be timber rim charge and sawdust, parquet floor bits etc.Other suitable ligno-cellulosic materials are for example flax, hemp, sisal hemp, jute, straw, coir, switchgrass (Panicum virgatum) and other natural fibers of natural fiber cellulosic material.Suitable ligno-cellulosic materials also obtains as the resistates in agricultural, as the resistates in the cereal of gathering (wheat straw, corn straw etc.), corn, sugarcane (bagasse) etc.Suitable ligno-cellulosic materials also obtains as the resistates in forestry, as the form with branch, bark, wood chip etc.Other good sources of ligno-cellulosic materials are the short rotation crops possible on relatively little area with high yield of biomass.
Be provided as the biomass material of step in a), preferably from the stream of the material containing xylogen of the ligno-cellulosic materials digestion for the preparation of Mierocrystalline cellulose (paper pulp), preferred black liquor, especially from the black liquor of Kraft digestion (vitriol digestion).
In a preferred embodiment, biomass material provides in the following manner: by the material digestion of lignocellulose-containing and from the material separation through digestion, go out the cut of enrichment cellulosic and the cut of enrichment xylogen (and being simultaneously meager set Mierocrystalline cellulose).Subsequently, the cut of enrichment xylogen is optionally used as the biomass material of the inventive method after further processing.In this embodiment, thereby the material of lignocellulose-containing is decomposed in a) for the first time in the step of the inventive method, the material that is rich in xylogen thus separated and subsequently at step b) in decompose for the second time.
The material of digestion lignocellulose-containing is known to prepare on cellulosic methodological principle.The stream of the material containing xylogen from all digestion methods well known by persons skilled in the art is suitable for use as biomass material in principle.These methods can be categorized as scale (aqueous-alkaline) method, water acid (aqueous-acidic) method and organic method substantially according to the treatment media of using.The general introduction of these methods and digestion condition can be referring to for example WO2010/026244.
For digesting the treatment media of the material of lignocellulose-containing, can at least dissolve part xylogen.On the other hand, the Mierocrystalline cellulose being contained in the material of lignocellulose-containing is conventionally insoluble to treatment media or only with not half, is dissolved in treatment media.Subsequently, preferably by the cut of filtration or centrifugation enrichment cellulosic.
Preferable separation except containing also contain xylogen be selected from following other components containing xylogen (fiber dilution) cut: for example, from hemicellulose, the Mierocrystalline cellulose of digesting material, the degradation production of mentioning component above, digestion chemical and composition thereof.
Under many circumstances, if by except containing xylogen, also contain at least one other component containing the raw material of xylogen as biomass material, step b) in decomposition be not crucial.
If by except containing xylogen, also contain at least one other component containing xylogen cut for the raw material containing xylogen is provided, the compound of at least a portion except xylogen can be at step b) decompose and remove before.From the component (organic constituent and/or inorganic process chemistry product (process chemicals)) removing containing xylogen cut, be preferably transferred to other processing and/or thermal utilization, preferably in obtaining the cellulosic preparation method of cellulose fraction, be transferred to other processing and/or thermal utilization.
In order to remove the compound of at least a portion except xylogen, first the pH that contains xylogen cut can be made as desired value.From scale method (as Kraft method), can mix to regulate with acid pH containing xylogen cut.Suitable acid is for example CO 2; Mineral acid example hydrochloric acid, sulfuric acid and phosphoric acid.CO 2(or CO 2react the carbonic acid obtaining with water) particularly preferably as acid.Preferably use from the inventive method or with the CO of the tail gas stream of the pulping process of the inventive method coupling 2.For example, the tail gas from black-liquor combustion (regeneration boiler) or limestone kiln is suitable.Tail gas for example can directly be introduced, containing the cut of xylogen or after separated (washing as Benfield by washing methods) other components and introduce.By adding CO 2and the carbonate forming and/or supercarbonate can be recycled in the pulping process of coupling in simple mode conventionally before xylogen regeneration, for example, be recycled in the black liquor of taking-up.Therefore, use CO 2to regulate, containing the pH of the cut of xylogen, the cost when using other acid is low, in addition conventionally can also good integration to pulping process.
The cut containing xylogen from water acid system can mix to regulate with alkali pH.Suitable alkali is that for example, alkali metal base, as sodium hydroxide or potassium hydroxide; Alkaline carbonate, as sodium carbonate or salt of wormwood; Alkali metal hydrocarbonate, as sodium bicarbonate or saleratus; And alkaline earth metal alkali, as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesiumcarbonate; And ammonia or amine.
Step a) in, the compound of at least a portion except xylogen is from containing removing preferably by filtering the cut of xylogen, centrifugal, extraction, precipitation, distillation, air lift or it is in conjunction with carrying out.Thereby those skilled in the art can control containing the composition of the cut of xylogen and control for step b via described separation method) composition of the raw material containing xylogen that decomposes.Removing at least partly of component except xylogen can be carried out in one or more stages.Conventional filter method is, for example, cake filtration and deep-bed filtration are (for example, as A.Rushton, A.S.Ward, R.G.Holdich:Solid-Liquid Filtration and Separation Technology, VCH Verlagsgesellschaft, Weinheim1996, 177 pages and after, K.J.Ives, in A.Rushton (editor): Mathematical Models and Design Methods in Solid-Liquid Separation, NATO ASI Series E No.88, Martinus Nijhoff, Dordrecht1985, 90 pages and later described in) and cross flow filter (for example, as J.Altmann, S.Ripperger, J.Membrane Sci.124 (1997), described in 119-128 page).Conventional separation method is described in, for example, and G.Hultsch, H.Wilkesmann, " Filtering Centrifuges, " in D.B.Purchas, Solid-Liquid Separation, Upland Press, Croydon1977,493-559 page and H.Trawinski, Die
Figure BDA0000455479010000111
?
Figure BDA0000455479010000112
von Zentrifugen, Chem.Ztg.83 (1959), in 606-612 page.The solvent not miscible with treatment media from slurrying can be for example used in extraction or at least one has xylogen and other optional required components are dissolved in the solvent of miscibility gap (miscibility gap) wherein with q.s and carry out.Without decomposing, can be undertaken by conventional distillating method well known by persons skilled in the art from the removing of component of the cut evaporation containing xylogen.For comprising that by distilling the suitable device of processing distillation tower is as being equipped with the tray column of bubble-cap, sieve plate, screen tray, regular packing, random packing element, valve, side relief outlet etc., vaporizer is as thin-film evaporator, falling-film evaporator, pump feed evaporator, Sambay vaporizer etc., and combination.
In a specific embodiment, come self-digestion ligno-cellulosic materials, also comprise that at least a portion comes the material stream containing xylogen of liquid treatment media of self-digestion for the step raw material containing xylogen a) is provided.Subsequently, preferably make the material stream containing xylogen be settled out the cut containing xylogen, subsequent portion or remove liquid ingredient completely to be provided for step b) in the raw material containing xylogen that decomposes.
Raw material containing xylogen preferably provides in the method for preparing xylogen (paper pulp), and wherein the product of the present invention of synthetic gas and at least one valuable organic liquid or liquefied material are integrated in described method.
In a specific embodiment, removing subsequently of at least a portion fluid cpds carried out in preparing the method for paper pulp.Therefore, for example, before the independent evaporation step of the female paste-making method of system or during the black liquor that takes out can be used for providing the raw material containing xylogen.
Preferably use the material containing xylogen from the ligno-cellulosic materials digesting by alkaline purification medium to flow to provide the biomass material of step in a).Preferably use black liquor, especially from vitriol, digest the black liquor of (Kraft digestion).For the material containing xylogen is provided, first acidifying from the black liquor of Kraft digestion to be settled out at least a portion xylogen existing, the separable xylogen through precipitation subsequently.Acid mentioned above is applicable to acidifying.Particularly, use CO 2.The pH of black liquor is preferably down to the value that is no more than 10.5.Xylogen through precipitation is preferably separated by filtration method.Suitable filter method be mentioned above those.As needs, separated xylogen can carry out other treatment steps of at least one step.These steps for example comprise and being further purified, and preferably use suitable washing medium washing.Suitable washing medium is for mineral acid is for example as sulfuric acid, preferably in the aqueous solution.In a specific embodiment, first pass through CO 2the black liquor that acidifying digests from Kraft, to be settled out at least a portion xylogen existing, leaches thing to prepare the material containing xylogen by filtering separation through the xylogen of precipitation and with sulfuric acid scrubbing subsequently.
A kind of by using CO 2precipitate and be described in WO2008/079072 from the method for black liquid separation xylogen, it includes this specification sheets in by reference at this.Another kind of specially suitable method is to be described in WO2006/038863(EP1797236A1) and WO2006/031175(EP1794363A1) in lignoboost method, it includes this specification sheets equally by reference in.
decompose (step b)
Step b in the inventive method), in, biomass material is decomposed to obtain following degradation production: the molecular-weight average of the component that the molecular-weight average of the component that it comprises significantly comprises lower than biomass material.
In a specific embodiment, by containing the raw material of xylogen for step b) decomposition.In this embodiment, the degradation production obtaining step b) mainly comprises molecular weight and is no more than 500g/mol, is particularly preferably no more than 400g/mol, is especially no more than the component of 300g/mol.
At step b) in decomposition principle on can carry out according to two modification, described two modification are described in more detail below.First modification comprises pyrolysis and correspondingly produces pyrolysis product.Second modification is included under the existence of liquid decomposition media reaction and correspondingly produces liquid metathesis product.
the 1st modification: pyrolysis
In first modification of the inventive method, by biomass material particularly containing the raw material of xylogen at step b) in pyrolysis.For object of the present invention, pyrolysis is thermal treatment biomass material, meanwhile, and as needs, only to introduce on a small quantity molecular oxygen.For object of the present invention, for being significantly less than the carbon comprising in biomass material, be completely oxidized to CO on a small quantity 2required amount.The amount of the molecular oxygen of introducing in pyrolysis is for to be completely oxidized to CO than the carbon comprising in biomass material 2the low preferably 50mol% at least of required amount, particularly preferably at least 75mol%, especially at least 90mol%.Pyrolysis conventionally heat absorption is carried out.In this modification of the inventive method, degradation production obtains with gaseous form at least partly.
