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WO2011138356A1 - Procédé de production de gaz de synthèse et d'au moins une matière valorisable organique liquide ou liquéfiable - Google Patents

Procédé de production de gaz de synthèse et d'au moins une matière valorisable organique liquide ou liquéfiable Download PDF

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Publication number
WO2011138356A1
WO2011138356A1 PCT/EP2011/057099 EP2011057099W WO2011138356A1 WO 2011138356 A1 WO2011138356 A1 WO 2011138356A1 EP 2011057099 W EP2011057099 W EP 2011057099W WO 2011138356 A1 WO2011138356 A1 WO 2011138356A1
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Prior art keywords
digestion
stream
aromatics
enriched
fraction
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German (de)
English (en)
Inventor
Roman Prochazka
Stefan Bitterlich
Otto Machhammer
Stephan Deuerlein
Dirk Klingler
Emmanouil Pantouflas
Alois Kindler
Bernd Zoels
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for the production of synthesis gas and at least one organic liquid or liquefiable recyclable material.
  • Low molecular weight aromatic compounds and especially phenolic compounds have found wide use as intermediate and value products. They serve z. As a precursor for various resins, surface-active compounds, specialty chemicals, etc. It is known to produce such compounds from biomass materials and especially from lignin-containing starting materials.
  • lignin-containing starting materials there remains a need for a simple, low cost process that enables the provision of a variety of different aromatic products for a variety of applications. It is advantageous if, in addition to the desired aromatic products, further valuable substances are obtained and, if possible, in the process for the preparation of aromatics or a process coupled therewith, eg. As a method for pulp production, can be used again.
  • synthesis gas a gas mixture containing carbon monoxide and hydrogen.
  • the fields of application of synthesis gas include, for.
  • US 2,057,117 describes a process for the preparation of vanillin in which a starting material selected from lignocellulose, a crude lignin extract and lignosulfonic acid, with an aqueous alkali metal hydroxide solution under elevated Heated pressure and the resulting reaction mixture with sulfuric acid to precipitate organic constituents and convert the vanillin into a soluble form.
  • WO 99/10450 describes a process for converting lignin into a hydrocarbon fuel. Lignin undergoes base-catalyzed depolymerization and subsequent hydroprocessing. This hydroprocessing involves hydrodeoxygenation and mild hydrocracking. The latter is carried out under conditions in which a partial hydrogenation of the aromatic rings takes place.
  • WO 2008/027699 A2 describes a process in which lignin originating from a pyrolysis of biomass is decarboxylated and hydrodeoxygenated after separation of water-soluble constituents and the organic products from this process step are subsequently subjected to hydrocracking.
  • WO 2010/026244 describes an integrated process for the production of pulp and of at least one low molecular weight valuable material in which
  • a cellulose-enriched fraction and a fraction enriched in lignin are isolated from the digested material, the lignin-enriched fraction is subjected to depolymerization, and an aromatic compound is isolated from the polymerization product.
  • WO 2009/108601 describes a process for producing a starting material for biorefinery processes for producing a biofuel from a lignin-containing starting material.
  • lignin from a black liquor of the pulping process or the black liquor itself, a hydroprocessing in the presence of a hydrogen-containing gas and a catalyst on an amorphous or subjected to crystalline oxidic carrier.
  • a heterogeneous molybdenum sulfide catalyst is used.
  • the hydroprocessing can also be carried out in two stages. The process can be carried out either at a refinery site to which lignin or black liquor is being transported, or directly at the site of a paper mill. The subsequent to the hydroprocessing biorefinery process is not described in detail.
  • WO 2009/108599 has a disclosure content comparable to WO 2009/108601 with a focus on papermaking.
  • US 2009/0227823 describes a process for preparing at least one liquid hydrocarbon product from a solid hydrocarbon feedstock (eg, a lignocellulosic material) by subjecting the feedstock to catalytic pyrolysis and subjecting the pyrolysis products to a catalyzed follow-up reaction to give liquid products.
  • a solid hydrocarbon feedstock eg, a lignocellulosic material
  • lignocellulosic materials can in principle be converted to three routes into liquid fuels which differ in their primary step: gasification to syngas, pyrolysis to bio-oil, hydrolysis to give sugars and lignin.
  • gasification to syngas gasification to syngas
  • pyrolysis to bio-oil pyrolysis to bio-oil
  • hydrolysis to give sugars and lignin.
  • the bio-oils obtained in the pyrolysis can then be subjected to hydrodeoxygenation in the presence of hydrogen or steam reforming.
  • a first object of the invention is a process for the production of synthesis gas and at least one organic liquid or liquefiable recyclable material comprising: a) providing a biomass feedstock which will digest the biomass feedstock, optionally the digested material obtained in step b) at least one aromatics-enriched fraction C1) and at least one aromatics-depleted fraction C2), the digestion product from step b) or the aromatics-enriched fraction C1) from step c) fed into a dealkylation zone and in the presence of hydrogen and / or steam is reacted, e) the dealkylation zone takes a discharge and subjected to a separation, wherein at least one organic liquid or liquefiable recyclable material and at least one lighter than the organic volatile components enriched stream is obtained, f) obtained in step e), on lei harder than the organic valuable volatile components enriched stream at least partially for the production of synthesis gas.
  • biomass refers to a plant material of non-fossil origin. Biomass also includes dead plants and parts of plants, such as deadwood, straw, leaves, etc.
  • biomass also includes products in which a vegetable material of non-fossil origin has undergone a chemical and / or physical treatment. These include, in particular, the products of the digestion and fractionation of lignocellulose, such as lignin.
  • biomass does not include coal, oil, natural gas, peat and their performance products, such as coke.
  • synthesis gas in the context of the invention refers to a carbon monoxide and hydrogen-containing gas mixture.
  • This gas mixture may additionally contain other gases, such as CO2, CH 4 , etc.
  • the inventive method allows the production of synthesis gas with a high content of carbon monoxide and hydrogen.
  • An organic liquid or liquefiable recyclable material is understood as meaning an organic compound or a composition of at least two organic compounds which are liquid under normal conditions (20 ° C., 1013 mbar) or liquefiable without decomposition.
  • Liquefaction refers to the transition from the solid to the liquid state of matter in the sense of melting and not solubilization with the addition of a solvent.
  • the organic valuable material is z. B. selected from unfunctionalized and functionalized aliphatic, cycloaliphatic and aromatic hydrocarbons. These include in particular alkanes (such as pentane, hexane, etc.), alkenes, alkadienes, alkanols (such as methanol, ethanol, etc.), aliphatic aldehydes (such as acetaldehyde, etc.), cyloalkanes, cycloalkenes, cycloalkadienes, cycloalkanols, cycloalkadienols , Cycloalkanpolyole with more than two OH groups and unfunctionalized and functionalized aromatic see hydrocarbons.
  • alkanes such as pentane, hexane, etc.
  • alkenes such as methanol, ethanol, etc.
  • alkanols such as methanol, ethanol, etc.
  • aldehydes such as acetal
  • the organic liquid or liquefiable recyclable material is preferably selected from non-functionalized and functionalized aromatics.
  • Functionalized aromatics preferably have at least one substituent selected from C 1 -C 4 alkyl, OH, C 1 -C 4 alkoxy, formyl, C 1 -C 4 acyl, and combinations thereof.
  • the organic valuable material is in particular selected from benzene, alkylated benzenes (eg toluene and xylenes), higher fused aromatic hydrocarbons, mono-, di- and polyalkylated, higher-fused aromatics, phenol, mono-, di- and polyalkylated phenols, higher fused aromatics having one, two or more than two OH groups, mono-, di- or higher alkylated, higher-fused aromatics having one, two or more than two OH groups, alkoxylated derivatives of the aforementioned aromatic alcohols and mixtures thereof.
  • alkylated benzenes eg toluene and xylenes
  • higher fused aromatic hydrocarbons eg toluene and xylenes
  • mono-, di- and polyalkylated, higher-fused aromatics phenol, mono-, di- and polyalkylated phenols
  • higher fused aromatics having one, two or more than two OH groups
  • the organic liquid or liquefiable recyclable material produced according to the invention is an aromatic compound with a high content of mononuclear, low or non-alkylated aromatics.
  • An aromatics composition with a high content of mononuclear, low or non-alkylated aromatics is understood to mean a composition which, based on its total weight, contains at least 50% by weight of mononuclear aromatic compounds.
