WO2011138357A1 - Procédé de préparation d'au moins une matière valorisable aromatique de faible poids moléculaire à partir d'une matière de départ contenant de la lignine - Google Patents

Procédé de préparation d'au moins une matière valorisable aromatique de faible poids moléculaire à partir d'une matière de départ contenant de la lignine Download PDF

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Publication number
WO2011138357A1
WO2011138357A1 PCT/EP2011/057101 EP2011057101W WO2011138357A1 WO 2011138357 A1 WO2011138357 A1 WO 2011138357A1 EP 2011057101 W EP2011057101 W EP 2011057101W WO 2011138357 A1 WO2011138357 A1 WO 2011138357A1
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Prior art keywords
stream
lignin
pyrolysis
dealkylation
aromatics
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PCT/EP2011/057101
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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
Joachim Werther
Ernst-Ulrich Hartge
Peng Wang
Bernhard Schult
Frank Rimoschat
Heiko Rohde
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Basf Se
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Publication of WO2011138357A1 publication Critical patent/WO2011138357A1/fr

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    • 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
    • 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
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • 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
    • C10G35/00—Reforming naphtha
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • 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
    • 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 preparation of low molecular weight aromatic recyclables from a lignin-containing starting material produced from biomass.
  • 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 prepare such compounds from 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.
  • US 2,057,117 discloses a process for producing vanillin which comprises heating a starting material selected from lignocellulose, a crude lignin extract and lignosulfonic acid with an aqueous alkali metal hydroxide solution under elevated pressure and adding sulfuric acid to the resulting reaction mixture to form organic To precipitate components 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
  • step d) isolated from the treatment product obtained in step c) the valuable material (s).
  • 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 else the black liquor itself is subjected to hydroprocessing in the presence of a hydrogen-containing gas and a catalyst on an amorphous or crystalline oxidic support. Specifically, a heterogeneous molybdenum sulfide catalyst is used.
  • black liquor 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 catalysed sequential 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 therefore a process for the preparation of a
  • Aromatic composition having a high content of mononuclear, low or unalkylated aromatics from a lignin-containing starting material comprising a) providing a lignin-containing starting material, b) pyrolysis of the lignin-containing starting material to obtain a pyrolysis gas stream, c) substantially the pyrolysis gas stream without separation of a material component in a Dealkyltechnikszone feeds and reacts in the presence of hydrogen and / or water vapor, d) the Dealkyl michszone takes a discharge and subjected to a separation to obtain the Aromatenzusammen arrangement.
  • 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.
  • pyrolysis is understood as meaning a thermal treatment of the lignin-containing starting material, molecular oxygen being not or only to a small amount being supplied.
  • a small amount is to be understood as an amount which is significantly less than the amount necessary for a complete oxidation of the carbon contained in the lignin-containing starting material to CO2.
  • the amount of molecular oxygen fed in the pyrolysis is preferably 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 material contained in the biomass starting material Carbon to CO2 is necessary.
  • Pyrolysis is generally endothermic.
  • 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 aromatic Cores containing nuclei are cleaved to compounds with fewer nuclei.
  • the hydrogen-substituted substituents are selected from alkyl groups, hydroxyl groups, alkoxy groups, aryloxy, etc.
  • the term “dealkylation” also encompasses various reactions associated with a reduction in molecular weight, such as dehydroxylation, dealkoxylation, Aromatenspalte.
  • Aromatea cleavage refers to a reaction in which essentially the number of aromatic nuclei per molecule is reduced without the aromatic nuclei themselves being destroyed.
  • step a Provision of a lignin-containing starting material (step a)
  • a lignin-containing starting material is provided in step a).
  • 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 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 which contain 10 to 100% by weight, particularly preferably 15 to 95% by weight, based on the dry mass of the material, of 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 components.
  • Other components of the plant cell wall and thus obtained lignocellulose-containing materials are, for.
  • silicates extractable low molecular weight organic compounds (so-called extract substances, 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 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. 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. the different types of wood, ie hardwoods, such as maple, birch, pear, oak, Er- leek, eucalyptus, hornbeam, cherry tree, linden, walnut, poplar, willow, etc. and conifers such as Douglas fir, spruce, yew, hemlock, pine, larch fir, cedar, etc.