Pyrolysis can be carried out in batches or continuously.Preferred continuous pyrolysis.
Pyrolysis is carried out at least one pyrolysis zone.Biomass material, particularly containing the raw material of xylogen, can be introduced into pyrolysis zone as worm conveyor or pneumatic transport by suitable transportation equipment.
For pyrolysis, biomass material, particularly containing the raw material of xylogen, preferably introduces to be mainly the form of solid.For object of the present invention, the form that is mainly solid means raw material for the pyrolysis content liquid under standard conditions (20 ℃, 1013 millibars) for being no more than 70 % by weight, is particularly preferably no more than 50 % by weight, the gross weight meter based on raw material.Then, biomass material, particularly containing the raw material of xylogen, as for example wet solid or pre-dried solid for pyrolysis.
Pyrolysis zone can configure in various embodiments, for example, as rotary tube furnace or fluidized bed configuration.Static fluidized-bed and circulating fluidized bed are all suitable.When pyrolysis zone is during as fluidized bed configuration, use fluidization gas steam or the gaseous mixture of (preferably from one of subsequent method step) and be introduced under (prevailing) condition at that time, be inertia microgranular additional materials as treating fluidised material.Silica sand is particularly suitable as additional materials.This bed process is described in for example US4, in 409,416A.In an alternate embodiment, pyrolysis zone comprises at least one fixed bed.Described fixed bed comprises the inertia fixed bed of at least one material and/or the catalytic activity fixed bed of at least one material.If the inventive method is used at least one fixed bed to operate as pyrolysis zone, advantageously periodical operation in this periodical operation, is carried out combustion phases to remove relative nonvolatile element from fixed bed after pyrolysis phase.
In order to carry out pyrolysis, fluidised gas can be dosed to pyrolysis zone.Preferred fluidization gas is the mixture of steam, carbonic acid gas, nitrogen etc. or these gases.
In first preferred embodiment, pyrolysis does not add hydrogen to carry out.In this embodiment, if hydrogenation reaction exists, it is mainly in dealkylation steps d) in generation.
In second preferred embodiment, pyrolysis adds hydrogen to carry out.This pyrolysis embodiment is also called hydrocracking.In hydrocracking, biomass material, particularly xylogen, the effect by hydrogen is cracked into low-molecular-weight fragment.Add the pyrolysis of hydrogen preferably in suspension, to carry out.Also preferably use catalyzer and/or carry out under super-atmospheric pressure.This method is described in for example US4, and 420,644 and H.L.Churn et al., Adv.Solar Energy, volume 4 (1988), in 91 pages.
In a further preferred embodiment, by by evaporating the black liquor from Kraft method that concentrates for pyrolysis.This method is described in for example US3, in 375,283.Black liquor mainly exists with solid form in this case.In the modification of the method, pyrolysis air-flow also obtains as product.The same solid residue obtaining can for example be recycled in pulping process.
In a specific embodiment, will be at the lower content liquid of standard conditions (20 ℃, 101 millibars) for the black liquor material that is no more than 70 % by weight, is particularly preferably no more than 50 % by weight based on black liquor material gross weight meter be for pyrolysis.
If needed, in step b), pyrolysis can be carried out under the existence of at least one pyrolysis catalysts.Suitable pyrolysis catalysts is, for example, and silicon-dioxide, aluminum oxide, aluminosilicate, the aluminosilicate with sheet structure and zeolite (as mordenite, faujusite, X zeolite, zeolite Y and ZSM-5), zirconium white or titanium dioxide.
Pyrolysis temperature is preferably 200 to 1500 ℃, and particularly preferably 250 to 1000 ℃, especially 300 to 800 ℃.
Synthesis pressure is preferably 0.5 to 250 bar (absolute value), more preferably 1.0 to 40 bar (absolute value).
The residence time under pyrolysis temperature can be several seconds to several days.In a specific embodiment, the residence time under pyrolysis temperature is 0.5 second to 5 minutes, particularly 2 seconds to 3 minutes.Particularly, the in the situation that of fluidized-bed reactor, the residence time ratio of the volumetric flow rate under pyrolytical condition by reactor cumulative volume and fluidizing gas obtains.
The appropriate method of the catalyse pyrolysis of xylogen or on-catalytic pyrolysis is for example also described in WO96/09350(Midwest Research Institute, 1996) or US4,409,416(Hydrocarbon Research Institute, 1983), in, it includes this specification sheets in by reference at this.
In pyrolysis zone, it is the pyrolysis product of gas (" pyrolysis gas ") at least partly that biomass material, particularly lignin conversion become under pyrolytical condition.In addition, pyrolysis can be created under pyrolytical condition the pyrolysis product that part exists as liquid and/or solid.
The composition of the degradation production obtaining step b) (pyrolysis product) can change along with biomass used.
Under any circumstance, the degradation production obtaining in pyrolysis step b) comprise in meaning of the present invention containing oxygen aromatic substance.Described degradation production for example, except also comprising other different aromatic substance and be selected from water vapour, rare gas element (nitrogen), non-aromatic compound, H containing oxygen aromatic substance 2, CO, CO 2, sulfocompound is as H 2other components of S etc. and composition thereof.Non-aromatic compound is preferably degraded product as methane.
The fractionation of the degradation production obtaining in pyrolysis step b) and other processing will be at step c) in describe in more detail.
the 2nd modification: the decomposition in liquid phase
In second modification of the inventive method, biomass material, particularly containing the raw material of xylogen, under the existence of liquid decomposition media at step b) in decomposition.In this modification, degradation production is at least partially in obtaining in liquid phase.
Decomposition in liquid phase can be carried out in many methods different aspect decomposition media by first-selection.Biomass material, particularly containing the raw material of xylogen, preferably under the existence of scale decomposition media, water acid decomposition medium or organic decomposition medium at step b) in decomposition.
For step b under the existence in liquid decomposition media) in decomposition for, preferably use at least one from the Mierocrystalline cellulose depleted fraction of pulping process.In a specific embodiment, this is the Mierocrystalline cellulose depleted fraction from pulping process, and it also comprises that at least a portion is from the fluid handling media of the digestion of the ligno-cellulosic materials for slurrying.
For step b) treatment media of decomposing comprises the compound that is liquid under at least one standard conditions (20 ℃ and 1013 millibars).This is preferably selected from water, acid, alkali, organic solvent and composition thereof.For being the bronsted lowry acids and bases bronsted lowry of liquid or containing acid or the liquid mixture of alkali under standard conditions, those skilled in the art can select those from mentioned below.Organic solvent is preferably selected from alcohol, as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol or phenol, glycol and many alcohol (as ethylene glycol and propylene glycol), amino alcohol (as thanomin), diethanolamine or trolamine; Aromatic substance is as benzene, toluene, ethylbenzene or dimethylbenzene; Halogenated solvent is as methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride or chlorobenzene; Aliphatic solvents is as pentane, hexane, heptane, octane, V.M.. naphtha, sherwood oil, hexanaphthene or naphthalane; Ether, as tetrahydrofuran (THF), diethyl ether, methyl tert-butyl ether or diethylene glycol monomethyl ether; Ketone, as acetone or methylethylketone; Ester, as ethyl acetate, methane amide, dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) (DMSO), acetonitrile and composition thereof.
Fluid cpds is preferably selected from water, water miscibility organic solvent and composition thereof.Described fluid cpds is particularly preferably selected from water, alcohol and composition thereof.What therefore, can be used as that fluid cpds uses is water, methyl alcohol, ethanol, water and the mixture of methyl alcohol and/or ethanol or the mixture of methyl alcohol and ethanol.
Step b) the liquid decomposition media of using in can comprise at least one alkali.Suitable alkali is alkali metal hydroxide and alkaline earth metal hydroxides, for example sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide; Alkali metal hydrocarbonate and alkali metal bicarbonates, for example sodium bicarbonate, saleratus, Calcium hydrogen carbonate or Magnesium hydrogen carbonate; Alkaline carbonate and alkaline earth metal carbonate, for example sodium carbonate, salt of wormwood, calcium carbonate or magnesiumcarbonate; Alkaline earth metal oxide, for example calcium oxide or magnesium oxide; And composition thereof.
Step b) the liquid decomposition media of using in can comprise at least one acid.
Figure BDA0000455479010000161
acid or Lewis acid are suitable in principle.Suitable
Figure BDA0000455479010000162
acid is mineral acid and acid salt and acid anhydrides.These comprise, for example, mineral acid example hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or thionamic acid, also comprise that ammonium salt is as Neutral ammonium fluoride, ammonium chloride, brometo de amonio or ammonium sulfate.Hydrosulfate as sodium pyrosulfate, sal enixum, calcium bisulfate or magnesium hydrogen sulfate be also suitable.Hydrosulphite as sodium bisulfite, Potassium hydrogen sulfite, calcium bisulfite or magnesium bisulfite be also suitable.Hydrophosphate and dihydrogen phosphate as sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium hydrogen phosphate or potassium primary phosphate be also suitable.SO 2, SO 3and CO 2also be suitable.
Other are suitable acid is organic acid and acid anhydrides thereof, for example formic acid, acetic acid, methanesulfonic, trifluoroacetic acid or tosic acid.
Suitable Lewis acid is all metal halide or semi-metal halogenide, and wherein said metal or semi-metal have electron pair gap (electron pair gap).Example is BF 3, BCl 3, BBr 3, AlF 3, AlCl 3, AlBr 3, ethylaluminum dichloride, diethyl aluminum chloride, TiF 4, TiCl 4, TiBr 4, VCl 5, FeF 3, FeCl 3, FeBr 3, ZnF 2, ZnCl 2, ZnBr 2, Cu (I) F, Cu (I) Cl, Cu (I) Br, Cu (II) F 2, Cu (II) Cl 2, Cu (II) Br 2, Sb (III) F 3, Sb (V) F 5, Sb (III) Cl 3, Sb (V) Cl 5, Nb (V) Cl 5, Sn (II) F 2, Sn (II) Cl 2, Sn (II) Br 2, Sn (IV) F 4, Sn (IV) Cl 4and Sn (IV) Br 4.