  • the content of non-alkylated, non-alkoxylated, at most simply hydroxylated and monoalkylated aromatics is, based on the total weight of the aroma composition, at least 50% by weight in total.
  • dealkylation refers to a reaction of the substituted and / or polynuclear aromatic compounds present in an aromatic composition in the presence of hydrogen and / or water vapor, which are at least partially converted so that substituents are replaced by hydrogen and / or several compounds containing aromatic nuclei are cleaved to compounds with fewer nuclei.
  • the substituents replaced by hydrogen are here selected from alkyl groups, hydroxyl groups, alkoxy groups, aryloxy groups, etc.
  • the term “dealkylation” also encompasses various reactions which are associated with a molecular weight reduction, such as dehydroxylation, dealkoxylation or
  • Aromatenspaltung refers to a reaction in which essentially the number of aromatic nuclei per molecule is reduced without the aromatic nuclei themselves being destroyed. Provision of a biomass starting material (step a))
  • a lignin-containing material is provided as biomass starting material.
  • Suitable lignin-containing starting materials are pure lignin and lignin-containing compositions.
  • the lignin content of the compositions is not critical over a wide range, only if the lignin contents are too low can the process no longer be operated economically.
  • a lignin-containing starting material is provided which contains at least 10% by weight, preferably at least 15% by weight, based on the dry matter of the material, of lignin.
  • lignin-containing compositions containing 10 to 100 wt .-%, particularly preferably 15 to 95 wt .-%, based on the dry matter of the material, lignin.
  • dry matter is understood in the sense of the standard ISO 1 1465.
  • Lignocellulose-containing materials are also suitable for providing a lignin-containing starting material for use in the process according to the invention.
  • Lignocellulose forms the structural framework of the plant cell wall and contains lignin, hemicelluloses and cellulose as main constituents.
  • Other components of the plant cell wall and thus obtained lignocellulose-containing materials are, for.
  • silicates extractable low molecular weight organic compounds (so-called extractives such as terpenes, resins, fats), polymers such as proteins, nucleic acids and gum (so-called exudate), etc.
  • Lignin is a biopolymer whose basic unit is essentially phenylpropane, which, depending on the natural source, may be substituted with one or more methoxy groups on the phenyl rings and with a hydroxy group on the propylene units. Therefore, typical structural units of lignin are p-hydroxyphenylpropane, guaiacylpropane and syringylpropane, which are linked by ether bonds and carbon-carbon bonds.
  • Suitable biomass starting materials for the process according to the invention are both lignocellulose-containing materials which are used without further chemical treatment in natural composition, such. As wood or straw, as well as lignocellulosic streams from the processing of lignocellulose, z. B. from processes for cellulose production (pulp process).
  • the lignocellulosic materials which can be used according to the invention are e.g. B. from wood and vegetable fibers available as starting material.
  • Preferred lignocellulosic materials are those of wood and residues of the woodworking industry. These include z. B.
  • wood ie hardwoods, such as maple, birch, pear, oak, alder, ash, eucalyptus, hornbeam, cherry, linden, walnut, poplar, willow, etc. and conifers such as Douglas fir, spruce, yew, hemlock, Pine, larch fir, cedar, etc.
  • Wood can be distinguished not only in deciduous and conifers, but also in so-called "hardwoods” and “softwoods”, which is not synonymous with the terms deciduous or coniferous wood.
  • Soft wood in contrast to hardwood, means lighter wood (ie wood with a density of less than 0.55 g / cm 3 , such as willow, cardboard, linden and almost all softwoods).
  • all hardwoods and all softwoods are suitable for use in the process according to the invention.
  • the wood used in the process according to the invention can also be used in ready-made form, for. In the form of pellets.
  • Suitable residues in the woodworking industry are in addition to wood waste and sawdust, parquet sanding dust, etc.
  • Suitable lignocellulosic materials are still natural fibers, such as flax, hemp, sisal, jute, straw, coconut fibers, switchgrass (Panicum virgatum) and other natural fibers.
  • Suitable lignocellulosic materials also fall as a residue in agriculture, z. As in the harvest of cereals (wheat straw, corn straw, etc.), corn, sugar cane (bagasse), etc. Suitable lignocellulosic materials also fall as a residue in the forest industry, z. In the form of branches, barks, woodchips, etc. A good source of lignocellulosic materials are also short rotation crops, which enable high biomass production in a relatively small area.
  • a lignocellulosic stream from the digestion of a lignocellulosic material for producing cellulose is preferably provided as the biomass feedstock.
  • a lignocellulose-containing material is subjected to digestion and from the digested material a cellulose-enriched fraction and a lignin-enriched (and simultaneously depleted in cellulose) fraction is isolated. The latter then serves, if appropriate after further workup, as biomass starting material for the process according to the invention.
  • a lignocellulose-containing material is thus subjected to a first digestion in step a) of the process according to the invention, from which a lignin-enriched material is isolated and subsequently subjected to a second digestion in step b).
  • lignin-containing streams are suitable for use as biomass starting material from all the digestion processes known to those skilled in the art.
  • these processes can be classified with regard to the treatment medium used in aqueous-alkaline processes, aqueous-acidic processes and organic processes. An overview of these methods and the digestion conditions can be found z. In WO 2010/026244.
  • the treatment medium used to digest the lignocellulosic materials is capable of solubilizing at least a portion of the lignin.
  • the cellulose contained in the lignocellulose-containing material is generally not or only partially solubilized in the treatment medium.
  • the separation of a cellulose-enriched fraction is then carried out by filtration or centrifugation.
  • a lignin-containing (cellulose-depleted) fraction is isolated from the digested material, which contains in addition to lignin at least one further component which is for example selected from hemicellulose, cellulose, degradation products of the aforementioned components, digestion chemicals and mixtures thereof.
  • the biomass starting material used is a lignin-containing starting material which contains at least one further component in addition to lignin. If a lignin-containing fraction which contains at least one further component in addition to lignin is used to provide the lignin-containing starting material, at least some of the compounds other than lignin can be removed before the digestion in step b).
  • the components removed from the lignin-containing fraction are preferably fed to a further work-up and / or thermal utilization, preferably in the course of the cellulose production process from which the lignin-containing fraction was obtained.
  • the pH of the lignin-containing fraction may first be adjusted to a suitable value.
  • Lignin-containing fractions from aqueous-alkaline processes can be mixed with an acid to adjust the pH.
  • Suitable acids are, for.
  • mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid.
  • Particularly preferred acid is CO2 (or the resulting carbon dioxide with water).
  • CO2 is used from an exhaust gas stream of the process according to the invention or a pulp process coupled to the process according to the invention.
  • Suitable is z.
  • the exhaust gas can be introduced into the lignin-containing fraction either directly or after separation from the other components (eg by means of a washing process, such as a Benfield wash).
  • a washing process such as a Benfield wash
  • the carbonates and / or bicarbonates resulting from the addition of CU2 can be easily recycled into the coupled pulp process, eg. B. in a previously taken to Lignin trenchung black liquor.
  • the use of CO2 to adjust the pH of the lignin-containing fraction is therefore associated with lower costs than with the use of other acids and also generally allows a good integration into a pulp process.
  • Lignin-containing fractions from aqueous-acidic processes can be mixed with a base to adjust the pH. Suitable bases are, for.
  • alkali metal bases such as sodium hydroxide or potassium hydroxide
  • alkali metal carbonates such as soda or potassium carbonate
  • alkali metal bicarbonates such as sodium bicarbonate or potassium bicarbonate
  • alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate, and ammonia or amines.
  • step a) the removal of at least a portion of the lignin-different compounds from the lignin-containing fraction) by filtration, centrifuging, extraction, precipitation, distillation, stripping or a combination thereof.
  • filtration centrifuging
  • extraction precipitation
  • distillation distillation
  • stripping stripping
  • the at least partial separation of the components other than lignin can be carried out in one or more stages.
  • Usual filtration methods are z. Cake and depth filtration (eg, described in A.
