EP1888713A2 - Procedes de conversion catalytique de lignine en biocarburants - Google Patents

Procedes de conversion catalytique de lignine en biocarburants

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Publication number
EP1888713A2
EP1888713A2 EP06758980A EP06758980A EP1888713A2 EP 1888713 A2 EP1888713 A2 EP 1888713A2 EP 06758980 A EP06758980 A EP 06758980A EP 06758980 A EP06758980 A EP 06758980A EP 1888713 A2 EP1888713 A2 EP 1888713A2
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EP
European Patent Office
Prior art keywords
lignin
reaction
partially
catalyst
product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06758980A
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German (de)
English (en)
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EP1888713A4 (fr
Inventor
Wlodzimierz W. Zmierczak
Jan D. Miller
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University of Utah Research Foundation UURF
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University of Utah Research Foundation UURF
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Publication of EP1888713A2 publication Critical patent/EP1888713A2/fr
Publication of EP1888713A4 publication Critical patent/EP1888713A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • 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 generally to conversion of biomass to fuels, fuel additives, and other commercially useful products. More particularly, the present invention relates to a multi-step catalytic process for production of hydrocarbon products from lignin.
  • Lignin a second to cellulose as the most plentiful renewable carbon source on Earth, is an amorphous three-dimensional energy-rich phenolic biopolymer, which is deposited in all vascular plants and provides rigidity and strength to their cell walls.
  • the lignin polymeric structure is composed primarily of three phenylpropanoid building units: p- hydroxyphenylpropane (Structure I), guaiacylpropane (Structure II), and syringylpropane (Structure III) interconnected by etheric and carbon-to-carbon linkages. Generally, in unprocessed lignins, two thirds or more of these linkages are ether bonds, while the remaining linkages are carbon-carbon bonds.
  • lignin bio-mass component can potentially be converted directly to liquid fuels, e.g., high-octane alkylbenzene and/or aromatic ether gasoline- blending components.
  • lignin appears as a residual material with limited opportunities for its utilization.
  • Other sources of lignin material can include agricultural products and wastes, municipal wastes, and the like.
  • a first step involves base-catalyst depolymerization (BCD) of lignin feed in a reaction medium such as an alcohol followed by catalytic hydroprocessing (HPR).
  • BCD base-catalyst depolymerization
  • HPR catalytic hydroprocessing
  • lignin is partially depolymerized, mostly by solvolysis of etheric linkages, to ether- soluble mono-, bi- and trimeric phenolic units, and some hydrocarbons.
  • HPR hydroprocessing
  • HDO simultaneous hydrodeoxygenation
  • HCR hydrocracking
  • the overall BCD-HPR procedure yields a low-sulfur, high-octane hydrocarbon gasoline additive consisting of a mixture of C 7 - Cu alkylbenzenes, and some Cg - Cn mono-, di-, tri- and polyalkylated naphthenes and C 5 - Cn (mostly multi-branched) paraffins.
  • the second two-stage method is a lignin-to-aromatic ethers (LTE) process and was designed primarily for production of partially oxygenated gasoline or for the selective production of C 7 - Cn methoxybenzenes as high-octane additives.
  • LTE lignin-to-aromatic ethers
  • This process uses a similar two-stage procedure as the first process briefly described above.
  • lignin is subjected to a mild base-catalyst depolymerization (BCD) in supercritical alcohol as a reaction medium.
  • BCD base-catalyst depolymerization
  • This step is then followed by non-deoxygenative hydrotreatment/mild hydrocracking (HT), and a subsequent etherification (ETR) of the intermediate phenolic product to yield a reformulated, partially oxygenated gasoline.
  • BCD base-catalyst depolymerization
  • HT non-deoxygenative hydrotreatment/mild hydrocracking
  • the resulting gasoline is typically a mixture of (substituted) phenyl methyl ethers (blending octane number, 124 - 166; boiling point, 154 - 195 0 C) and cycloalkyl methyl ethers, C 7 - C] 0 alkybenzenes, C 5 - Ci 0 (mostly multi-branched) paraffins, and polyalkylated cycloalkanes.