Step b) the liquid decomposition media of using in can comprise at least one salt except compound mentioned above.These salt are preferably selected from salt and oxidation products or the reduzate of bronsted lowry acids and bases bronsted lowry mentioned above.Suitable salt is that for example, the vitriol of ammonium, basic metal or alkaline-earth metal, as sodium sulfate, potassium sulfate, calcium sulfate or magnesium sulfate.The sulphite of ammonium, basic metal or alkaline-earth metal as S-WAT, potassium sulfite, calcium sulfite or magnesium sulfite be also suitable.The sulfide of ammonium, basic metal or alkaline-earth metal as sodium sulphite, potassium sulphide, sulfurated lime or magnesium sulfide be also suitable.Basic metal sulfohydrate as Sodium sulfhydrate or potassium bisulfide be also suitable.
Step b) the liquid decomposition media of using in can comprise other compounds except compound mentioned above.These particularly come the raw material of free lignocellulose-containing to prepare the well known by persons skilled in the art conventional process chemistry product of the various digestion methods of paper pulp.Use therein method and process chemistry product are well known by persons skilled in the art.
In first particularly preferred embodiment, at step b) in use alkaline decomposition media.Particularly, at least one Mierocrystalline cellulose depleted fraction from pulping process is for step b) decomposition, described Mierocrystalline cellulose depleted fraction comprises that at least a portion is from the alkaline digest medium of aforementioned pulping process.
Then, the decomposition step b) is preferably used from the Mierocrystalline cellulose depleted fraction of Kraft method (sulphate process) and is carried out.So, step b) in the decomposition media used comprise NaOH and the Na in aqueous medium 2s.In a specific embodiment, the treatment media of using in step a) comprises NaOH, the Na in aqueous medium 2s, Na 2cO 3and Na 2sO 4.
Step b) decomposition in is particularly preferably used by Kraft legal system and is carried out for the black liquor obtaining in paper pulp.In this article, can use the black liquor (" rare black liquor ") that paper pulp fiber after separating is directly obtained or the concentration stage black liquor obtaining by evaporation.If Clark and Green are at Tappi, 51 (1), 1968,44ff, middle description, it is particularly advantageous in alkaline water, decomposing.
Step b) decomposition in also can be used from the Mierocrystalline cellulose depleted fraction of soda process (sodium carbonate method) and carry out.So, step b) in the treatment media used comprise as substantially not containing the NaOH of the main ingredient in the aqueous medium of sulfocompound.
Step b) decomposition in also can be used from the Mierocrystalline cellulose depleted fraction of alkali-oxygen (alkali-oxygen) digestion and carry out.
Step b) decomposition in also can be used from the cut of the Mierocrystalline cellulose dilution of alkali-superoxide (alkali-peroxide) digestion and carry out.
Step b) decomposition in also can be used the Mierocrystalline cellulose depleted fraction digesting under the existence of comfortable anthraquinone and carry out.
Step b) decomposition in also can be used the Mierocrystalline cellulose depleted fraction from ligno-cellulosic materials digestion to carry out (also referred to as organic solvent (Organosolv) method) by organic solvent.Suitable organic solvent be mentioned above those.Especially, use and be selected from C 1-C 4alkanol, C 1-C 4the mixture of alkanol and at least one C 1-C 4the organic solvent of the mixture of alkanol and water.C 1-C 4alkanol is preferably selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol and propyl carbinol.Particular methanol, ethanol and composition thereof.At least one C 1-C 4the mixture of alkanol and water preferably comprises 10 to 99 % by weight, at least one C of 20 to 95 % by weight particularly preferably 1-C 4alkanol, the gross weight meter based on mixture.In addition the decomposition media of using in step b), also can comprise to make by oneself the additive of female paste-making method.Described additive comprises, for example, alkali metal hydroxide is as sodium hydroxide; Ammonium bisulfite and basic metal hydrosulphite and alkaline-earth metal hydrosulphite are as sodium bisulfite and magnesium bisulfite.They also comprise mineral acid example hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or thionamic acid and ammonium salt, an alkali metal salt and alkaline earth salt.Organic acid is also suitable as acid as oxalic acid, formic acid or acetic acid.Peracid is also applicable to as persulfuric acid or peracetic acid.
Comprise at least a portion and be also suitable for use in step b of the present invention from the Mierocrystalline cellulose depleted fraction of the fluid handling media of following commercial organic solvent method) in:
Alkali ethanol (Alcell) method: ethanol/water mixture is as treatment media;
Utilize alkaline sulfite (ASAM) method of anthraquinone and methyl alcohol: alkaline sulfite-anthraquinone-methyl alcohol treatment media;
Organic cellulose (Organocell) method: two-phase method, in the first stage, use organic medium and in subordinate phase, use alkaline medium, for example, in the first stage, by methyl alcohol and/or ethanol, digest and by methyl alcohol and/or ethanol, NaOH and optional anthraquinone, digest in subordinate phase;
Acetic acid (Acetosolv) method: acetic acid/hydrochloric acid mixture is as treatment media.
Decomposition in step b) under the existence of liquid decomposition media can be carried out in one or more stages.In the simplest situation, the decomposition in step b) is carried out in a stage.
Decomposition in step b) is preferably higher than carrying out under envrionment temperature.Described temperature is preferably approximately 40 to 300 ℃, particularly preferably 50 to 250 ℃.In a specific embodiments, temperature first progressively or continuously rises until reach required outlet temperature in treating processes.
Step b) decomposition in can be under reduced pressure, under environmental stress or higher than carrying out under environmental stress.The pressure of step in a) is generally 0.01 bar to 300 bar, preferably 0.1 bar to 100 bar.
The time length of the decomposition step b) is generally 0.5 minute to 7 days, preferably 5 minutes to 96 hours.
If by the Mierocrystalline cellulose depleted fraction from pulping process for step b) decomposition, decompose near the low cost transportation of advantageously carrying out keeping Mierocrystalline cellulose depleted fraction (particularly black liquor) slurrying place.Transportation is preferably carried out via pipeline.
Under any circumstance, the degradation production obtaining in the decomposition under liquid decomposition media exists in step b) comprise in meaning of the present invention containing oxygen aromatic substance.
The fractionation of the degradation production obtaining under liquid decomposition media exists step b) and other are processed at step c) in describe in more detail.
In principle, can be by step b) in the degradation production without further fractionation and/or processing that obtains for steps d) dealkylation or step e) in amination.If the degradation production obtaining step b) obtains as liquid, described product is preferably being introduced into steps d) or step e) evaporate before.A preferred embodiment of evaporation is shown in Fig. 1 and is described in below.
In another embodiment of the inventive method, step b) degradation production obtaining in is for dealkylation, (step d) or amination (are carried out fractionation and/or processing (step c) before step e).
the fractionation of degradation production and/or processing (step c)
Step b) material through decomposing obtaining in is preferably at step c) in be separated into the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one meager set aromatic substance).
Distillation method, extraction process, absorption process, membrane method are preferably passed through in fractionation or it is in conjunction with enforcement.Fractionation is particularly preferably by distillation, extraction or its combination.
If the decomposition step b) is carried out in liquid phase, step c) fractionation in is preferably undertaken by distilling and/or extracting.
In the first special embodiment of the inventive method, the biomass material that step is provided in a) is at step b) in liquid phase, decompose, and at step c) in obtain the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one meager set aromatic substance) fractionation preferably include extraction and/or distillation.
Before the fractionation of step c), from the pH of the ejecta decomposing in step b) liquid phase, be preferably made as desirable value.In a specific embodiment, will be used in step c by decompose the degradation production obtaining under the existence of alkaline decomposition media) in.Especially at least one the Mierocrystalline cellulose depleted fraction from pulping process, the especially black liquor from Kraft method are used for decomposing.Then, before degradation production fractionation, by adding acid that pH is preferably made as, be no more than 9, be particularly preferably no more than 8 value.Suitable acid is, for example, and mineral acid example hydrochloric acid, sulfuric acid and phosphoric acid and become acid compound as CO 2and H 2s.Preferably use the CO from the tail gas stream of the inventive method or the pulping process of being combined with the inventive method 2.For example, the tail gas from black-liquor combustion (regeneration boiler) or limestone kiln is suitable.At this, tail gas can directly be introduced degradation production or in other components, remove (for example by washing methods, washing as Benfield) and introduce afterwards degradation production.By adding CO 2and the carbonate and/or the supercarbonate that form are recycled in the pulping process of being for example combined with decomposition method in simple mode conventionally, for example, be recycled to the black liquor for xylogen regeneration of prior taking-up.Therefore, use CO 2cost while regulating pH than other acid of use is low, in addition CO 2use also conventionally can good integration to pulping process.The hydroxy aromatic compound obtaining in the decomposition of step b) is greater than the approximately 9 times almost salt (phenates) of conduct existence completely in pH value.In advance pH is down to <9, preferably the value of <8, can help effectively separation by distilling and/or extracting.
The fractionation distillation of the product decomposing from liquid phase obtaining step b) can be undertaken by ordinary method well known by persons skilled in the art.Preferred vapor distillation, wherein obtains the overhead product of enrichment aromatic substance.This operator scheme is utilized step b) decomposition in the aromatics fragment that obtains steam-volatile so that they from degradation production, isolate.Preferably multistage method, is wherein used for the vapor condensation heat at least one stage the evaporation in another stage.Compare with degradation production used, the product of distillation obtaining is rich in aromatic substance, and is applicable to---optionally after removing water---as raw material for optional steps d) dealkylation or step e) in amination.
Step b) fractionation from the product decomposing in liquid phase obtaining in is also preferably undertaken by extraction.At this, preferably in the method for the invention or in the integrated approach of preparing with the paper pulp of its coupling, isolate at least a portion step b) decomposition in the aromatic substance that obtains, and the resistates staying (aromatic substance, the low organic constituent of inorganic process chemistry product equal size) can be delivered to other processing and/or thermal utilization process.
Extraction can be used a kind of solvent (extraction agent) to carry out, and the aromatic substance obtaining in decomposing in described solvent is dissolved in wherein with q.s and it just forms miscibility gap with degradation production originally.Then, make extraction agent and step b) in the degradation production close contact that obtains and being separated subsequently.Described extraction can have one or more stages.