  • Rushton AS Ward, RG Holdich: Solid-Liquid Filtration and Separation Technology, VCH Verlagsgesellschaft, Weinheim 1996, pages 177ff., KJ Ives, in A. Rushton (A. Hg.): Mathematical Models and Design Methods in Solid-Liquid Separation, NATO ASI Series E No. 88, Martinus Nijhoff, Dordrecht 1985, pages 90ff.) And crossflow filtrations (eg described in J. Med. Altmann, S. Ripperger, J. Membrane Sci. 124 (1997), pages 1 19-128). Usual centrifugation methods are z. See, for example, G. Hultsch, H.
  • Suitable apparatus for working up by distillation include distillation columns, such as tray columns, which may be equipped with bells, sieve plates, sieve trays, packings, random packings, valves, side draws, etc., evaporators, such as thin film evaporators, falling film evaporators, forced circulation evaporators, Sambay evaporators, etc., and combinations from that.
  • a lignin-containing stream from the digestion of a lignocellulosic material which comprises at least part of the liquid treatment medium from the digestion is used to provide the lignin-containing starting material in step a).
  • the lignin-containing stream is then subjected to precipitation of a lignin-containing fraction, followed by partial or complete removal of the liquid components, to provide the lignin-containing starting material for digestion in step b).
  • the lignin-containing starting material is provided in the context of a process for the production of cellulose (pulp) into which the synthesis of synthesis gas according to the invention and at least one organic liquid or liquefiable recyclable material is integrated.
  • the removal of at least a portion of the liquid compounds then takes place in the context of the process for the production of pulp.
  • a black liquor can be used which is taken before or during the course of the individual evaporation steps of the underlying pulp process.
  • a lignin-containing stream from the digestion of a lignocellulosic material with an alkaline treatment medium is used.
  • a black liquor in particular a black liquor from the sulphate digestion (power digestion).
  • a black liquor from the Kraft digestion can first be acidified to precipitate at least a portion of the lignin contained and then the precipitated lignin can be isolated.
  • the aforementioned acids are suitable.
  • CO2 is used.
  • the pH of the black liquor is lowered to a value of at most 10.5.
  • the isolation of the precipitated lignin is preferably carried out by a filtration process. Suitable filtration methods are those mentioned above. If desired, the isolated lignin may be subjected to at least one further work-up step. This includes z. B. a further cleaning, preferably a wash with a suitable washing medium. Suitable washing media are for. For example, mineral acids such as sulfuric acid, preferably in aqueous solution.
  • a black liquor from the kraft digestion is first acidified with CO 2 to precipitate at least part of the lignin contained, then the precipitated lignin is isolated by filtration and the filtrate is subjected to scrubbing with sulfuric acid.
  • step b) of the process according to the invention the biomass starting material is subjected to digestion to obtain a digestion product which contains components whose average molecular weight is significantly below the average molecular weight of the components contained in the biomass starting material.
  • a lignin-containing starting material is used for the digestion in step b).
  • the digestion product obtained in step b) predominantly comprises components having a molecular weight of at most 500 g / mol, more preferably of at most 400 g / mol, in particular of at most 300 g / mol.
  • the digestion in step b) can in principle take place according to two variants, which are described in detail below.
  • the first variant comprises a pyrolysis and leads accordingly to a pyrolysis product.
  • the second variant comprises an implementation in the presence of a liquid digestion medium and accordingly leads to a product of the liquid digestion.
  • pyrolysis In a first variant of the process according to the invention, the biomass starting material, especially the lignin-containing starting material, is subjected to pyrolysis in step b).
  • pyrolysis is understood as meaning a thermal treatment of the biomass starting material, molecular oxygen being not or only to a small amount being supplied.
  • a small amount is to be understood as an amount that is significantly less than the amount necessary for a complete oxidation of the carbon contained in the biomass starting material to CO2.
  • the amount of molecular oxygen fed in the pyrolysis is at least 50 mol%, more preferably at least 75 mol%, in particular at least 90 mol%, below the amount necessary for complete oxidation of the carbon contained in the biomass starting material to CO2 is necessary.
  • Pyrolysis is generally endothermic.
  • the digestion product is at least partially gaseous.
  • the pyrolysis can be carried out batchwise or continuously. Continuous pyrolysis is preferred.
  • the pyrolysis takes place in at least one pyrolysis zone.
  • the biomass starting material especially the lignin-containing starting material, by means of suitable transport devices, such. B. screw conveyor or pneumatic conveying, are registered in a pyrolysis zone.
  • the biomass starting material is preferably used in predominantly solid form.
  • Predominantly solid Form means in the context of the invention that the starting material used for pyrolysis under normal conditions (20 ° C, 1013 mbar) has a liquid content of at most 70 wt .-%, more preferably of at most 50 wt .-%, based on the total weight of the starting material ,
  • the biomass starting material, especially the lignin-containing starting material then z. B. used as a moist or predried solid.
  • the pyrolysis zone may be designed in various embodiments, for. B. as a rotary kiln or fluidized bed. Both stationary and circulating fluidized beds are suitable.
  • a fluidizing gas preferably water vapor or a gas mixture from one of the subsequent process steps
  • quartz sand Particularly suitable as an additive is quartz sand.
  • Such a fluidized bed process is z.
  • the pyrolysis zone comprises at least one fixed bed.
  • the fixed beds may comprise at least one inert fixed bed and / or at least one catalytically active fixed bed. If the process according to the invention is operated with at least one fixed bed as the pyrolysis zone, then an interval operation may be advantageous in which a pyrolysis phase is followed by a combustion phase in order to remove low-volatility components from the fixed bed.
  • a fluidizing gas can be fed into the pyrolysis zone.
  • Preferred fluidizing gases are water vapor, carbon dioxide, nitrogen, etc., or mixtures of these gases.
  • the pyrolysis is not carried out with the addition of hydrogen.
  • the hydrogenating reaction takes place essentially in the dealkylation step d).
  • This embodiment of the pyrolysis can also be referred to as hydrocracking.
  • hydrocracking the biomass feedstock, specifically lignin, is split by the action of hydrogen into small-molecule fragments.
  • the pyrolysis with the addition of hydrogen is preferably carried out in suspension. It is furthermore preferably carried out using a catalyst and / or under high pressure.
  • a catalyst and / or under high pressure Such a method is z.
  • a vaporized black liquor from the kraft process is used for pyrolysis.
  • Such a method is z. As described in US 3,375,283.
  • the black liquor is predominantly in solid form.
  • the also incurred solid residue can, for. B. be returned to the pulping process.
  • pyrolysis is carried out using a black liquor material which under normal conditions (20 ° C., 1013 mbar) has a liquid content of at most 70% by weight, particularly preferably at most 50% by weight, based on the total weight of the black liquor material having.
  • the pyrolysis in step b) can be carried out in the presence of at least one pyrolysis catalyst.
  • pyrolysis catalyst for example, silica, alumina, aluminosilicates, layered aluminosilicates and zeolites such as mordenite, faujasite, zeolite X, zeolite-Y and ZSM-5, zirconia or titania.
  • the temperature in the pyrolysis is preferably in a range of 200 to 1500 ° C, more preferably 250 to 1000 ° C, especially 300 to 800 ° C.
  • the pressure in the pyrolysis is preferably in a range of 0.5 to 250 bar (absolute), preferably 1, 0 to 40 bar (absolute).
  • the residence time at the pyrolysis temperature can be a few seconds to several days. In a specific embodiment, the residence time at the pyrolysis temperature is 0.5 second to 5 minutes, more specifically 2 seconds to 3 minutes.
  • the residence time especially in the case of a fluidized-bed reactor, results from the quotient of the total volume of the reactor to the volume flow of the fluidizing gas under the pyrolysis conditions.
  • Suitable processes for the catalyzed or uncatalyzed pyrolysis of lignin are e.g. Also described in WO 96/09350 (Midwest Research Institute, 1996) or US 4,409,416 (Hydrocarbon Research Institute, 1983), which is incorporated herein by reference.
  • the biomass starting material especially the lignin
  • a pyrolysis product which is at least partly gaseous ("pyrolysis gas") under the conditions of pyrolysis.
  • pyrolysis gas gaseous
  • a pyro- lyse alloy that are partially liquid and / or solid under the conditions of pyrolysis.
  • the digestion product obtained in the pyrolysis in step b) contains substituted aromatics and / or polynuclear aromatics.
  • the digestion product may contain, in addition to aromatics, other components selected from water vapor, inert gas (eg, nitrogen), non-aromatic hydrocarbons, H, CO, CO2, sulfur-containing compounds, such as e.g. As H2S, etc. and mixtures thereof.