  • a process for conversion of a lignin material to bio-fuels can include subjecting the lignin material to a base catalyzed depolymerization reaction to produce a partially depolymerized lignin.
  • the partially depolymerized lignin can then be subjected to a stabilization/partial hydrodeoxygenation reaction to form a partially hydrodeoxygenated product.
  • the partially hydrodeoxygenated product can be reacted in a refining step to form a bio-fuel.
  • Each of these reaction steps can be performed in single or multiple steps, depending on the design of the process.
  • the based catalyzed depolymerization reaction can include dissolving the lignin material in an aqueous base catalyst in the presence of a polar solvent.
  • the dissolved lignin material can then be subjected to reaction conditions sufficient to partially depolymerize the lignin material.
  • the partially depolymerized phenolic lignin products can be recovered and optionally separated from other products as a part of the based catalyzed depolymerization reaction.
  • the base catalyst can be NaOH, KOH, Ca(OH) 2 , Mg(OH) 2 , and mixtures thereof, although other base catalysts could be used.
  • a number of polar solvents can be used; however, water is currently preferred.
  • the base catalyzed depolymerization reaction can be carried out under conditions which are substantially free of alcohols.
  • the stabilization/partial hydrodeoxygenation reaction can include exposing the partially depolymerized lignin to a solid catalyst at a temperature below about 300 0 C, e.g., from about 200 0 C to about 300 0 C.
  • the solid catalyst can include a support material and a catalyst material.
  • the support material can be a non-acidic material such as activated carbon, silicon dioxide, aluminum oxide, or combinations thereof.
  • the choice of material for the catalyst material portion of the solid catalyst can also be an important consideration.
  • particularly suitable catalyst material can include Co-Mo, Rh-Mo, Ru-Mo, Pt-Mo, Pd-Mo, and combinations, alloys or composites thereof.
  • the stabilization/partial hydrodeoxygenation reaction can occur at conditions sufficient to convert greater than about 95%, and preferably greater than about 98%, of methoxyphenols and benzenediols to phenol- based products having a single oxygen moiety.
  • the refining step can include a hydrodeoxygenation reaction, a mild hydrocracking reaction, an etherification reaction, a hydrogenation reaction, and/or combinations thereof.
  • the refining step can be a hydroprocessing reaction which includes a hydrodeoxygenation step and a subsequent hydrocracking step.
  • process conditions can vary, the hydroprocessing reaction can occur at a temperature from about 250 0 C to about 400 0 C, and in some cases from about 320 0 C to about 450 0 C.
  • the refining step can include a mild hydrocracking reaction followed by an etherification reaction.
  • the partially hydrodeoxygenated product can be fractionated into a first monomeric fraction and a second oligomeric fraction (e.g., dimers, trimers, and heavily substituted rings).
  • the first low molecular weight fraction can be treated in an etherification reaction with methanol or ethanol to form aromatic ethers which are particularly useful as fuel additives.
  • the second high molecular weight alkylphenol fraction can then be treated in a hydroprocessing reaction and an optional hydrogenation reaction to form bio-fuels such as aromatic gasolines and/or jet fuels.
  • FIG. 1 is a flow diagram of a three stage process for conversion of lignin to alkylbenzene gasoline blending components in accordance with an embodiment of the present invention.
  • FIG. 2 is a flow diagram of a four stage process for conversion of lignin to aromatic ether gasoline blending components in accordance with an embodiment of the present invention.
  • FIG. 3 is a flow diagram of an integrated process for conversion of lignin to liquid transportation fuels in accordance with another embodiment of the present invention.
  • reaction is intended to cover single step and multi-step reactions which can be direct reactions of reactants to products or may include one or more intermediate species which can be stable or transient.
  • bio-fuels refers to any fuel, fuel additive, aromatic, and/or aliphatic compound derived from a biomass starting material such as lignin.