Suitable extraction agent is organic compound as aromatic hydrocarbon or non-aromatic hydrocarbon, alcohol, aldehyde, ketone, acid amides, amine and composition thereof.These comprise, for example benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, V.M.. naphtha, sherwood oil, hexanaphthene, naphthalane, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, 1-amylalcohol, 1-hexanol, 1-heptanol, 1-octanol, methylethylketone and composition thereof.
Extraction can be carried out in batches or continuously, referring at K.Sattler, and Thermische Trennverfahren, Wiley-VCH, third substantially revised and expanded edition, the description in July2001.A plurality of lock out operation in batches can carry out by series system successively, wherein will be in all cases from extraction phase isolated resistates contact with a certain proportion of fresh extraction agent and/or extraction agent adverse current carried.Batch extraction in order to carry out, in suitable container, make degradation production for example by stirring, contact by mechanical agitation with extraction agent, mixture is standing so that be separated and can occur and advantageously remove a wherein phase by removing the heavier phase of container bottom.In order to carry out continuous extraction, extraction agent and degradation production with described in being similar in batches the mode of modification in suitable device, carry continuously.
Extraction is for example carried out at least one mixer-settler associating or at least one column extractor.Suitable mixing tank comprises dynamic mixer and static mixer.
In a preferred embodiment, for obtaining the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one meager set aromatic substance) at step c) in the fractionation carried out comprise step by step following:
C1) by step b) in the degradation production that obtains extract to obtain a kind of extract of enrichment aromatic substance and a kind of resistates of meager set aromatic substance,
C2) optionally described extract is separated into the cut of extracting and enriching agent and meager set aromatic substance and the cut of enrichment aromatic substance and meager set extraction agent,
C3) by step c1) in extract or the step c2 of the enrichment aromatic substance that obtains) in the cut of the enrichment aromatic substance that obtains be introduced into steps d) and/or step e).
The pH of the degradation production obtaining before extraction, step b) can be by adding at least one acid or at least one alkali to regulate.In addition, in the situation that the multistage extracts, be introduced into the first stage degradation production pH and extract from each stage mutually the pH of isolated resistates can be by adding at least one acid or becoming acid compound or at least one alkali to regulate.Suitable acid is, for example, and mineral acid example hydrochloric acid, sulfuric acid and phosphoric acid; Or become acid compound as CO 2and H 2o.Suitable alkali is that for example, alkali metal base is as sodium hydroxide or potassium hydroxide; Alkaline carbonate is as sodium carbonate or salt of wormwood; Alkali metal hydrocarbonate is as sodium bicarbonate or saleratus; With alkaline earth metal alkali as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesiumcarbonate; And ammonia or amine.
By step c2) in extracting and separating become the cut of extracting and enriching agent and the cut C1 of enrichment aromatic substance) preferably by distillation, undertaken.
The fractionation evaporation of the extraction step c2) can be undertaken by ordinary method well known by persons skilled in the art.Suitable method is described in K.Sattler, Thermische Trennverfahren, and Wiley-VCH, third substantially revised and expanded edition, in July2001.The device that is applicable to fractionation evaporation comprises that distillation tower is as provided bubble-cap, sieve plate, screen tray, have the tray column of advising filler, internals, valve, side relief outlet etc.The divided wall column that can provide side relief outlet, recirculation unit etc. is specially suitable.Two or can be used for distillation more than the combination of two distillation towers.Vaporizer is as thin-film evaporator, falling-film evaporator, Sambay vaporizer etc. and in conjunction with being also applicable to.
If the decomposition step b) comprises pyrolysis, step c) fractionation in is preferably undertaken by absorption.
In second embodiment of the inventive method, the biomass material that step is provided in a) is at step b) in pyrolysis decompose implementing, and at step c) in fractionation to obtain the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one meager set aromatic substance), described fractionation comprises absorption.
From the ejecta of pyrolysis zone, pyrolysis gas be can not only comprise and a large amount of solid ingredients and/or liquid ingredient also comprised.These are, for example, and the relatively nonvolatile component (for example carbonaceous material) forming in pyrolysis.If by least one solid additional materials for step b) pyrolysis, the ejecta from pyrolysis zone also can comprise a large amount of described annexing ingredients.If needed, these solid ingredients and/or liquid ingredient can be at step c) in separated from pyrolysis gas by suitable device (as cyclonic separator).Separated solid additional materials is preferably recycled to pyrolysis zone.Separated other components except additional materials can be used for other purposes, for example, burn to produce heat, and this heat preferably recycles to the inventive method or in integrated approach.The CO mainly containing herein obtaining 2and water and optional O 2tail gas can utilize equally.Also can make the ejecta from pyrolysis zone that contains at least one additional materials and relatively nonvolatile component under pyrolytical condition contact in the combustion zone being physically separated with pyrolysis zone with oxygen-containing gas (preferably air), this makes relatively nonvolatile component (" the carbonaceous material ") burning forming in pyrolysis.Then, by suitable separating device, described additional materials is separated from the tail gas obtaining, and turn back to pyrolysis zone by suitable handling equipment.
In a suitable embodiment, can be direct from the ejecta of pyrolysis---without removing condensable component---be dosed to optional dealkylation district subsequently.Yet, in this embodiment, relatively non-volatile under the pyrolytical condition from the component (it is at step b) of the ejecta of pyrolysis zone and the ejecta from pyrolysis zone non-with gas form but with solid or liquid form, exist) can before being introduced into dealkylation district, isolate.In a specific embodiment, on the other hand, condensable pyrolysis product (product existing as liquid or solid under standard conditions) is isolated (after removing solid/liquid) from the ejecta of pyrolysis.This can carry out as condensation method, absorption process, absorption method, membrane separation process etc. by suitable separation method well known by persons skilled in the art.
A particularly preferred modification is to absorb.At this, make from the ejecta of pyrolysis zone and the material stream Ab1 that contains suitable solvent) contact.Contact is preferably carried out after the cooling step that can make high boiling component generation condensation.Contact for example, is carried out in suitable device (tower).The liquid stream Ab2 that contains absorbing medium and aromatics pyrolysis product) with from the ejecta of pyrolysis, compare the gas streams Ab3 of enrichment aromatics pyrolysis product) from contact device, flow out.Material stream Ab2) be preferably separated by distillation into and Ab2) compare the fraction A b4 of enrichment aromatics pyrolysis product) with Ab2) compare the fraction A b5 of meager set aromatics pyrolysis product).If needed, Ab4) further after aftertreatment as material stream C1) be dosed to the optional steps d of dealkylation subsequently) or amination step e), and Ab5) after further cooling, be recycled to absorption, i.e. Ab5) be Ab1) principal constituent.Other compositions are a certain proportion of solvents that add for compensating solvent loss.
The solvent that is suitable as absorbing medium is organic compound as aromatic hydrocarbon or non-aromatic hydrocarbon, alcohol, aldehyde, ketone, acid amides, amine and composition thereof.These comprise, for example, benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, V.M.. naphtha, sherwood oil, hexanaphthene, naphthalane, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, 1-amylalcohol, 1-hexanol, 1-heptanol, 1-octanol, acetaldehyde, acetone, methylethylketone, N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE and composition thereof.
The boiling point of solvent is preferably under the same conditions lower than the boiling point of phenol.The boiling point of solvent is particularly preferably under the same conditions than the low at least 10K of the boiling point of phenol.Solvent also preferably has high-dissolvability in water.Described solvent comprises, for example, and methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol and the trimethyl carbinol.
Many solvents as absorbing medium have vapour pressure under acceptance condition, and this makes air-flow Ab3) load leave absorption together with absorbing medium.This is particularly useful for boiling point lower than the solvent of phenol boiling point.Subsequently, leave the air-flow Ab3 of absorption) preferably remove at least partly contained solvent.From air-flow Ab3) removing preferably of solvent with the form of washing, carry out.Herein, the good aqueous solubility for the solvent that absorbs is particularly advantageous.Be loaded with solvent and optionally the washing current of aromatic hydrocarbons can for example by distilling, process.Isolated absorbing medium (optionally together with aromatic substance) is recycled to absorption step.
The degradation production obtaining in step b) not only can carry out fractionation mentioned above in step c), and can carry out other treatment steps at least one times.Other treatment steps can be before fractionation, during or carry out afterwards.
The degradation production obtaining in step b) or by the cut C1 of step c) separation) mainly comprise molecular weight 500g/mol at the most, particularly preferably 400g/mol, the especially at the most component of 300g/mol at the most.
In a specific embodiments of the present invention, by the cut C2 of the meager set aromatic substance of step c) separation) at least partly for the synthesis of the preparation of gas.
dealkylation (step d)
From step b) degradation production or from step c) the cut C1 of arene rich) be optionally dosed to dealkylation district and react under the existence of hydrogen and/or water vapour.In dealkylation, at step b) pyrolysis in form and optionally at step c) in as cut C1) separated aromatics degradation production can transform at least partly by the effect of hydrogen and/or water vapour, thereby by hydrogen and/or the cracking compound vicarious substitute base that contains a plurality of aromatic rings to form the compound with even lower level number ring.As mentioned above, " dealkylation " therefore also refers to the reaction being replaced by hydrogen without alkyl substituent, such as dehydroxylation, de-alkoxylate, aromatic substance cracking etc.The substituting group being replaced by hydrogen is preferably selected from alkyl group.
Be applicable to steps d) in dealkylation method comprise hydrodealkylation, steam dealkylation or its mixed form.The in the situation that of the pure hydrodealkylation of the present invention, by the molecular hydrogen except pyrolysis gas stream (with pure form or with other components form of mixtures of CO for example) but do not have water to be dosed to dealkylation district.The in the situation that of the pure steam dealkylation of the present invention, the water (with pure form or with the form of mixtures with other components) except pyrolysis gas stream but be dosed to dealkylation district without molecular hydrogen.Steps d) the dealkylation method in is also as the mixed form of hydrodealkylation and steam dealkylation and configure.In this case, water and the molecular hydrogen except pyrolysis gas stream is all dosed to dealkylation district.Suitable and preferred method parameter partly explanation hereinafter for hydrodealkylation and steam dealkylation.This information makes those skilled in the art can be identified for the suitable and preferred method parameter of the mixed form of hydrodealkylation and steam dealkylation.So, for dealkylation by H 2and H 2the reactant gases that O forms preferably has the H of 0.1:99.9 to 99.9:0.1 2with H 2the ratio of mixture of O.H 2with H 2the specially suitable ratio of mixture of O is about 40:60 to 60:40.