  • the non-aromatic hydrocarbons are preferably degradation products, such as methane.
  • the biomass starting material is subjected to digestion in the presence of a liquid digestion medium in step b).
  • the digestion product falls at least partially in the liquid phase.
  • the digestion in the liquid phase is possible by a variety of methods, which differ mainly with regard to the digestion medium.
  • the biomass starting material, in particular the lignin-containing starting material is preferably subjected to digestion in the presence of an aqueous-alkaline, aqueous-acidic or organic disintegration medium in step b).
  • At least one cellulose-depleted fraction from a pulp process is preferably used.
  • One particular embodiment is a cellulose-depleted fraction from a pulp process which still contains at least a portion of the liquid treatment medium from pulping the lignocellulosic material for pulping.
  • the treatment medium used for the digestion in step b) comprises at least one compound which is liquid under normal conditions (20 ° C. and 1013 mbar). This is preferably selected from water, acids, bases, organic solvents and mixtures thereof. Under normal conditions, liquid acids and bases or liquid mixtures containing acids or bases may be selected by one skilled in the art from those listed below.
  • the organic solvents are preferably selected from alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol or phenol, diols and polyols, such as ethanediol and propanediol, aminoalcohols, such as ethanolamine, diethanolamine or triethanolamine, aromatic hydrocarbons, such as benzene, toluene, ethylbenzene or xylenes, halogenated solvents, such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane or chlorobenzene, aliphatic solvents, such as pentane, hexane, heptane, octane, ligroin, petroleum ether, cyclohexane or decalin, ethers, such as tetrahydrofuran , Diethyl ether
  • the liquid compound is selected from water, water-miscible organic solvents and mixtures thereof.
  • the liquid compound is selected from water, alcohols and mixtures thereof.
  • water, methanol, ethanol, a mixture of water with methanol and / or ethanol or a mixture of methanol and ethanol can be used.
  • the liquid digestion medium used in step b) may comprise at least one base.
  • Suitable bases are alkali and alkaline earth metal hydroxides, e.g. For example, sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide, alkali metal and Erd- alkali metal bicarbonates, z.
  • sodium bicarbonate, potassium hydrogen carbonate, calcium bicarbonate or magnesium hydrogen carbonate, alkali metal and Erd- alkali metal carbonates eg.
  • Sodium carbonate, potassium carbonate, calcium carbonate or magnesium carbonate, alkaline earth metal oxides such as calcium oxide or magnesium oxide, and mixtures thereof.
  • the liquid digestion medium used in step b) may comprise at least one acid.
  • Brönsted acids or Lewis acids are suitable.
  • Suitable Brönsted acids are inorganic acids, their acid salts and anhydrides. These include, for example, mineral acids, such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or amidosulfonic acid, but also ammonium salts, such as ammonium fluoride, ammonium chloride, ammonium bromide or ammonium sulfate.
  • mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or amidosulfonic acid
  • ammonium salts such as ammonium fluoride, ammonium chloride, ammonium bromide or ammonium sulfate.
  • hydrogen sulfates such as sodium hydrogen sulfate, potassium hydrogen sulfate, calcium umhydrogen sulfate or magnesium hydrogen sulfate.
  • hydrogen sulfites such as sodium hydrogen sulfite, potassium hydrogen sulfite, calcium hydrogen sulfite or magnesium hydrogen sulfite.
  • hydrogen phosphates and dihydrogen phosphates such as sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate or potassium dihydrogen phosphate.
  • SO2, SO3 and C0 2 are also suitable.
  • Suitable Bronsted acids are also organic acids and their anhydrides, such as formic acid, acetic acid, methanesulfonic acid, trifluoroacetic acid or p-toluenesulfonic acid.
  • Suitable Lewis acids are any metal or semimetallic halides in which the metal or metalloid has an electron pair gap. Examples of these are BF 3 , BCl 3 , BBr 3 , AIF 3 , AICI 3 , AIBr 3 , ethylaluminum dichloride, diethylaluminum chloride, TiF 4 , TiCl 4 , TiBr 4 , VCIs, FeF 3 , FeCl 3 , FeBr 3 , ZnF 2 , ZnCl 2 , ZnBr 2 , Cu ( l) F, Cu (I) Cl, Cu (I) Br,
  • the liquid digestion medium used in step b) may comprise at least one salt other than the abovementioned compounds.
  • the salts are preferably selected from salts of the abovementioned acids and bases and also their oxidation or reduction products. Suitable salts are, for. For example, ammonium, alkali metal or alkaline earth metal sulfates, such as sodium sulfate, potassium sulfate, calcium sulfate or magnesium sulfate. Also suitable are ammonium, alkali metal or alkaline earth metal sulfites, such as sodium sulfite, potassium sulfite, calcium sulfite or magnesium sulfite.
  • ammonium, alkali metal or alkaline earth metal sulfides such as sodium sulfide, potassium sulfide, calcium sulfide or magnesium sulfide.
  • alkali metal hydrogen sulfides such as sodium hydrogen sulfide or potassium hydrogen sulfide.
  • the liquid digestion medium used in step b) may contain other compounds which are different from the abovementioned compounds. These are in particular the customary process chemicals known to the person skilled in the art for the various digestion processes for the production of pulp from a lignocellulose-containing starting material. Such processes and the process chemicals used therein are known to the person skilled in the art.
  • an alkaline digestion medium is used in step b). Specifically, for digestion in step b) at least one cellulose-depleted fraction from a pulp process is used, which at least partially comprises the alkaline digestion medium from the previous pulp process.
  • a cellulose-depleted fraction from the kraft process is then preferably used.
  • the digestion medium used in step b) then contains NaOH and Na 2 S in an aqueous medium.
  • the treatment medium used in step a) contains NaOH, Na 2 S, Na 2 CO 3 and Na 2 SO 4 in an aqueous medium.
  • a black liquor obtained during pulp production after the kraft process is used. Either the weak liquor (“weak black liquor") arising directly after the separation of the pulp fibers or a more concentrated quality resulting from evaporation can be used for this purpose.
  • Particularly advantageous is the digestion in alkaline aqueous phase, as described by Clark and Green in Tappi, 51 (1), 1968, 44 ff.
  • a cellulose-depleted fraction from the soda process can also be used.
  • the treatment medium used in step b) then contains as the main component NaOH in an aqueous medium which is essentially free of sulfur-containing compounds.
  • a cellulose-depleted fraction from the alkali-oxygen digestion can also be used.
  • a cellulose-depleted fraction from the alkali peroxide digestion can also be used.
  • step b For the digestion in step b), it is also possible to use a cellulose-depleted fraction from the digestion in the presence of anthraquinone.
  • a cellulose-depleted fraction from the digestion of the lignocellulosic material with organic solvents can be used.
  • organic solvents are those mentioned above.
  • an organic solvent is used, which is selected from C 1 -C 4 -alkanols, mixtures of C 1 -C 4 -alkanols and mixtures of at least one C 1 -C 4 -alkanol with water.
  • the C 1 -C 4 -alkanols are preferably selected from methanol, ethanol, n-propanol, isopropanol and n-butanol. Preferred are methanol, ethanol and mixtures thereof.
  • Mixtures of at least one C 1 -C 4 -alkanol with water preferably contain 10 to 99% by weight. %, particularly preferably 20 to 95 wt .-%, of at least one Ci-C4-alkanol, based on the total weight of the mixture.
  • the digestion medium used in step b) can then additionally contain an additive from the underlying pulp process. These include z. Alkali metal hydroxides, such as sodium hydroxide; Ammonium hydrogen sulfite and alkali and alkaline earth metal hydrogen sulfites, such as sodium hydrogen sulfite and magnesium hydrogen sulfite.
  • mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or amidosulfonic acid and their ammonium, alkali metal and alkaline earth metal salts.
  • organic acids such as oxalic acid, formic acid or acetic acid.
  • peracids such as persulfuric acid or peracetic acid.
  • step b) of the process according to the invention are the cellulose-depleted fractions which contain at least part of the liquid treatment medium from one of the following commercially used organosolv processes:
  • Alcell method ethanol / water mixture as treatment medium.
  • ASAM method Alkaline sulfite-anthraquinone-methanol treatment medium.