  • Wood can be found not only in deciduous and Softwoods differ, 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 willows, poplars, lime trees 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. B. in the harvest of grain (wheat straw, corn straw, etc.), corn, sugar cane (bagasse), etc. Suitable lignocellulosic materials are also available as a residue in forestry, 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 lignin-containing stream from the digestion of a lignocellulosic material is used to produce cellulose (pulp).
  • the digestion permits at least partial separation of the lignocellulose-containing starting material into cellulose and cellulose accompanying substances, the lignin also being among the latter.
  • a lignocellulose-containing material is provided in step a) of the process according to the invention, subjected to digestion and isolated from the digested material, a cellulose-enriched fraction and a lignin-enriched (and simultaneously depleted in cellulose) fraction.
  • lignin-containing streams are suitable for use in the process according to the invention 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.
  • 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 selected from hemicellulose, cellulose, degradation products of the aforementioned components, pulping chemicals and mixtures thereof.
  • a lignin-containing starting material which contains at least one further component in addition to lignin.
  • 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 pyrolysis 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 treated 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 (for example by means of a washing process such as Benfield scrubbing).
  • the carbonates and / or hydrogencarbonates resulting from addition of CU2 can generally be easily incorporated into the coupled pulp process bring back, z. B. in a previously taken to Lignin gapung 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.
  • the person skilled in the art can control the composition of the lignin-containing fraction and thus of the lignin-containing starting material for the pyrolysis in step b) via the separation process.
  • 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 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 lignocellulose 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 a lignin-containing fraction precipitation followed by partial or complete removal of the liquid components to provide the lignin-containing starting material for the pyrolysis 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 production according to the invention of low molecular weight aromatic recyclables is integrated.
  • the removal of at least a portion of the liquid compounds is then carried out in the context of the process for the production of pulp.
  • a black liquor are used, which is taken before or during 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 to provide the lignin-containing starting material in step a).
  • a black liquor is used, in particular a black liquor from the sulfate 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.
  • 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.
  • 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 or filter cake? subjected to a wash with sulfuric acid.
  • a process for isolating lignin from a black liquor by precipitation with CO2 is described in WO 2008/079072, to which reference is made here.
  • lignoboost process which is described in WO
  • step b) of the process according to the invention the lignin-containing starting material is subjected to pyrolysis, a pyrolysis gas stream being obtained.
  • the pyrolysis can be carried out batchwise or continuously. Continuous pyrolysis is preferred.
  • the pyrolysis takes place in at least one pyrolysis zone.
  • the ligninhal- term starting material z. B. as a moist or predried solid by means of suitable transport facilities, such. B. screw conveyor or pneumatic conveying, are registered in a pyrolysis zone.
  • 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 accompanied by the addition of hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring compounds carried out.
  • the hydrogenating reaction takes place essentially exclusively in the dealkylation step c).
  • the pyrolysis is carried out with the addition of hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring compounds. This embodiment of the pyrolysis can also be referred to as hydrocracking.
  • the pyrolysis can be carried out in the presence of at least one pyrolysis catalyst.
  • pyrolysis catalyst for example, silica, alumina, aluminosilicates, aluminosilicates with layered structures and zeolites, such as mordenite, faujasite, zeolite-X, zeolite-Y and ZSM-5, zirconium oxide or titanium dioxide.
  • 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.
  • Dwell time especially in a fluidized bed reactor results from the quotient of total volume of the reactor to the volume flow of the fluidizing gas under the pyrolysis.
  • 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 lignin is converted into a mixture of components which under the conditions of pyrolysis are partly gaseous ("pyrolysis gas”) and partly solid and / or liquid (eg tarry or "coke”) ,
  • a discharge is taken, which can still contain fractions of solid and / or liquid components in addition to the pyrolysis gases. These are z. B. to low-volatility components formed during pyrolysis (coke). 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 can be prepared by means of a suitable method. direction, z. 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.
  • Example a combustion for heat recovery, which is preferably used again in the inventive method or an integrated method.
  • the fuel gas thus obtained which contains mainly CO2 and water and optionally O2, can also be recycled. It is also possible to bring a discharge from the pyrolysis zone, which contains at least one additive and components which have low volatility under the pyrolysis conditions, into contact with an oxygen-containing gas, preferably air, in a combustion zone which is spatially separate from the pyrolysis zone, which causes it to burn off of low-volatility components ("coke”) produced during pyrolysis.