The in the situation that of steam dealkylation, the hydrogen of reaction needed forms by water and (being mainly organic) component reaction original position, and described component is included in and is dosed to adding in material mixture or in the process of steam dealkylation of steam dealkylation and forms.By water and methyl alcohol according to reaction formula CH 4+ H 2o → CO+3H 2forming the mode that hydrogen can example at this mentions.
The temperature in dealkylation district is preferably 400 to 900 ℃, particularly preferably 500 to 800 ℃.
The absolute pressure in dealkylation district is preferably 1 to 100 bar, particularly preferably 1 to 20 bar.
In first preferred embodiment, from step b) degradation production or the cut C1 of enrichment aromatic substance) carry out hydrodealkylation.For this reason, the reaction steps d) is carried out under the existence of hydrogen.
The temperature that is used for the dealkylation district of hydrodealkylation is preferably 500 to 900 ℃, particularly preferably 600 to 800 ℃.
The absolute pressure that is used for the dealkylation district of hydrodealkylation is preferably 1 to 100 bar, particularly preferably 1 to 20 bar, especially 1 to 10 bar.
The H using in hydrodealkylation 2with H 2the ratio of (stoichiometry) is preferably 0.02:50, particularly preferably 0.2:10.Herein, H 2(stoichiometry) changes into benzene required H in theory completely for the aromatic substance that is dosed to dealkylation district 2amount, supposes every mole of ring substituents reaction 1molH 2.
The residence time that is used for the dealkylation district of hydrodealkylation is preferably 0.1 to 500s, and particularly preferably 0.5 to 200s.
In second preferred embodiment, by from step b) degradation production or from step c) the cut C1 of enrichment aromatic substance) carry out steam dealkylation.For this reason, the reaction steps d) is carried out under the existence of water vapour.
The temperature that is used for the dealkylation district of steam dealkylation is preferably 400 to 800 ℃, and particularly preferably 475 to 600 ℃, especially 525 to 600 ℃.
The absolute pressure that is used for the dealkylation district of steam dealkylation is preferably 1 to 100 bar, particularly preferably 1 to 20 bar, especially 1 to 10 bar.
The H using in steam dealkylation 2o is preferably 0.1:20mol/mol, particularly preferably 0.5:2mol/mol with the ratio of C*.Herein, C* for by method known to those skilled in the art by the carbon back balance of pyrolysis or by measuring the molar weight of the carbon that the product amount of discharging from steam dealkylation measures.
H in the dealkylation district of steam dealkylation 2with CH 4mol ratio be preferably <50:1, <25:1 particularly preferably.
The situation of carrying out in the presence of not at dealkylation catalyst for steam dealkylation, wherein R=H, alkyl of OR(in dealkylation district) and C alwaysmol ratio be preferably >0.05:1,0.1:1-0.2:1 particularly preferably.
The situation of carrying out in the presence of not at dealkylation catalyst for steam dealkylation, wherein R=H, alkyl of OR(in dealkylation district) and C can eliminateratio be preferably >0.5:1, particularly preferably 1:1-10:1, especially 1:1-2:1.
WHSV for steam dealkylation is preferably 0.05 to 10kg/L*h, and particularly preferably 0.1 to 2kg/L*h.
Steam dealkylation can be carried out in catalyzer existence or not.In a specific embodiment, steam dealkylation is carried out in the presence of not at catalyzer.The catalysis process of steam dealkylation is described in WO2008/148807A1.The full content of this document and the reference about suitable catalyst wherein quoted is included this specification sheets in by reference at this.Other information about the catalyst type in steam dealkylation and method steps are found in WO2007/051852A1, WO2007/051851A1, WO2007/051855A2, WO2007/051856A1, WO2008/135581A1 and WO2008/135582A1(EP2008055585) in, these do not form the restriction to this specification sheets.US3,775,504 have described the combination that in fact steam dealkylation comprises steam dealkylation and hydrodealkylation, this is because in this system, the hydrogen of generation at least partly immediately again secondary response be intrinsic.
Dealkylation steps d) obtain at least one containing oxygen aromatic substance composition, the ratio of the following component that should have containing oxygen aromatic substance composition is less than conventionally from step b) degradation production or from step c) the fraction C1 of arene rich) ratio of the following component that has: monoalkylation phenol, dialkyl group phenol and many alkylated phenols; Alkoxy phenol is as methoxyphenol; Many alkylated benzenes; The compound that contains two or more aromatic rings.These components hereinafter will be referred to as " not dealkylation or only with the aromatic substance of little degree dealkylation ".
-from the fractionation of the ejecta in dealkylation district
Ejecta from dealkylation district can directly be dosed to step e) in amination in.
In an alternate embodiment, ejecta takes out and is being introduced into step e from dealkylation district) amination before carry out fractionation.Obtain at least one enrichment dealkylation containing the material stream D1 of oxygen aromatic substance herein) and the material of at least one enrichment volatile constituent flow D2).Have high-content not alkylation or the alkylating monocycle of low degree containing oxygen aromatic substance containing oxygen aromatic substance composition preferably as product D 1) obtain.
Preferably the ejecta fractionation of autospasy alkylation zone is in the future to obtain following three kinds of material streams:
D1) enrichment not alkylation or the alkylating monocycle of low degree containing the material stream of oxygen aromatic hydrocarbons,
D2) enrichment dealkylation or only with the material stream of the aromatic hydrocarbons of little degree dealkylation not,
D3) concentration ratio D1) and the D2) material of more volatile by product stream.
Optionally the ejecta fractionation of autospasy alkylation zone is in the future to obtain another kind of material stream as aqueous streams.
Material stream D1) for amination step e) be favourable.
Material stream D1) preferably comprise at least 70 % by weight, particularly preferably at least 80 % by weight, the especially monocyclic aromatics of at least 90 % by weight, based on D1) total amount meter.
Material stream D1) preferably comprise and be no more than 30 % by weight, be particularly preferably no more than 20 % by weight, be especially no more than the not dealkylation of 10 % by weight or only with the aromatic substance of little degree dealkylation, based on D1) total amount meter.
Material stream D2) preferably comprise at least 70 % by weight, particularly preferably the not dealkylation of at least 80 % by weight, especially at least 90 % by weight or only with the aromatic substance of little degree dealkylation, based on D2) total amount meter.
Material stream D3) comprise and be selected from for example component of non-aromatic hydrocarbon and especially methane, hydrogen, carbon monoxide, carbonic acid gas and composition thereof.Depend on the raw material containing xylogen providing during step is a), material stream D3) can contain other components.When use from Kraft method the raw material containing xylogen time, these comprise sulfur byproduct species, especially H 2s.
Preferably gaseous emission is taken out from dealkylation district and also carry out subsequently fractionation.
For fractionating method, can use known thermal separation method conventionally.From steps d) the fractionation of ejecta in dealkylation district preferably include absorption.In described absorption, make to contact with solvent (absorbing medium) from the gaseous emission in dealkylation district, part is contained in component in air-flow and is absorbed and separation thus.
Be absorbed in suitable device such as counter-current tower, bubble-plate column etc. and carry out.Absorb and preferably in counter-current tower, carry out.
Absorption can have one or more stages.
Absorb and preferably to use solvent (load: absorption agent, load: absorbate) carry out, described solvent is that the aromatic substance that obtains in dealkylation can q.s be dissolved in wherein and other volatile byproducts are insoluble to solvent wherein substantially.Herein, not dealkylation or only with the aromatic substance of little degree dealkylation also with alkylation not or have together with the monocyclic aromatics (=target product) of low alkylation degree and be absorbed.
Therefore, absorb the absorbate that first obtains being loaded with aromatic substance.Be contained in aromatic component in absorbate aspect its composition with material stream D1) and D2) in aromatic substance and be optionally contained in absorbing medium in the summation of aromatic substance corresponding.The component being contained in residual gas stream flows D3 with material aspect composition) corresponding.If needed, described air-flow can carry out other purification step to remove aromatic substance.Subsequently, these can with in solvent, comprise separated for the aromatic substance combination in conjunction with aftertreatment.Yet the separation of this aromatic substance from separated air-flow is normally non-essential.
In a preferred embodiment, from steps d) fractionation of the ejecta in dealkylation district comprises step by step following:
D1) make to contact to obtain the absorbate of enrichment dealkylation aromatics principal product and the air-flow D3 of meager set dealkylation aromatics principal product with absorbing medium from the ejecta in dealkylation district),
D2) absorbate is separated into enrichment not alkylation or the alkylating monocycle of low degree containing the material stream D1 of oxygen aromatic hydrocarbons), enrichment not dealkylation or only with the material stream D2 of the aromatic hydrocarbons of little degree dealkylation) and the material that optionally contains absorbing medium flow,
D3) if existed, the material stream that contains absorbing medium is recycled to steps d 1),
D4) optionally will expect at least partly to flow D2) be recycled to steps d) in dealkylation district.
The boiling point of absorbing medium is preferably greater than the boiling point of material stream D1 maximum boiling point component.
In first suitable embodiment, use and to be different from material stream D1) and the absorbing medium of component D2).For the suitable absorbing medium of this embodiment, be non-aromatic hydrocarbon, non-aromatic alcohol, non-aromatic aldehyde, ketone, acid amides, amine and composition thereof.Absorbing medium for this embodiment is preferably selected from pentane, hexane, heptane, octane, V.M.. naphtha, sherwood oil, hexanaphthene, naphthalane, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, 1-amylalcohol, 1-hexanol, 1-heptanol, 1-octanol, acetaldehyde, acetone, methylethylketone, N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE and composition thereof.