  • Organocell method Two-stage process with an organic medium in the first stage and an alkaline medium in the second stage, eg. B. digestion with methanol and / or ethanol in the first stage and with methanol and / or ethanol, NaOH, and optionally anthraquinone in the second stage.
  • Acetosolv process acetic acid / hydrochloric acid mixture as treatment medium.
  • the digestion in the presence of a liquid digestion medium in step b) can be carried out in one or more stages. In the simplest case, the digestion in step b) takes place in one stage.
  • the digestion in step b) preferably takes place above the ambient temperature.
  • the temperature is preferably in a range of about 40 to 300 ° C, more preferably 50 to 250 ° C. In a specific embodiment, the temperature is initially increased successively or continuously in the course of treatment until the desired final temperature is reached.
  • the digestion in step b) can be carried out at reduced pressure, at ambient pressure or above the ambient pressure.
  • the pressure in step a) is generally in a range of 0.01 bar to 300 bar, preferably 0.1 bar to 100 bar.
  • the duration of the digestion in step b) is generally 0.5 minutes to 7 days, preferably 5 minutes to 96 hours.
  • the digestion is advantageously carried out in close proximity to the location of pulp production, in order to minimize the transport costs for the cellulose-depleted fraction, especially a black liquor .
  • the transport preferably takes place via pipeline.
  • the digestion product obtained in the digestion in the presence of a liquid digestion medium in step b) contains substituted aromatics and / or polynuclear aromatics.
  • step c The separation and further treatment of the digestion product obtained in the presence of a liquid digestion medium in step b) is described in more detail in step c).
  • step b) It is in principle possible to use the digestion product obtained in step b) without further separation and / or treatment for dealkylation in step d). If the digestion product obtained in step b) is obtained in the liquid phase, this is preferably subjected to evaporation before the feed in step d). A preferred embodiment of the evaporation is depicted in FIG. 2 and described below.
  • the digestion product obtained in step b) is subjected to separation and / or treatment (step c) prior to its use in dealkylation (step d).
  • step c) the digested material obtained in step b) is separated into at least one aromatic-enriched fraction C1) and at least one aromatic-depleted fraction C2).
  • the separation is preferably carried out by distillation, extraction, absorption, membrane method or a combination thereof.
  • the separation is particularly preferably carried out by distillation, extraction or a combination thereof.
  • the separation in step c) preferably takes place by means of distillation and / or extraction.
  • the biomass starting material provided in step a) is subjected to liquid phase digestion in step b) and comprises, in step c), the separation into at least one aromatics-enriched fraction C1) and at least one of aromatics fraction C2), an extraction and / or a distillation.
  • the pH of the discharge from a digestion in the liquid phase in step b) is set to a desired value.
  • a digestion product obtained by digestion in the presence of an alkaline digestion medium is used in step c).
  • at least one cellulose-degraded fraction from a pulp process, in particular a black liquor from the kraft process was used.
  • Suitable acids are, for.
  • mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid and acid-forming compounds such as CO2 and H2S.
  • CO2 is used from an exhaust gas stream of the process according to the invention or a pulp process coupled with the process according to the invention.
  • Suitable is z. B. the exhaust gas from a
  • Black liquor combustion recovery boiler
  • the exhaust gas can be introduced into the digestion product either directly or after separation from the other components (eg by means of a washing process, such as a Benfield wash).
  • the resulting by CÜ2 addition carbonates and / or bicarbonates can be easily z. B. in a coupled to the pulping process pulp process, z. B. in a previously extracted for Ligninge- winning black liquor.
  • the use of CO2 to adjust the pH value is therefore associated with lower costs than with the use of other acids and also generally allows a good integration into a pulp process.
  • the hydroxyaromatics obtained in the digestion in step b) are virtually completely present as salts (phenolates) at pH values above about 9.
  • the distillative separation of the product obtained in step b) from the digestion in the liquid phase can be carried out by customary methods known to the person skilled in the art. Preference is given to a steam distillation, wherein an aromatics-enriched distillate is obtained. In this procedure, one uses the water vapor volatility of the obtained in the digestion in step b) aromatic fragments, to separate these from the digestion product. Preference is given to a multi-stage process in which the heat of condensation of the vapors of at least one stage is used for evaporation in another stage. The distillation product obtained is enriched in aromatics with respect to the pulping product used and is suitable, if appropriate after separation of the aqueous phase, as a feedstock for the dealkylation in step d).
  • the separation of the product obtained in step b) from the digestion in the liquid phase is also preferably carried out by extraction.
  • at least part of the aromatics obtained in the digestion in step b) is separated off, while the remaining residue (low-aromatic organic components, inorganic process chemicals, etc.) for further processing and / or thermal utilization, preferably in the context of the inventive method or a coupled therewith integrated process for pulp process, can be supplied.
  • a solvent for extraction, a solvent (extractant) can be used in which the aromatics obtained in the digestion are soluble in a sufficient amount and otherwise forms a miscibility gap with the digestion product.
  • the extractant is then intimately contacted with the digestion product obtained in step b), followed by phase separation.
  • the extraction can be configured in one or more stages.
  • Suitable extractants are organic compounds, such as aromatic or non-aromatic hydrocarbons, alcohols, aldehydes, ketones, amides, amines and mixtures thereof. These include z. Benzene, toluene, ethylbenzene, xylenes; Pentane, hexane, heptane, octane, ligroin, petroleum ether, cyclohexane, decalin, n-butanol, sec-butanol, tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, methyl ethyl ketone, and mixtures thereof , Extraction may be discontinuous or continuous as described in: K.
  • the separation into at least one aromatics-enriched fraction C1) and at least one aromatic-depleted fraction C2) in step c) comprises the following substeps: c1) extraction of the digestion product obtained in step b) to obtain an aromatic compound c2) optionally separating the extract into an extractant-enriched (and aromatics-depleted) fraction and an aromatics-enriched (and depleted-in) fraction, c3) feeding the feedstock in step c1) to an enriched extract and an aromatic-depleted residue; obtained in aromatics enriched extract or obtained in step c2), aromatics-enriched fraction in step d).
  • the pH of the digestion product obtained in step b) can be adjusted by adding at least one acid or at least one base.
  • the pH of the digestion product used in the first stage and the pH of the residue separated from the extractant phase at the respective stage can be adjusted by adding at least one acid or acid-forming compound or at least one base.
  • Suitable acids are, for.
  • mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, or acid-forming compounds such as CO2 and H2S.
  • Suitable bases are, for.
  • alkali metal bases such as sodium hydroxide or potassium hydroxide
  • alkali metal carbonates such as soda or potassium carbonate
  • alkali metal bicarbonates such as sodium bicarbonate or potassium bicarbonate and alkaline earth metal bases, such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate and ammonia or amines.
  • the separation of the extract in step c2) into an extractant-enriched fraction and an aromatic-enriched fraction C1) is preferably carried out by distillation.
  • the distillative separation of the extract in step c2) can be carried out by customary methods known to the person skilled in the art. Suitable methods are described in: K. Sattler, Thermal Separation Methods, Wiley-VCH, Third Essentially Revised and Extended Edition, July 2001.
  • Suitable apparatus for distillative separation include distillation columns, such as tray columns containing bells, sieve plates, sieve trays, packages , Internals, valves, side vents, etc. may be provided. Particularly suitable partition wall columns, which can be provided with Soabmann, returns, etc. For distillation, a combination of two or more than two distillation columns can be used. Also suitable are evaporators, such as thin film evaporators, falling film evaporators, Sambay evaporators, etc., and combinations thereof.
  • the separation in step c) is preferably carried out by absorption.
  • the biomass starting material provided in step a) is subjected to pyrolysis for digestion in step b) and comprises the separation in step c) into at least one aromatics-enriched fraction C1) and at least one aromatic-depleted fraction C2) an absorption.
  • the discharged from the pyrolysis discharge can in addition to the pyrolysis still contain fractions of solid and / or liquid components. These are z. For example, low-volatility components (eg coke) formed during pyrolysis. If at least one solid aggregate is used for the pyrolysis in step b), the discharge from the pyrolysis zone may also contain fractions of the aggregate. These solid and / or liquid components may, if desired, in step c) by means of a suitable device, for. As a cyclone, are separated from the pyrolysis gas. Separate solid additives are preferably recycled to the pyrolysis zone. From aggregates different separated components are supplied to another utilization, eg.