  • an oxygen-containing gas preferably air
  • the pyrolysis gas stream obtained in step b) contains substituted aromatics and / or polynuclear aromatics.
  • the pyrolysis gas stream may contain, in addition to aromatics, other components selected from water vapor, inert gas (e.g.
  • non-aromatic hydrocarbons H2, CO, CO2, sulfur-containing compounds, such as. As H2S, etc. and mixtures thereof.
  • the non-aromatic hydrocarbons are preferably degradation products, such as methane.
  • the aromatic lignin decomposition products formed during the pyrolysis in step b) are at least partially converted by the action of hydrogen and / or water vapor so that substituents are replaced by hydrogen and / or several compounds containing aromatic nuclei are converted into compounds with less Number of cores are split.
  • dealkylation thus also denotes reactions in which no alkyl substituent is exchanged for hydrogen, such as dehydroxylation, dealkoxylation, aromatic cleavage, etc.
  • the substituents replaced by hydrogen are preferably selected from alkyl groups, hydroxy groups, alkoxy groups and aryl oxy groups.
  • Dealkylation processes suitable for use in step c) include hydrodekylation, vapor dealkylation or mixtures thereof.
  • hydrodekylation 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.
  • a pure steam dealkylation in addition to the pyrolysis gas stream, water is fed into the dealkylation zone in addition to the pyrolysis gas stream (in pure form or in a mixture with other components), but no molecular hydrogen.
  • the dealkylation process in step c) can also be used as a mixed form of hydrodealkylation and
  • the reaction gas used for dealkylation then has a mixing ratio of H2 to H2O in the range from about 0.1: 99.9 to 99.9: 0.1.
  • a particularly suitable mixing ratio of H2 to H2O is in the range of about 40:60 to 60:40.
  • the hydrogen required for the reaction is formed in situ in the case of steam dealkylation by reaction of water with (mainly organic) components which are either present in the educt mixture of the steam dealkylation or are formed during steam dealkylation.
  • the formation of hydrogen from methane and water can be named according to the equation CH 4 + H2O - CO + 3 H2.
  • the pyrolysis gas stream from step b) is fed into the dealkylation zone essentially without removal of a material component.
  • components which are difficult to volatilize under the conditions of pyrolysis in step b) and which are not gaseous in the discharge from the pyrolysis zone but solid or liquid are not added to the pyrolysis gas stream.
  • Substantially without separation of a material component in the context of this invention means that of the pyrolysis gas stream obtained in step b). 10 vol .-% are separated before the pyrolysis gas is fed into the Dealkyl michszone. Preferably, at most 1% by volume, more preferably at most 0.5% by volume, of the pyrolysis gas stream obtained in step b) are separated off before the pyrolysis gas stream is fed into the dealkylation zone.
  • substantially no components contained therein are condensed out of the pyrolysis gas stream obtained in step b) before it enters the dealkylation zone.
  • the pyrolysis gas stream obtained in step b) from the pyrolysis gas stream obtained in step b) at most 10 wt .-%, particularly preferably at most 5 wt .-%, in particular at most 0.5 wt .-%, especially at most 0.1 wt .-%, of the condensable contained therein Components condensed out before the pyrolysis gas stream is fed into the Dealkyltechnikszone.
  • the pyrolysis gas stream is maintained under suitable conditions which substantially preclude condensation of components contained therein.
  • the temperature of the pyrolysis gas stream before entering the Dealkyl istszone always at most 200 ° C, more preferably always at most 100 ° C, below the outlet temperature from the pyrolysis zone.
  • 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, particularly preferably from 1 to 20 bar, in particular from 1 to 10 bar.
  • the pyrolysis gas stream is subjected to a hydrodealkylation in step c).
  • the reaction in step c) takes place in the presence of hydrogen.
  • the temperature in the dealkylation zone for the hydrodealkylation is preferably in the range from 500 to 900 ° C., particularly preferably from 600 to 800 ° C.
  • the absolute pressure in the dealkylation zone for the hydrodealkylation 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 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 is theoretically straightforward full conversion of the aromatics supplied to the dealkylation zone to benzene is required, assuming that 1 mole H is reacted per nuclear substituent.
  • the residence time in the dealkylation zone is preferably in the range from 0.1 to 500 s, more preferably from 0.5 to 200 s.