Other suitable absorbing mediums are for being different from material stream D1) and the aromatic hydrocarbon of component D2).These aromatic hydrocarbons are preferably selected from the phenyl methyl ketone of optional replacement, the optional benzophenone replacing, the optional biphenyl replacing, the optional terphenyl replacing, optional phenyl ether replacing and composition thereof.If will be also, as by product, be included in material stream D1) or D2) in component as absorbing medium, by instrument means well known by persons skilled in the art, can guarantee that this component removes from this process continuously with its resulting amount.
When use is different from material stream D1) and during the absorbing medium of component D2), from steps d) the fractionation of ejecta in dealkylation district preferably include step by step following:
D1) make to contact to obtain the absorbate of enrichment dealkylation aromatics principal product and the air-flow D3 of meager set dealkylation aromatics principal product with absorbing medium from the ejecta in dealkylation district) (or air-flow D3 of concentration ratio D1 and the more volatile by product of D2))
D2) absorbate is separated into enrichment not alkylation or the alkylating monocycle of low degree containing the material stream D1 of oxygen aromatic substance), enrichment not dealkylation or only with the material stream D2 of the aromatic substance of little degree dealkylation) and the material that contains absorbing medium flow,
D3) the material stream that contains absorbing medium is recycled to steps d 1),
D4) optionally will expect stream D2) be recycled at least partly steps d) in dealkylation district.
In a concrete modification, the aromatic substance composition that can obtain by the inventive method is as absorbing medium.Especially the mixture of the aromatic substance of unreacted or incomplete reaction in dealkylation.In a preferred modification, by integral part or completely corresponding with material stream D2 or be used as absorbing medium with the corresponding aromatic substance composition of the mixture of D1 and D2.The mixture of material stream D2 or D1 and D2 can optionally carry out at least one treatment step as before absorbing medium.
When use to form most of or completely with material flow D2 corresponding or during with the corresponding absorbing medium of the mixture of D1 and D2, from steps d) the fractionation of ejecta in dealkylation district preferably include step by step following:
D1) make to contact to obtain the absorbate of enrichment dealkylation aromatics principal product and the air-flow D3 of meager set dealkylation aromatics principal product with absorbing medium from the ejecta in dealkylation district),
D2) absorbate is separated into enrichment not alkylation or the alkylating monocycle of low degree containing the material stream D1 of oxygen aromatic hydrocarbons) and enrichment not dealkylation or only with the material of the aromatic hydrocarbons of little degree dealkylation, flow D2),
D4) optionally will expect at least partly to flow D2) be recycled to steps d) in dealkylation district.
In this modification, the partial condensation of the air-flow of the material stream of solvent by from dealkylation or the high boiling product that tentatively removes from dealkylation downstream obtains., advantageously between above-mentioned partial condensation and water suction, introduce further partial condensation herein, wherein, especially water is condensed out.Equally in this modification, at least part of absorption of the aromatic substance of unreacted or not complete reaction is carried out together with the absorption of required product, that is to say, equally in this modification, the aromatic component comprising in absorbate aspect its composition with material stream D1) and the summation of aromatic substance D2) corresponding.
In steps d 2) in, the absorbate of arene rich is preferably by distillation fractionation.Recovered solvent---optionally after removing absorption water---is recycled in absorption (d1 of step).As described above and below, further process aromatic substance.
In steps d 2) in, the preferably distillation fractionation at least one tower (" regenerator column ") of the absorbate of enrichment aromatic substance.Preferably select distillation condition, so that alkylation or the alkylating aromatic substance of low degree and water (if existence) do not obtain as top product substantially, and dealkylation or the aromatic substance of little degree dealkylation of only usining do not obtain as bottoms substantially.
Self-evident, in steps d 2) thus distillation fractionation in the bottom temp selected is too low has substantially avoided the undesirable side reaction of bottoms.This can especially realize by the content of the low boilers of suitable bottom column pressure and/or bottom is set (content of low boilers can be further air lift by subsequently reduce).
Steps d 2) top product obtaining in distillation can be used as material stream d1) directly take out and for step e) amination.
As an alternative, steps d 2) distillation in the top product that obtains can be further processed.
The water comprising in top product can be isolated by currently known methods.For this reason, after by the vapor condensation from distillation, top product can be dosed to phase separator with separated water outlet.Using the water obtaining as other material streams from this process, discharge.Organic phase from phase separator can flow D1 as material at least partly) take out or be further processed.Organic phase from phase separator can part be back to tower and/or be further processed by distillation as backflow.This is preferably used for removing water and/or the undesirable organic constituent still containing.
Steps d 2) bottoms obtaining in distillation is included in unreacted in dealkylation or the abundant aromatic substance of reaction only, i.e. its enrichment is dealkylation or only with the aromatic substance of little degree dealkylation not.Described bottoms can be used as material stream D2) directly take out or be further processed.Steps d 2) bottoms obtaining in distillation is preferably divided at least two share streams.The first share stream is preferably recycled to the steps d from the absorption fractionation of the ejecta in dealkylation district as absorbing medium).For this reason, if needed, this subflow is down to suitable temperature.The second share stream is as material stream D2) take out.Material stream D2) can be recycled to steps d) in dealkylation district before remove the composition that does not belong to material stream D2.For example, when using not the lyosorption obtaining as the intermediate of the inventive method, this is favourable.In addition, advantageously in this point, expect in the future stream D2) another strand purify material stream and take out and be for example delivered to combustion unit and under dealkylation condition, do not react or the accumulation of sluggish component to reduce.
Before being dosed to dealkylation, material stream D2) preferably evaporate.A preferred modification is shown in Fig. 1 and in the associated description of Fig. 1 to be explained.
In a specific embodiment, steps d) the material stream D3 obtaining in)---it is meager set aromatic hydrocarbons enrichment volatile byproducts---is at least partly for the preparation of synthetic gas.According to the above-mentioned preferred embodiment of the inventive method, if from steps d) the fractionation of ejecta in dealkylation district comprise absorption, leave the air-flow (material stream D3) of absorption unit optionally---after removing the purification step of absorbing medium and/or aromatic substance---at least in part for the preparation of synthetic gas.
Except preparing synthetic gas, steps d) the material stream D3 obtaining in) can partly be delivered to multiple other purposes.These comprise burning.If the inventive method, near pulping process, advantageously can flow D3 by material) be dosed in the device of pulping process.Material stream D3) be particularly preferably dosed to incineration of liquor (regeneration boiler).This embodiment has the following advantages: do not need other devices for steam-electric power or dynamic power or at material stream D3) flue gas desulfurization (FGD) under combustion case.In another modification, material stream D3) burning is undertaken by desulfurization, for example, with the formation of gas scrubbing, carry out, thereby remove hydrogen sulfide, subsequently by the H forming 2s changes into elementary sulfur.The formation of sulphur can by currently known methods for example Crouse (Claus) method carry out.After burning, also can follow desulfurization unit.
For synthetic gas preparation, except material stream E3), optionally use at least one other material that contains water vapour for example and/or oxygen to flow.
In a specific embodiments of the inventive method, the cut C2 of separated meager set aromatic substance in step c)) at least partly for the preparation of synthetic gas.In synthetic gas preparation process, can also use the tail gas stream from the dealkylation of the decomposition of step b) and/or optional step d).Described tail gas stream can be (burning-off) gas that burnouts for example burning from relative volatility component.The introducing of this tail gas stream can reduce the H of synthetic gas 2/ CO ratio.
The preparation of synthetic gas preferably includes following steps:
-reforming step,
-step of converting (wherein, if needed, introducing other water), wherein, carries out water-gas shift reaction (CO+H 2o
Figure BDA0000455479010000321
h 2+ CO 2)
-optionally for part, remove sour gas as CO 2step.
The preparation of synthetic gas is carried out according to prior art, as at for example Ullmann's Encyclopedia of Industrial Chemistry, and article " Gas Production ", described in DOI:10.1002/14356007.a12_169.pub2.
In a preferred modification, and the synthetic gas of preparing in the inventive method (if needs, for would removing water, sulfur component, CO 2deng own known be further purified step after) wholly or in part for consuming at least one method of the mixture of hydrogen, CO or hydrogen and CO.Described method comprises, for example, and hydrogenation, hydroformylation, carbonylation, synthesizing methanol, by the synthetic hydrocarbon of fischer-tropsch (Fischer-Tropsch) method etc.
In a preferred embodiment of the inventive method, the material stream of the material stream containing synthetic gas producing in the method or the enrichment hydrogen being produced by synthetic gas is dosed to step b) decomposition in and/or be dosed to optional steps d) dealkylation in.As mentioned above, the enrichment of the synthetic gas of hydrogen can be undertaken by water-gas shift reaction.
Preferably the material stream of the material stream containing synthetic gas producing in the method or the enrichment hydrogen that produced by synthetic gas is dosed to steps d) in dealkylation in.The concrete advantage of this modification is, in dealkylation product, the ratio of phenol is higher than the ratio of the phenol of (not introducing hydrogen) in pure steam dealkylation situation.Higher phenol forms and represents important advantage prepared by polymeric polyisocyanate of the present invention.
amination (step e)
By biomass material by decompose and optionally other reactions and/or treatment step obtain containing the amination in step g) of oxygen aromatic substance composition.Containing oxygen aromatic substance composition, preferably in Yu An source, amination district, react to obtain corresponding aromatic amine herein.
In step e), preferably by the degradation production from step b) or from the cut C1 of the arene rich of step c)) or from the ejecta in the dealkylation district of step d) or from the material stream D1 of the enrichment dealkylation aromatic hydrocarbons of step d)) by reacting and amination with ammonia source.
Can be undertaken by ordinary method well known by persons skilled in the art with reacting of ammonia source, as at for example DE-B-1289530, US3,578,714, US5,214,210 and EP-A-0321275 described in.The specification sheets of these files is included this specification sheets in by reference at this in full.
Carry out in the ammonia source that amination can be used ammonia or can form ammonia under reaction conditions.Described ammonia source comprises, for example, forms the compound of ammonia under thermolysis, as volatile salt and ammonium sulfate.As an alternative, be preferably selected from following organic amine and can be used for amination: methylamine, ethamine, Tri N-Propyl Amine, dimethylamine, diethylamine, dipropyl amine, methylethyl amine, hexahydroaniline, aminopyridine, aniline, monomethylaniline, ethylaniline, n-propyl aniline, isopropyl aniline, xylidine, Diethyl Aniline, dipropyl aniline, methylethyl aniline and methyl-propyl aniline.Preferably use ammonia for amination.