  • the resulting exhaust gas which contains mainly CO2 and water and optionally O2, can also be recycled. It is also possible to carry out a discharge from the pyrolysis zone which at least NEN additive and pyrolysis under the pyrolysis contains volatile components in a spatially separate from the pyrolysis zone combustion zone with an oxygen-containing gas, preferably air, in contact, resulting in the burning of resulting in the pyrolysis low volatility components ("coke").
  • an oxygen-containing gas preferably air
  • the discharge from the pyrolysis can be directly, i. H. without separation of condensable components, are led into the subsequent Dealkylierungs- zone.
  • components of the discharge from the pyrolysis zone which are difficult to volatilize under the conditions of pyrolysis in step b) and are not gaseous in the discharge from the pyrolysis zone, but solid or liquid, can be separated before entry into the dealkylation zone.
  • condensable pyrolysis products i.e., products which are present under normal conditions as liquids or solids
  • suitable separation processes known to the person skilled in the art, such as condensation, absorption, adsorption, membrane separation processes, etc.
  • a particularly preferred variant is an absorption d1.
  • the discharge from the pyrolysis zone is brought into contact with a stream D1) which contains a suitable solvent.
  • the contacting is preferably carried out after a cooling step in which a condensation of high-boiling components can take place.
  • the contacting takes place in a suitable device (eg a column).
  • the contact device emanates a liquid stream D2), which contains the absorbent and aromatic pyrolysis products and a gaseous stream D3), which is depleted compared to the discharge from the pyrolysis of aromatic pyrolysis products.
  • Stream D2) is, preferably by distillation, fractionated into a fraction D4) enriched in aromatic pyrolysis products relative to D2) and a fraction D5 depleted in aromatic pyrolysis products relative to D2).
  • D4) if necessary after further work-up, as stream C1) in the subsequent Dealkylierungsitz and D5), after further cooling, led back into the absorption, d. H.
  • D5 is the main component of D1).
  • Another ingredient is a solvent portion, which is added to compensate for solvent losses.
  • Solvents suitable as absorbents are organic compounds, such as aromatic or non-aromatic hydrocarbons, alcohols, aldehydes, ketones, Amides, amines and mixtures thereof. These include z. Benzene, toluene, ethylbenzene, xylenes; Pentane, hexane, heptane, octane, ligroin, petroleum ether, cyclohexane, decalin, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, 1-pentanol, 1-hexanol, 1 - Heptanol, 1-octanol, acetaldehyde, acetone, methyl ethyl ketone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and mixtures thereof.
  • organic compounds such
  • the solvent preferably has a boiling point which, under identical conditions, is below that of the phenol.
  • the solvent particularly preferably has a boiling point which, under identical conditions, is at least 10 K below the boiling point of the phenol.
  • the solvent additionally preferably has a high solubility in water. These include z. As methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
  • the solvents used as absorbents have a vapor pressure under the conditions of absorption, which leads to a loading of the gas stream D3 leaving the absorption with the absorbent. This is especially true for the preferred solvents used having a boiling point below the boiling point of phenol.
  • the gas stream D3) leaving the absorption is then subjected to at least partial removal of the solvent contained.
  • the separation of the solvent from the gas stream D3) takes place in the form of a water wash.
  • a good water solubility of the solvent used for absorption is particularly advantageous.
  • the loaded with solvent and optionally aromatics wash water stream may, for. B. be worked up by distillation.
  • the thereby separated absorbent is (optionally together with the aromatics) moved back to the absorption step d1).
  • the digestion product obtained in step b) can be subjected to at least one further treatment step in step c) in addition to the separation described above. Additional treatment steps can be carried out before, during or after the separation.
  • the digestion product obtained in step b) or the fraction C1) isolated therefrom in step c) predominantly comprises components having a molecular weight of at most 500 g / mol, more preferably of at most 400 g / mol, in particular of at most 300 g / mol , on.
  • the aromatics-depleted fraction C2) isolated in step c) is used at least partially for the production of synthesis gas.
  • dealkylation the aromatic degradation products formed during pyrolysis in step b) and, if appropriate, isolated in step c) as fraction C1) are at least partially converted by the action of hydrogen and / or water vapor so that substituents are replaced by hydrogen and / or several aromatic nuclei containing compounds are cleaved to compounds with a smaller number of nuclei.
  • dealkylation also refers to reactions in which no alkyl substituent is replaced by hydrogen, such as dehydroxylation, dealkoxylation, aromatic cleavage, etc.
  • the hydrogen-substituted substituents are preferably selected from alkyl groups, hydroxy groups, and alkoxy groups.
  • Suitable dealkylation processes for use in step d) include hydrodealkylation, steam dealkylation or mixtures thereof.
  • hydrodealkylation in addition to the pyrolysis gas stream, molecular hydrogen is fed into the dealkylation zone (in pure form or mixed with other components, such as CO), but no water.
  • water in pure form or in a mixture with other components is fed into the dealkylation zone in addition to the pyrolysis gas stream, but no molecular hydrogen.
  • the dealkylation process in step d) can also be designed as a mixed form of hydrodealkylation and steam dealkylation.
  • both water and molecular hydrogen are fed into the dealkylation zone.
  • suitable and preferred process parameters are given in part for the hydrodealkylation and the steam dealkylation.
  • the person skilled in the art is able to determine suitable and preferred process parameters for a mixed form of hydrodealkylation and steam dealkylation.
  • the reaction gas used for dealkylation of H2 and H2O then has a mixing ratio of H2 to H2O in the range of about 0.1: 99.9 to 99.9: 0.1.
  • a particularly suitable mixing ratio of H2 to H2O is in the range from about 40:60 to 60:40.
  • the hydrogen required for the reaction is formed in the case of Dampfdealkyltechnik in situ by reaction of water with (mainly organic) components, either in the educt mixture of Dampfdealkylierung are included or arise in the course of Dampfdealkyltechnik.
  • exemplary here the emergence of Hydrogen from methane and water according to the equation CH 4 + H2O - CO + 3 H2.
  • the temperature in the dealkylation zone is in a range from 400 to 900 ° C, more preferably from 500 to 800 ° C.
  • the absolute pressure in the dealkylation zone is preferably in the range from 1 to 100 bar, more preferably from 1 to 20 bar.
  • the pyrolysis gas stream is subjected to a hydrodealkylation in step c). For this, the reaction in step c) takes place in the presence of hydrogen.
  • the temperature in the dealkylation zone for the hydrodealkylation is in a range of 500 to 900 ° C, more preferably 600 to 800 ° C.
  • the absolute pressure in the dealkylation zone for the hydrodealkylation is preferably in the range from 1 to 100 bar, particularly preferably from 1 to 20 bar, in particular from 1 to 10 bar.
  • the feed ratio of H 2 to H 2 is preferably in a range from 0.02 to 50, particularly preferably from 0.2 to 10.
  • H 2 stands for the amount H 2, which theoretically is just the complete one Reaction of the supplied to the Dealkyltechnikszone aromatics to Benzol is required, assuming that per core substituent 1 mole of H2 reacts.
  • the residence time in the dealkylation zone is preferably in the range from 0.1 to 500 s, particularly preferably from 0.5 to 200 s, for the hydrodealkylation.
  • the pyrolysis gas stream is subjected to a steam dealkylation in step c).
  • the reaction in step c) takes place in the presence of water vapor.
  • the temperature in the dealkylation zone for the vapor dealkylation is preferably in the range from 400 to 800 ° C., particularly preferably from 475 to 600 ° C., in particular from 525 to 600 ° C.
  • the absolute pressure in the dealkylation zone for the vapor dealkylation is preferably in a range from 1 to 100 bar, particularly preferably from 1 to 20 bar, in particular from 1 to 10 bar.
  • the amount ratio of H 2 O to C * is preferably in a range from 0.1 to 20 mol / mol, particularly preferably from 0.5 to
  • C * stands for the molar amount of carbon, determined by carbon-based balancing of the pyrolysis or by determining the amounts of the product exhausts from the steam dealkylation by methods known to the person skilled in the art.
  • the molar ratio of H2 to CH4 in the dealkylation zone is preferably in a range of ⁇ 50: 1, particularly preferably ⁇ 25: 1.
  • WHSV is preferably in a range from 0.05 to 10 kg / (L * h), particularly preferably from 0.1 to 2 kg / (L * h).