  • 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 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 sampled and subjected to separation to yield the target aromatics composition having a high content of mononuclear, low or unalkylated aromatics.
  • the effluent from the dealkylation zone is subjected to separation to give the following three streams:
  • D2) an enriched in low or non dealkylated aromatics stream
  • D3) an enriched lighter than D1) and D2) by-products stream.
  • the effluent from the dealkylation zone may be subjected to separation to yield additional streams, such as e.g. B. a hydrous stream.
  • Stream D1) is the aromatic compound prepared in the process according to the invention with a high content of mononuclear, low or non-alkylated aromatics.
  • stream D1) can be subjected to a further work-up to obtain the aroma composition prepared according to the invention.
  • the stream D1) contains, based on the total amount of D1), preferably at least 70 wt .-%, more preferably at least 80 wt .-%, in particular at least 90 wt .-%, of mononuclear aromatic.
  • the stream D1) based on the total amount of D1), preferably at most 30 wt .-%, more preferably at most 20 wt .-%, in particular at most 10 wt .-%, of low or non-dealkylated aromatics.
  • dealkylation also refers to the replacement of substituents other than alkyl groups (such as alkoxy groups, aryloxy groups, hydroxy groups, etc.) by hydrogen.
  • stream D1) then also has a high content of aromatics in which one substituent other than alkyl groups has been replaced by hydrogen.
  • stream D1) has a high content of low-alkoxylated or non-alkoxylated aromatics.
  • the stream D2) based on the total amount of D2), preferably at least 70 wt .-%, more preferably at least 80 wt .-%, in particular at least 90 wt .-%, of low or non-dealkylated aromatics.
  • the stream D3) contains components that z. B. are selected from non-aromatic hydrocarbons, especially methane, hydrogen, carbon monoxide, carbon dioxide and mixtures thereof.
  • the stream D3) 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 d).
  • the well-known thermal Trennver- can be used as a method for separation.
  • the separation of the discharge from the dealkylation zone in step d) 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) is preferably used in which the aromatics obtained in the dealkylation are soluble in a sufficient amount and the volatile by-products which differ from them are substantially insoluble.
  • an aromatics-laden absorbent is obtained on the one hand.
  • the aromatic components contained in the absorbate correspond in composition to the sum of the aromatics in the streams D1) and D2) plus any aromatics optionally present in the absorbent.
  • the components contained in the remaining gas stream correspond in their composition to stream D3).
  • 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 d) comprises the following substeps: Contacting the discharge from the dealkylation zone obtained in step c) with an absorbent to obtain an aromatics-enriched absorbent and a gas stream D3 enriched in aromatics (or a by-product which is lighter than D1) and D2),
  • the absorbent has a boiling point which is above the components of stream D1). Further preferably, the absorbent has a high dissolving power for the aromatics formed in the dealkylation step.
  • Suitable solvents are, for.
  • aliphatic, cycloaliphatic and aromatic hydrocarbons aliphatic, cycloaliphatic and aromatic alcohols, amides, such as N-methylpyrrolidone or dimethylformamide.
  • Aliphatic, cycloaliphatic and aromatic hydrocarbons preferably have a carbon atom number of at least 6.
  • Aliphatic, cycloaliphatic and aromatic alcohols preferably have a carbon atom number of at least 4.
  • the solvent 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 solvent used is a partial stream of stream D2) or a mixture of D1) and D2).
  • 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.
  • step d2) the aromatics-enriched absorbate is preferably separated by distillation.
  • the thereby recovered solvent is, optionally after removal of absorbed water, in the absorption (step d1)) recycled.
  • the aromatics are processed further as described above and below.
  • the aromatics-enriched absorbate is preferably 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 by the low-boiling content in the bottoms (the low-content content can be further reduced by a downstream stripping).
  • the top product obtained in the distillation in step d2) contains the target product of the process according to the invention. It can either be withdrawn directly as stream D1) 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 D1) 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 during the distillation in step d2) contains the aromatics which are not or not sufficiently converted 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 D2) or subjected to further work-up.
  • Prefers is the resulting in the distillation in step d2) bottom product divided into at least two partial streams.
  • As a solvent recycled.
  • this partial stream if necessary, cooled to a suitable temperature.
  • a second partial stream is withdrawn as stream D2).