Amination is preferably carried out under the existence of suitable catalyst.Preferably use at least one catalyzer based on Al oxide compound or Si-Al oxide compound.
If needed, raw material can preheat before amination, and preheating can be relevant to evaporation.
The temperature in amination district is preferably 100 to 600 ℃, particularly preferably 200 to 450 ℃.
The absolute pressure in amination district is preferably 1 to 100 bar, particularly preferably 1 to 30 bar.
For amination reaction device, preferably use fixed bed or fluidized-bed.
In amination, ammonia is preferably 5:1-30:1 with the mol ratio containing oxygen aromatic substance.
The gas that leaves amination district preferably comprises molar ratio than containing the higher amine of oxygen aromatic substance.
In order to process the ejecta taking out from amination district, this ejecta preferably passes through fractionation.Ejecta from amination district takes out with gas form conventionally.In a preferred embodiment, the ejecta from amination district is cooling and be dosed to first distillation tower to isolate excess ammonia.It is preferably recycled to amination district.The amine forming as with water and optionally the mixture of a small amount of by product bottom first distillation tower, obtain.Bottoms from first distillation tower is dosed to second distillation tower with separated water outlet.Further fractionation is preferably carried out at least one other distillation tower.Obtain the material stream E1 of at least one enrichment aromatic amine herein) and at least one enrichment containing the material of oxygen aromatic substance, flow E2).The utilization of divided wall column technology also can make a plurality of towers be combined in a tower that provides one or more side relief outlets.The suitable tower with side relief outlet---it is thermal coupling in a specific embodiment---is well known to those skilled in the art with divided wall column.
The material stream E1 of enrichment aromatic amine) be dosed to phosgenation (step g).Enrichment is containing the material stream E2 of oxygen aromatic substance) be preferably recycled to amination district.
If needed, the material stream E1 of enrichment aromatic amine) can pass through further fractionation.In a specific embodiment, as the material stream E1 of enrichment aromatic amine) contain monoamine and (there is a NH 2the amine of group) and polyamines (there is more than one NH 2group is as two, three or four NH 2the amine of group), time, carry out further fractionation.Further fractionation is preferably undertaken by distillation.So, preferably obtain the material stream E1m of enrichment aromatic monoamine) and the material of enrichment aromatic polyamine flow E1p).In a specific embodiment, the material of enrichment aromatic monoamine stream E1m) before the phosgenation of step g) at step f) in formaldehyde source condensation.The material stream E1p of enrichment aromatic polyamine) can be in step g) phosgenation before at step f) in carry out condensation or be directly used in step g with formaldehyde source) phosgenation.
In a specific embodiment, by least one non-amine (hereinafter referred to as " conventional amine ") obtaining from biomass at step f) and/or g) reaction be added to from step e before) aminate.As noted, for object of the present invention, term " biomass " refers to non-fossil origin vegetable material.The amine adding is preferably from being selected from coal, oil, Sweet natural gas and upgrading products thereof as the fossil feedstock source of coke.
For step f) and/or the amine of reaction g) preferably comprise at least 50 % by weight, the amine of being prepared by biomass material according to the present invention of at least 75 % by weight, especially at least 90 % by weight, especially at least 99 % by weight particularly preferably, based on for step f) and/or the total amount meter of the amine of reaction g).
-conventional amine
Suitable conventional aromatic amine can be prepared as benzene or toluene by corresponding aromatic substance by the known method of prior art.These especially comprise nitrated and subsequently by nitryl group hydrogenation to form corresponding amine.Nitro-aromatics can be prepared by batch process or continuous processing.Nitrating agent is preferably the mixture of nitric acid and sulfuric acid or independent nitric acid.In liquid phase, the appropriate method of continuous production is described in for example Meissner et al., Continuous production of nitrotoluenes, and Ind.Eng.Chem., in 464 (1954), 718 – 24 and US2, in 773,911.Use independent nitric acid nitrating to be described in US2, in 739,174 and the vaporphase nitration of hydrocarbon be described in GB586732.The general view of suitable commercial run is found in for example Leslie A.Carmichael, Aromatic Amines, and SRI Stanford Research Institute, in 1972.EP-A-748788 and EP-A-0597361 have described thermal insulation and Continuous Liquid Phase is nitrated to prepare nitrotoluene.US5,302,763 have described the nitrated without sulfuric acid of use nitric acid.EP-A-1350787 has described by acid zeolite heterogeneous catalyst methylbenzene nitration to improve optionally method.EP-A-0184569 has described by the nitrated method of mixed oxide heterogeneous catalyst in gas phase.The summary of preparation dinitrotoluene (DNT) is found in Hermann et al., Industrial nitration of toluene to dinitrotoluene, and ACS Symp.Series623 (nitration), in 234 – 249.EP-A-1880989 has described the fine chemicals embodiment of the method.In liquid phase, implement the method isothermal and be described in WO2005/075407 and EP-A-0903336.Wastewater treatment details is described in DE10329303, and is integrated into integrated approach widely and is described in EP-A-1132347 and EP-A-0976718.CN1854114 has instructed and has added nitrated under metal-salt.The importance of the sulphuric acid concentration of use is described in DE-A-4230099.Like the dinitrotoluene (DNT) info class as TDI precursor, be applicable to the single oil of mirbane as the precursor of MDA/MDI.In liquid phase, the description of suitable continuation method is found in US2, in 849,497 and US2,773,911.Possible reactor is for example to have the stirred vessel of heat exchanger or stream pipe.In stream pipe, adiabatic enforcement reaction is described in BE724918, DE4428460 and DE4428461.Herein, nitric acid is assimilated the reaction heat of reaction.The heat storing in this way can be used for by step-down separating by-products water from reaction mixture.For implement a specific embodiments of the adiabatic flow pipe of aromatic compound nitrification in liquid phase, be found in DE10223483, EP0489211 and WO01/64333.Owing to needn't consider selectivity with regard to forming isomer, the adiabatic reaction in the liquid phase in therefore preparing with nitrotoluene is compared, and the adiabatic reaction in the preparation of single oil of mirbane in liquid phase is particularly preferred.The enforcement of safety monitoring and nitrifying method is described in EP-A-1445246.Quadros et al., Ind.Eng.Chem.Res.2004,43,4438 – 4445 relate to wastewater problem.The full text of document disclosure mentioned above is included this specification sheets in by reference at this.
Aromatic nitro compound by nitrated acquisition is by being hydroconverted into corresponding amine.Water obtains as hydrogenation byproduct.Hydrogenation preferably carries out under the existence of catalyzer.It can industrial multiple industrial implementation scheme as fluidized-bed or fixed bed in or in liquid phase or gas phase, carry out.The high calorie of reaction is advantageously used in generate energy and/or is integrated in integrated hot system (referring to EP-A-1137623, US7,064,237, EP-A-0696573, EP-A-0748789).In the microchannel applying, implementing reaction is described in DE-A-102006011497.The full text of the disclosure of file mentioned above is included this specification sheets in by reference at this.
-ring hydrogenation
The aminate obtaining in step e) (especially the material of enrichment aromatic polyamine stream E1p) can be in step f) optionally with formaldehyde source condensation before or in step g), before phosgenation, encircle hydrogenation.Can obtain by this way economically with ecology on favourable aliphatic polymeric isocyanate.Suitable ring method of hydrotreating is described in, for example, and US6,429,338, in WO2006/066762 and EP-A-799817.The full text of the disclosure of these files is included this specification sheets in by reference at this.
condensation (step f) with formaldehyde source
In order to obtain the polymeric polyisocyanate with high nco value, step e) in the aminate that obtains can be in step g) in phosgenation partly or entirely carry out the condensation with formaldehyde before.In addition the amine of condensation can be mixed for step g with the amine of not condensation) in phosgenation.
As for the appropriate method of aromatic amine and formaldehyde condensation, DE-A-19961973, DD295628 and DD238042 include this specification sheets by reference in.
For step f) the suitable formaldehyde source that reacts be formalin solution, formaldehyde oligomer as the polymkeric substance of trioxane and formaldehyde as paraformaldehyde.Preferably use paraformaldehyde or formalin solution.Certainly also can use gaseous formaldehyde.
The amine using and the mol ratio of formaldehyde are preferably 1.5:1-10:1, especially 2:1-6:1.
Condensation reaction preferably adds an acidic catalyst to carry out.For an acidic catalyst, can use the catalyzer that conventionally becomes known for this reaction, for example mineral acid is as phosphoric acid, sulfuric acid and hydrochloric acid.Hydrochloric acid is preferably used as step f) in the catalyzer of condensation.
The mol ratio of catalyzer and amine is preferably 0.01 to 1, and especially 0.1 to 0.5.
Condensation reaction conventionally 20 to 150 ℃, preferably at the temperature of 20 to 130 ℃, carry out.In a preferred modification, first add aniline and an acidic catalyst, then add formaldehyde.
Acid amine mixt from condensation can be by ordinary method as neutralized, being separated and distilling and process.
phosgenation (step g)
Step e) the amine product obtaining in (the especially material of enrichment aromatic polyamine stream E1p) or step f) in the phosgenation of the condensation product that obtains can be undertaken by ordinary method well known by persons skilled in the art.
Be applicable to step g) in the liquid phase phosgenation of phosgenation be described in, for example, in EP-A-1616857, WO2004/056756, WO2006/130405, EP-A-1509496, EP-A-1270544 and DE-A-19961973.The full text of the disclosure of these files is included this specification sheets in by reference at this.
As an alternative, the phosgenation step g) can be used as gas phase phosgenation and carries out.At high temperature in gas phase, the advantage of phosgenation is, conventionally can avoid forming undesirable amine hydrochlorate intermediate.The method is described in EP-A-593334, WO2003/045900, WO2008/086922 and the phosgenation of WO2008/006775(aerosol) in, it includes this specification sheets in equally by reference at this.