  • the steam dealkylation can be carried out in the presence or absence of a catalyst. In a specific embodiment, steam dealkylation is carried out in the absence of a catalyst.
  • a catalyzed process for steam dealkylation is in
  • At least one low molecular weight aromatic valuable substance is formed as the target product of the process according to the invention.
  • the low molecular weight aromatic valuable substances are preferably selected from benzene and phenolic compounds, such as phenol and / or dihydroxybenzenes.
  • the dealkylation zone is removed from a discharge and subjected to separation.
  • at least one organic liquid or liquefiable recyclable material is obtained as the first desired product and at least one stream enriched in components which are more volatile than the organic valuable material. It is preferred to obtain, as the first desired product, an aromatic compound with a high content of mononuclear, low or non-alkylated aromatics.
  • the effluent from the dealkylation zone is subjected to separation to give the following three streams:
  • the effluent from the dealkylation zone may be subjected to separation to yield additional streams, such as e.g. B. a hydrous stream.
  • Stream E1) is the first value product produced in the process according to the invention.
  • E1) is preferably an aromatics composition with a high content of mononuclear, low or unalkylated aromatics.
  • stream E1) can be subjected to a further workup to obtain the aroma composition prepared according to the invention.
  • the stream E1) preferably contains at least 70% by weight, more preferably at least 80% by weight, in particular at least 90% by weight, based on the total amount of E1) of mononuclear aromatic compounds.
  • the stream E1) preferably contains at most 30% by weight, particularly preferably at most 20% by weight, in particular at most 10% by weight, based on the total amount of E1) of slightly or not dealkylated aromatics.
  • the stream E2) preferably contains at least 70% by weight, more preferably at least 80% by weight, in particular at least 90% by weight, based on the total amount of E2) of aromatics which are less or not dealkylated.
  • the stream E3) contains components that z. B. are selected from non-aromatic see hydrocarbons, especially methane, hydrogen, carbon monoxide, carbon dioxide and mixtures thereof. Depending on the lignin-containing starting material provided in step a), the stream E3) may contain further components.
  • a lignin-containing starting material from the Kraft process include sulfur-containing by-products, especially h S.
  • a gaseous effluent is removed from the dealkylation zone and subjected to separation in step e).
  • the well-known thermal Trennver- can be used as a method for separation.
  • the separation of the discharge from the dealkylation zone in step e) preferably comprises an absorption.
  • the gaseous effluent from the dealkylation zone is contacted with a solvent (absorbent), whereby a part of the components contained in the gas stream is absorbed and thus separated.
  • the absorption is carried out in a suitable apparatus, e.g. B. a countercurrent column, bubble column, etc.
  • a suitable apparatus e.g. B. a countercurrent column, bubble column, etc.
  • the absorption is carried out in a countercurrent column.
  • the absorption can be configured in one or more stages.
  • a solvent unloaded: absorbent, loaded: absorbate
  • the aromatics obtained in the dealkylation are soluble in a sufficient amount and the volatile by-products which differ from them are substantially insoluble.
  • the absorption thus contains on the one hand an aromatics-laden absorbate.
  • the aromatic components contained in the absorbate correspond in composition to the sum of the aromatics in the streams E1) and E2) plus aromatics optionally present in the absorbent.
  • the components contained in the remaining gas stream correspond in their composition to the stream E3).
  • the gas stream may be subjected to an additional aromatic aromatics removal step. These can then be combined again with the aromatics contained in the separated solvent for joint workup. In general, however, such isolation of aromatics from the separated gas stream is not required.
  • the separation of the discharge from the dealkylation zone in step e) comprises the following substeps:
  • the absorbent has a boiling point which is above the boiling point of the highest boiling components of stream E1.
  • an absorbent is used, which is different from the components of the streams E1) and E2).
  • Suitable absorbents for this embodiment are non-aromatic hydrocarbons, non-aromatic alcohols, non-aromatic aldehydes, ketones, amides, amines and mixtures thereof.
  • the absorbent for this embodiment is selected from pentane, hexane, heptane, octane, ligroin, petroleum ether, cyclohexane, decalin, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, 1 Pentanol, 1-hexanol, 1-heptanol, 1-octanol, acetaldehyde, acetone, methyl ethyl ketone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and mixtures thereof.
  • Suitable absorbents are furthermore from the components of the streams E1) and E2) different aromatic hydrocarbons. These aromatic hydrocarbons are preferably selected from optionally substituted acetophenones, optionally substituted benzophenones, optionally substituted biphenyls, optionally substituted terphenyls, optionally substituted diphenyl ethers and mixtures thereof. If the absorption medium used is a component which is also present in the streams E1) or E2) as by-product, measurement and control measures known to the person skilled in the art can ensure that this component is continuously present in the amount in which they are present incurred, is led out of the process.
  • the separation of the discharge from the dealkylation zone in step e) preferably comprises the following partial steps:
  • the absorbent used is an aromatic compound which can be obtained by the process according to the invention. This is specifically a mixture of aromatics that are not or not fully converted in the dealkylation.
  • the absorption medium used is an aromatic composition whose composition corresponds, in part or in full, to the stream E2 or to a mixture of E1 and E2.
  • the stream E2 or the mixture of E1 and E2 may be subjected to at least one work-up step prior to use as an absorbent.
  • the separation of the discharge from the dealkylation zone in step e) preferably comprises the following substeps:
  • the solvent can be obtained by partial condensation of the stream from the dealkylation or a gas stream from a downstream of the dealkylation high boiler pre-separation.
  • at least partial absorption of the aromatics which are not reacted or not fully converted takes place.
  • the aromatic components contained in the absorbate correspond to of their composition of the sum of the aromatics of the streams E1) and E2).
  • step e2) the aromatics-enriched absorbate is preferably separated by distillation.
  • the solvent thus recovered optionally after separation of absorbed water, is recycled to the absorption (step e1)).
  • the aromatics are processed further as before and described below.
  • the aromatics-enriched absorbate is separated by distillation in at least one column ("regeneration column").
  • the distillation conditions are preferably selected so that substantially low or non-alkylated aromatics and, if present, water and, as the bottom product, substantially low or non-dealkylated aromatics are obtained as top product.
  • the bottom temperature is chosen so low that undesirable side reactions of the bottom product are substantially avoided. This can be achieved in particular by setting a suitable column pressure and / or the low boiler content in the bottoms (the low boiler content can be further reduced by a downstream stripping).
  • the top product obtained in the distillation in step e2) contains the target product of the process according to the invention. It can either be withdrawn directly as stream E1) or subjected to further work-up.
  • Water contained in the overhead product can be separated off by known processes.
  • the overhead product after condensation of the vapors from the distillation, can be fed to a phase separator for the removal of water.
  • the resulting water is discharged as another stream from the process.
  • the organic phase from the phase separator can either be at least partially withdrawn as stream E1) or subjected to further work-up.
  • the organic phase from the phase separator can be partly recycled as reflux to the column and / or subjected to a further distillative work-up. This is preferably used for the removal of water still contained and / or undesirable organic components.
  • the bottom product obtained in the distillation in step e2) contains the aromatics which are not or not sufficiently reacted in the case of dealkylation, ie it is enriched in aromatics which are sparingly or not dealkylated. It can either be withdrawn directly as stream E2) or subjected to further work-up.
  • Prefers is the resulting in the distillation in step e2) bottom product divided into at least two partial streams.
  • a first partial stream is recycled in step e) of the absorptive separation of the discharge from the dealkylation zone as an absorbent. For this purpose, this partial flow is, if necessary, cooled to a suitable temperature.
  • a second partial stream is withdrawn as stream E2).
  • Stream E2 may be subjected to separation of non-stream D2 components prior to recycling to the dealkylation zone of step c). This is z. B. advantageous if an absorption solvent is used which is not obtained as an intermediate of the process according to the invention. It is also advantageous at this point of stream E2) deduct a purge stream and z. B. in one
  • Combustion device to reduce the accumulation of under the conditions of Dealkylierung not or slowly reacting components.
  • the stream E2) is preferably subjected to evaporation before it is fed into the dealkylation.
  • a preferred variant is shown in FIG. 2 and explained in the associated description of the figures.
  • the stream E3) obtained in step e), which is depleted of aromatics and enriched in highly volatile by-products, is used at least partially for the production of synthesis gas.