  • lignin and “lignin material” are used interchangeably and refer to a biomass material which is an amorphous three-dimensional energy-rich phenolic biopolymer. Lignin is typically deposited in nearly all vascular plants and provides rigidity and strength to their cell walls. As mentioned above, the lignin polymeric structure is composed primarily of three phenylpropanoid building units interconnected by etheric and carbon-to-carbon linkages.
  • Non-limiting examples of lignin material can include agricultural lignin, wood lignin, lignin derived from municipal waste, Kraft lignin, organosolve lignin, and combinations thereof. Wood lignin is currently a widely available and renewable resource which can be particularly suitable for use in the present invention.
  • oxygen moiety refers to any oxygen-containing substituent to an aromatic ring or other main group.
  • oxygen moieties present on the compounds of the present invention can include hydroxyl groups, however other groups such as methoxy, alkoxy, carboxy, and the like can also be included.
  • Compounds containing a single oxygen moiety are stabilized, or in other words, are not polymerizable under identified process conditions, e.g. phenol or other aromatics containing a single oxygen moiety.
  • compounds containing two or more oxygen moieties tend to be poymerizable to form undesirable coking, e.g. methoxyphenol, benzenediol, and the like.
  • non-acidic support material refers to a solid catalyst support which is non-acidic.
  • pH and pKa are generally unhelpful because these terms are measures of fluid conditions.
  • the acidity of a solid can be measured as a complex function expressed as a Hammett indicator. Actual Hammett indicator values for the catalyst support materials of the present invention are currently unknown.
  • non-acidic support materials for SPHDO stabilization/partial hydrodeoxygenation are those which are substantially free of acidic sites sufficient to avoid poisoning by coking.
  • catalyst support materials are most often provided as acidic support materials; however, non-acidic support materials can be formed or prepared by adjusting the method of preparation, subsequent treatment with bases or other available methods to remove or neutralize any acidic sites.
  • non-acidic support materials can be formed or prepared by adjusting the method of preparation, subsequent treatment with bases or other available methods to remove or neutralize any acidic sites.
  • alumina support materials can be acidic or non-acidic depending on the method of preparation or subsequent treatments.
  • substantially when used in reference to a quantity or amount of a material, or a specific characteristic thereof, refers to an amount that is sufficient to provide an effect that the material or characteristic was intended to provide. The exact degree of deviation allowable may in some cases depend on the specific context.
  • substantially free of or the like refers to the lack of an identified element or agent in a composition. Particularly, elements that are identified as being “substantially free of are either completely absent from the composition, or are included only in amounts which are small enough so as to have no measurable effect on the composition.
  • partial or “partially” when used in connection with the phrase “stabilization/partial hydrodeoxygenation” or “SPHDO” refer to the percentage of oxygen moieties eliminated from the end products of the base-catalyzed depolymerization (BCD) reaction of lignin.
  • the percentage of the total oxygen removed from the BCD end product can range from 30% to 60%, and preferably average about 50%. As such, more than about 95% and preferably more than about 99% of polymerizable BCD end products (i.e. products having multiple oxygen moieties) can be converted to stabilized products having single oxygen moieties.
  • the "partial" hydrodeoxygenation occurs when the methoxy and/or hydroxyl groups are removed from methoxyphenol or benzenediol compounds to yield single oxygen containing phenolic compounds.
  • refining step(s) refers to any single reaction or combination of reactions or reaction steps which processes the partially hydrodeoxygenated products of the SPHDO reaction into a biofuel.
  • refining steps include but are not limited to hydroprocessing reactions such as hydrodeoxygenation reactions, mild hydrocracking reactions, etherification reactions, hydrogenation reactions, and combinations thereof.
  • bio-fuels can be produced using a three-step process including based-catalyzed depolymerization, stabilization/ partial hydrodeoxygenation, and a refining step.
  • LTG U.S. Patent No. 5,959,167
  • LTE U.S. Patent No. 6,172,272
  • the BCD product was treated in hydroprocessing (HPR) and selective hydrocracking (HC) steps, respectively, with acidic catalysts at temperatures above 350 0 C.