  • This stream D2) is preferably at least partially recycled to the dealkylation zone of step c).
  • Stream D2) may be subjected to separation of constituents other than stream D2) 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 D2) deduct a purge and z. B. in a combustion device to reduce the accumulation of under the conditions of dealkylation not or slowly reacting components.
  • the stream D2) 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 D3) obtained in step d), which is depleted of aromatics and enriched in highly volatile by-products, can be put to various uses. 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 D3) into an apparatus of the pulp process.
  • the stream D3) is fed into the waste liquor combustion (recovery boiler).
  • Embodiment has the advantage that no additional devices for the steam or power generation or the flue gas desulfurization in the combustion of the stream D3) are needed.
  • the combustion of the stream D3) is a desulfurization, z. B. upstream in the form of a hydrogen sulfide removing gas, followed by a conversion of the formed H2S in elemental sulfur.
  • the formation of sulfur can by known methods, for. As the Claus process done.
  • the stream D3) obtained in step d) is used at least partly for the production of synthesis gas.
  • the separation of the discharge from the dealkylation zone in step d) comprises an absorption, the gas stream leaving the absorption device (stream D3), if appropriate after a cleaning step for the removal of absorbent and / or aromatics, preferably at least partially used for the production of synthesis gas.
  • 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.
  • at least one further stream can be used for synthesis gas production, the z. B. water vapor and / or oxygen.
  • the synthesis gas production preferably comprises the following stages:
  • the synthesis gas stream 1 1 produced in the process according to the invention (if necessary after further purification steps known per se for removing water, sulfur-containing components, CO 2, etc.) is used completely or partially for use in at least one process comprising hydrogen, CO or mixtures of both consumed used. These include z.
  • a hydrogenation hydroformylation, carbonylation, methanol synthesis, synthesis of hydrocarbons Fischer-Tropsch, etc.
  • a synthesis gas-containing stream produced in the process or a hydrogen-enriched stream prepared from the synthesis gas is introduced into the pyrolysis in step b). and / or into the dealkylation in step c).
  • 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 c).
  • phenol is a higher value material than oxygen-free aromatics, such as benzene.
  • 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 lignin-containing starting material (1) is subjected to pyrolysis.
  • the pyrolysis gas (2) is fed together with a hydrogenation gas stream (5) into a dealkylation unit, essentially without any condensation or other separation of the stream being carried out.
  • 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 shown in FIG. 2 and described below.
  • the stream (9) from the separation containing the volatile byproducts can be used for various purposes, such as e.g. B. a suitable combustion, are supplied, wherein it is 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.
  • the combustion is a deflagration, z. B. in the form of a hydrogen sulfide removing gas scrubber, followed by a conversion of the F S in elemental sulfur (eg Claus process) upstream.
  • stream (9) is fed to a reforming unit in which, optionally with the introduction of an optional stream (10) containing water or oxygen, the organic components contained are converted to a synthesis gas (11) containing CO and H. ,
  • 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 conducted into the pyrolysis.
  • FIG. 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 D2) (in Figure 1 with (8) denotes) 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.
  • the thus preheated stream (stream 100) is in an apparatus B with a gaseous stream (stream 200) merged, the amount, temperature and composition are chosen so that the stream 100 partially or completely evaporated.
  • Stream 200 contains dealkylation reactants, ie steam in the case of steam dealkylation and hydrogen-containing gas in case of hydrodealkylation (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.
  • well-known compressor or fans can be used.

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Abstract

L'invention concerne un procédé de préparation de matières valorisables aromatiques de faible poids moléculaire à partir d'une matière de départ contenant de la lignine produite à partir de biomasse.
PCT/EP2011/057101 2010-05-07 2011-05-04 Procédé de préparation d'au moins une matière valorisable aromatique de faible poids moléculaire à partir d'une matière de départ contenant de la lignine WO2011138357A1 (fr)

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US8993819B2 (en) 2011-07-12 2015-03-31 Basf Se Process for preparing cycloheptene
WO2015047085A1 (fr) * 2013-09-26 2015-04-02 Biobtx B.V. Procédé de préparation de composés aromatiques
WO2016107823A1 (fr) * 2014-12-29 2016-07-07 Shell Internationale Research Maatschappij B.V. Procédé de production de composés aromatiques par pyrolyse de matières comprenant de la lignine
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