  • the separation of the discharge from the dealkylation zone in step e) comprises absorption, the gas stream leaving the absorption device (stream E3), optionally after a removal step for removing absorbent and / or aromatics, becomes at least partially used for the production of synthesis gas.
  • the stream E3) obtained in step e) can be partly supplied to various other uses in addition to synthesis gas production. This includes on the one hand the combustion.
  • the process according to the invention is spatially close to a pulp process, it may be advantageous to feed stream E3) into an apparatus of the pulp process.
  • the stream E3) is fed into the waste liquor combustion (recovery boiler).
  • the combustion of the stream E3) is a desulfurization, z.
  • At least one further stream can be used, the z. B. water vapor and / or oxygen.
  • the aromatic-depleted fraction C2) isolated in step c) is used at least partly for the production of synthesis gas. It is also possible to use an offgas stream from the digestion in step b) and / or the dealkylation in step d) in the syngas production. It may be z. B. to act as a combustion gas from the combustion of volatile components. By feeding such an exhaust gas stream, the h / CO ratio of the synthesis gas can be reduced.
  • the synthesis gas production preferably comprises the following stages:
  • a conversion stage in which, if necessary, additional water is performed, in which the water gas shift reaction (CO + H 2 0 H 2 + C0 2 ) takes place, - optionally a stage for the partial separation of acid gases, such as. B.
  • the synthesis gas produced in the process according to the invention (if necessary after further purification steps known per se for the removal of water, sulfur-containing components, CO2, etc.) is completely or partially used in at least one process comprising hydrogen, CO or mixtures both consumed, used. These include z.
  • a hydrogenation hydroformylation, carbonylation, methanol synthesis, synthesis of hydrocarbons Fischer-Tropsch, etc.
  • hydrogen-enriched stream in the digestion in step b) and / or in the dealkylation in step d) fed An enrichment of the synthesis Segases on hydrogen can, as described above, be carried out by water gas shift reaction.
  • a synthesis gas-containing stream produced in the process or a hydrogen-enriched stream prepared from the synthesis gas is fed into the dealkylation in step d).
  • the particular advantage of this variant is that the proportion of phenol (s) in the products of dealkylation is higher than in pure steam dealkylation, ie. H. without hydrogen supply.
  • the higher phenol formation represents an economic advantage, since phenol is a higher-value material than oxygen-free aromatic compounds such as benzene and also with respect to the reactant lignin more mass is retained.
  • hydrogen which is not produced in the process according to the invention, more expensive and in many cases not or only with great effort available, especially if the dealkylation is to be performed away from a chemical Verbundortortsorts.
  • FIG. 1 A preferred embodiment of the method according to the invention is shown in FIG. 1
  • a biomass starting material (1) in particular a lignin-containing starting material (1), is subjected to digestion.
  • the digestion product (2) is optionally subjected to separation and / or treatment, whereby an aromatics-enriched stream (4) and an aromatics-enriched stream (3) are obtained.
  • the aromatics-depleted stream (3) is fed to reforming / conversion for syngas production.
  • the digestion product (2) or the aromatics-enriched stream (4) obtained therefrom is fed into a dealkylation unit together with a stream of hydrogenating gas (5).
  • the discharge from the dealkylation zone (6) is subjected to separation into the following three streams:
  • stream (8) not or incompletely dealkylated product
  • Stream (9) contains substances that have not been dealkylated or to a lesser extent than the desired product;
  • Stream (9) containing volatile by-products. These are selected from methane and other hydrocarbons, H2O, CO, CO2 and sulfur-containing by-products (in the case of lignin from the Kraft process, especially H2S).
  • a stream of water is separated and discharged from the discharge from the dealkylation zone (6).
  • Stream (7) is withdrawn, optionally after further work-up, as a product stream.
  • the enriched in only slightly or non-dealkylated aromatics stream (8) is returned via an evaporation of the dealkylation.
  • a preferred embodiment of the evaporation is depicted in FIG. 2 and described below.
  • the stream (9) from the separation containing the volatile by-products is at least partially fed to a reforming / conversion for the production of synthesis gas.
  • the organic components contained in stream (9) are converted to a synthesis gas (11) containing CO and H2.
  • a partial stream of stream (9) can also be used for various other uses, such as. B. a suitable combustion, are supplied, it being advantageous in spatial proximity to a pulp process to lead current (9) in an apparatus of the same, particularly preferably in the waste liquor combustion (recovery boiler).
  • This design has the advantage that no additional apparatus for steam or electricity generation or flue gas desulfurization are needed.
  • a desulfurization for. B. in the form of a hydrogen sulfide removing gas scrubber, followed by a conversion of the H 2 S in elemental sulfur (eg Claus process) upstream.
  • a hydrogen-containing stream (12) obtained from synthesis gas production can be passed into the dealkylation.
  • a hydrogen-containing stream (13) obtained from synthesis gas production can be passed into the digestion.
  • Figure 2 shows the evaporation of an aromatics-containing stream, as z. B. in the absorptive and distillative separation of the discharge from the Dealkyltechnikszone as stream E2) (in Figure 1 with (8)) is obtained.
  • Stream (8) is preferably subjected to evaporation before being returned to the dealkylation, as shown in FIG.
  • the Aromatenstrom (8) is preheated in apparatus A to a temperature at which no significant decomposition takes place in the liquid phase and this preheated stream (stream 100) will be combined in an apparatus B with a gaseous stream (stream 200), the amount thereof , Temperature and composition are chosen so that the stream 100 partially or completely evaporated.
  • Stream 200 contains dealkylation reactants, i. H. in the case of steam deacylation, water vapor and in the case of hydrodealkylation a hydrogen-containing gas (stream 5 in FIG. 1).
  • the amounts of streams 100 and 200 are adjusted so that stream 300 leaving in apparatus B gives a composition favorable for the type of dealkylation chosen.
  • Apparatus B is designed as a liquid-gas contact apparatus according to the prior art, for. B. as a container with jet nozzle or column, wherein stream 100 is supplied at the top. Liquid and gas are passed in cocurrent or countercurrent, in the lower part, if necessary, a low-volatile residue (stream 250) are deducted.
  • apparatus B can also be designed as a fluidized bed. Via the externally heated fluidized material, additional energy can be efficiently entered into the stream 100.
  • stream 300 is split into streams 400 and 500, with dealkylation stream 400 and stream 500 returned to apparatus B via heat exchanger C.
  • This variant allows limiting the temperatures of the streams 100, 200 and 500 (after heat exchangers) to limit values that result from the availability of the heat sources, the thermal stability of the materials and the stability of the materials.
  • the naturally occurring pressure loss along the streams 300, 400 and 500 is compensated by a suitable means for compression.
  • a suitable means for compression for this purpose, well-known compressor or fans can be used, but it is also possible to carry out the apparatus B completely or partially as a liquid jet fan, wherein current 100 is used as a driving medium. In this case, if the amount of stream 100 is not sufficient for the required compaction performance, liquid can be circulated via apparatus B in the circuit.

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Abstract

L'invention concerne un procédé de production de gaz de synthèse et d'au moins une matière valorisable organique liquide ou liquéfiable, selon lequel a) un produit de départ de biomasse est préparé, b) le produit de départ de biomasse est soumis à une décomposition, c) au moins une fraction C1) enrichie en composés aromatiques et au moins une fraction C2) appauvrie en composés aromatiques sont éventuellement isolées de la matière décomposée obtenue à l'étape b), d) le produit de décomposition de l'étape b) ou la fraction C1) enrichie en composés aromatiques de l'étape c) sont introduits dans une zone de désalkylation et mis à réagir en présence d'hydrogène et/ou de vapeur d'eau, e) un produit de rejet est extrait de la zone de désalkylation et soumis à une séparation, au moins une matière valorisable organique liquide ou liquéfiable et au moins un écoulement enrichi en composants volatils plus légers que la matière valorisable étant obtenus, f) l'écoulement obtenu à l'étape e), enrichi en composants volatils plus légers que la matière valorisable, est au moins partiellement utilisé pour produire un gaz de synthèse.
PCT/EP2011/057099 2010-05-07 2011-05-04 Procédé de production de gaz de synthèse et d'au moins une matière valorisable organique liquide ou liquéfiable Ceased WO2011138356A1 (fr)

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US8993819B2 (en) 2011-07-12 2015-03-31 Basf Se Process for preparing cycloheptene
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