In addition the phosgenation step g) can be carried out (WO2008/049783) in supercritical solvent.Isocyanic ester itself (EP-A-1401802, US6,683,204) or ionic liquid (WO2006/048141BASF, WO2006/048171BASF) also can be used as solvent.
In a suitable embodiment, step g) phosgenation in is carried out in the solvent that is inertia under phosgenation condition.Suitable solvent is that for example, aromatic substance is as toluene, monochloro benzene or dichlorobenzene.Step g) phosgenation in can be carried out in popular response device, for example, at stirred vessel or in stirring tower, carry out.
The temperature of phosgenation is preferably 50 to 150 ℃, particularly preferably 70 to 100 ℃.
The pressure of phosgenation is preferably 0.5 to 10 bar, particularly preferably 0.8 to 5 bar.
Step g) in the phosgenation in, obtain thick isocyanic ester and can pass through for example distillation purifying of ordinary method.The device that can be used for this object is falling-film evaporator or thin-film evaporator or packing tower.Described purifying can carry out in two method stepss.First, phosgene, HCl and solvent by 50 to 150 ℃ of temperature, air lift under reduced pressure or isolate from thick isocyanic ester by introducing rare gas element optionally.Subsequently, remaining solvent and possible chlorine-containing compound at the temperature of 150 to 190 ℃ again by air lift or under reduced pressure remove.

Claims (36)

1. a method of preparing polymeric polyisocyanate, is wherein used biomass material to prepare C 14with C 12the ratio of isotropic substance is 0.5x10 -12to 5x10 -12aromatic amine composition and the composition of described aromatic amine is carried out to phosgenation.
2. the method for claim 1, wherein the biomass material for the preparation of aromatic amine composition is carried out at least primary first-order equation, described reaction comprises digestion with the aromatic substance composition (" containing oxygen aromatic substance composition ") that obtains containing per molecule and have the aromatic substance of at least one oh group and/or at least one alkoxy base and will describedly contain oxygen aromatic substance composition carries out amination.
3. the method for claim 2, wherein saidly contains at least 75 % by weight based on gross weight meter, the preferred at least 90 % by weight monocyclic aromatics of at least 95 % by weight especially containing oxygen aromatic substance composition.
4. a method of preparing polymeric polyisocyanate, wherein
-biomass material is provided, and (step a) also makes its reaction that comprises digestion (aromatic substance composition (" containing oxygen aromatic substance composition ") that step b) has the aromatic substance of at least one oh group and/or at least one alkoxy base to obtain containing per molecule
-make containing the amination of oxygen aromatic substance composition (step e),
-optionally make aminate and formaldehyde source condensation (step f),
-make the condensation product phosgenation (step g) of aminate or aminate and formaldehyde source.
5. a method of preparing polymeric polyisocyanate, wherein
A) provide biomass material,
B) make biomass material digestion,
C) material through digestion obtaining in step b) is optionally separated into the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one meager set aromatic substance),
D) from the digestion product of step b) or from the cut C1 of the enrichment aromatic substance of step c)) be optionally dosed to dealkylation district and react under the existence of hydrogen and/or water vapour,
From dealkylation district, take out ejecta, and
In the future the ejecta of autospasy alkylation zone is optionally separated to obtain at least material stream D1 of one enrichment dealkylation aromatic substance) and at least one enrichment more the material of volatile components flow D2),
E) by the digestion product from step b) or from the cut C1 of the enrichment aromatic substance of step c)) or from the ejecta in the dealkylation district in step d) or the material of enrichment dealkylation aromatic substance stream D1) amination by the reaction of Yu Anyuan amination district
F) make from step e) aminate optionally with formaldehyde source condensation,
G) make from step e) aminate or from step f) with the condensation product phosgenation of formaldehyde source.
6. the method for arbitrary aforementioned claim, wherein the material containing xylogen provides as biomass material.
7. the method for arbitrary aforementioned claim, wherein the digestion product of ligno-cellulosic materials or ligno-cellulosic materials provides as biomass material.
8. the method for arbitrary aforementioned claim, wherein will be from the stream of the material containing xylogen of the digestion of the ligno-cellulosic materials for the preparation of Mierocrystalline cellulose (paper pulp)---preferred black liquor, especially from the black liquor of Kraft digestion (vitriol digestion)---as biomass material, provide.
9. the method for claim 2 to 8 any one, the biomass material wherein providing carries out pyrolysis for step b) in decomposition.
10. the method for claim 9, wherein pyrolysis does not add under hydrogen compound and carries out.
The method of 11. claims 9, wherein pyrolysis adds hydrogen to carry out (hydrocracking).
The method of 12. claim 9 to 11 any one, wherein, by the content liquid under standard conditions (20 ℃, 1013 millibars) for gross weight meter based on black liquor material is no more than 70 % by weight, the black liquor material that is preferably no more than 50 % by weight is for pyrolysis.
The method of 13. claim 2 to 8 any one, the biomass material wherein providing is at step b) in liquid phase, decompose.
The method of 14. claims 13, wherein biomass material, preferably containing the raw material of xylogen at step b) under the existence of scale decomposition media, water acid decomposition medium or organic decomposition medium, decompose.
The method of 15. claims 13 or 14 any one, is wherein used for the cellulosic cut of at least one meager set from pulping process, the especially black liquor from Kraft method to decompose.
The method of 16. claim 5 to 15 any one, wherein at step c) in the cut C1 of at least one enrichment aromatic substance) with the cut C2 of at least one meager set aromatic substance) separated by distillation, extraction, absorption, membrane method or its in conjunction with and preferably by distillation, extraction, absorb or it is in conjunction with carrying out.
The method of 17. claim 9 to 12 any one, the biomass material pyrolysis wherein step being provided in a) is for step b) in decomposition, and at step c) in for obtaining the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one meager set aromatic substance) fractionation carried out comprises absorption.
The method of any one in 18. claims 13 to 15, the biomass starting material that wherein step provided in a) are at step b) in carry out the decomposition in liquid phase, and at step c) in for obtaining the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one meager set aromatic substance) fractionation carried out comprises extraction and/or distillation.
The method of 19. claims 18, wherein at step c) in obtain the cut C1 of at least one enrichment aromatic substance) and the cut C2 of at least one meager set aromatic substance) fractionation comprise step by step following:
C1) by step b) in the degradation production that obtains extract to obtain a kind of extract of enrichment aromatic substance and a kind of resistates of meager set aromatic substance,
C2) optionally described extract is separated into the cut of extracting and enriching agent and meager set aromatic substance and the cut of enrichment aromatic substance and meager set extraction agent,
C3) by step c1) in extract or the step c2 of the enrichment aromatic substance that obtains) in the cut of the enrichment aromatic substance that obtains be introduced into steps d) and/or step e) in.
The method of 20. arbitrary aforementioned claims, wherein steps d) in reaction comprise hydrodealkylation or steam dealkylation or its mixed form.
The method of 21. arbitrary aforementioned claims, wherein the temperature in dealkylation district is 400 to 900 ℃, preferably 500 to 800 ℃.
The method of 22. arbitrary aforementioned claims, wherein the absolute pressure in dealkylation district is 1 to 100 bar, particularly preferably 1 to 20 bar, especially 1 to 10 bar.
The method of 23. claim 5 to 22 any one, wherein by from steps d) in the ejecta fractionation in dealkylation district to obtain following three kinds of material streams:
D1) enrichment not alkylation or the alkylating monocycle of low degree containing the material stream of oxygen aromatic substance,
D2) enrichment dealkylation or only with the material stream of the aromatic substance of little degree dealkylation not,
D3) concentration ratio D1) and the D2) material of more volatile by product stream.
The method of 24. claim 4 to 23 any one, the wherein amination for step e) by ammonia.
The method of 25. claim 4 to 24 any one, wherein by from step e) in the ejecta fractionation in amination district to obtain the material stream E1 of at least one enrichment aromatic amine) and at least one enrichment containing the material of oxygen aromatic substance, flow E2).
The method of 26. claims 25, wherein obtains the material stream E1 of at least one enrichment aromatic amine) and at least one enrichment containing the material of oxygen aromatic substance, flow E2) fractionation comprise step by step following:
E1) ejecta from amination district is distilled to fractionation to obtain the cut of enriched ammonia and the cut of meager set ammonia,
E2) optionally by distillation from from step e1) the cut Separation of Water of meager set ammonia,
E3) distillation fractionation is to obtain the material stream E1 of at least one enrichment aromatic amine) and at least one enrichment containing the material of oxygen aromatic substance, flow E2).
The method of 27. claims 25 or 26 any one, wherein makes the material of enrichment aromatic amine flow E1) at least part of and formaldehyde source condensation (step h).
The method of 28. claim 25 to 27 any one, wherein by the material stream E1 of enrichment aromatic amine) at least partly without in advance with formaldehyde source condensation for phosgenation (step g).
The method of 29. claim 25 to 28 any one, wherein makes the material stream E1 of enrichment aromatic amine) further fractionation to be to obtain the material stream E1m of enrichment aromatic monoamine) and the material of enrichment aromatic polyamine flow E1p).
The method of 30. claims 29, the material stream E1m of wherein enrichment aromatic monoamine) before the phosgenation of step g) in step f) with formaldehyde source condensation.
The method of 31. claims 29 or 30 any one, the wherein material of enrichment aromatic polyamine stream E1p) in step g) phosgenation before at step f) in formaldehyde source condensation or be directly used in step g) phosgenation.
The method of 32. claim 25 to 31 any one, wherein enrichment is containing the material stream E2 of oxygen aromatic substance) be recycled to step e) in amination district.
The method of 33. claim 4 to 32 any one, wherein at least one non-amine obtaining from biomass is at step f) and/or g) reaction before be added to from step e) aminate.
34. 1 kinds of polyisocyanate compositions, wherein C 14with C 12the ratio of isotropic substance is 0.4x10 -12to 4.5x10 -12.
35. 1 kinds of polyisocyanate compositions that can obtain by the method for claims 1 to 33 any one definition.
36. claims 34 or 35 polyisocyanate composition, the nco value of described polyisocyanate composition is at least 30.
CN201280034368.9A 2011-05-24 2012-05-23 Process for preparing polyisocyanates from biomass Pending CN103649044A (en)

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