  • HPR hydroprocessing
  • HC selective hydrocracking
  • This approach can be useful in some circumstances; however, the high temperatures required can result in a reduction in reliability during scale-up and extended production runs.
  • This application is related to U.S. Provisional Patent Application Serial No. 60/677,662, filed on May 2, 2005, which is herein incorporated in by reference.
  • lignin BCD products are primarily phenolic compounds including mono-, di-, and polyalkylated phenols, methoxyphenols, benzenediols, and some polyalkylated benzenes (e.g. 2-10%), and dimeric and trimeric aromatic non-phenolic compounds.
  • Such a product if used in the LTG process, requires further upgrading, e.g., removal of oxygen via a hydrodeoxygenation process and a simultaneous (using a hybrid catalyst) or consecutive hydrocracking, which results in a higher chemical stability and increases H/C ratio, heating value, etc.
  • the BCD process tends to produce a relatively high content of very reactive, thermally unstable methoxyphenols and benzenediols.
  • a low temperature stabilization/partial hydrodeoxygenation (SPHDO) treatment can be considered preceding the HPR process in order to alleviate the problem of catalyst deactivation and repolymerization.
  • SPHDO treatment can be performed at a low temperature range (e.g. 200 0 C - 400 0 C, and often less than about 300 0 C, depending on the catalyst); however, other temperature ranges can be suitable depending on the catalyst and associated reaction kinetics.
  • the SPHDO treatment process can result in conversion of methoxyphenols to benzenediols and methane, and then subsequently eliminate one OH group from benzenediols to produce phenols.
  • Equation I a reaction scheme for partial hydrodeoxygenation/stabilization of guaiacol (2-methoxyphenol) is shown.
  • the bond dissociation energy of the oxygen atom attached to aromatic carbons in phenols and ethers is about 84 kJ/mol greater than that of an oxygen atom attached to aliphatic carbons. This can at least partially explain why removal of a methyl group from a methoxy group is easier than removal of entire methoxy groups. Production of methane is quite low and is dominantly CO 2 , with some H 2 and hydrocarbons. This product can be useful as a fuel source and can be combusted on site as an additional heating source.
  • the partial hydrodeoxygenation/stabilization reactions of the present invention can act to remove polymerizable moieties to reduce or prevent undesirable polycondensation products from forming.
  • the resulting SPHDO phenolic products can then be subjected to a variety of refining steps such as hydroprocessing (HPR) without formation of substantial polycondensation products.
  • HPR hydroprocessing
  • the SPHDO step can allow for reduced catalyst coking, reduced reaction temperatures and reduced costs, as well as allow subsequent high-temperature (>300 0 C) hydroprocessing (HPR), i.e. substantially complete hydrodeoxygenation (HDO) and hydrocracking (HCR) to break interaromatic C - C linkages.
  • HPR high-temperature
  • HDO hydrodeoxygenation
  • HCR hydrocracking
  • HDO and HCR reactions can be carried out either separately or in a single processing step. Careful selection of HDO and
  • HCR catalysts and process conditions is desirable for selective conversion of BCD-SPHDO product to a monomeric, mostly aromatic product.
  • HDO catalysts can be chosen based on low hydrogenation activity and HCR catalysts based on optimizing acidity and low hydrogenation activity. Aromatic ring hydrogenation during these reactions should be minimized by careful choice of the catalyst and associated temperatures.
  • a SPHDO catalyst can be prepared by altering typical HDO catalysts.
  • an acidic alumina support can be replaced with alternative, non-acidic supports such as non-acidic alumina (neutralized with NaOH, KOH, etc.), active carbon, silica, and composites thereof.
  • non-acidic supports such as non-acidic alumina (neutralized with NaOH, KOH, etc.), active carbon, silica, and composites thereof.
  • noble metals can be incorporated into the active phase of the catalyst.
  • SPHDO catalysts such as supported or unsupported transition metal nitrides and carbides can be useful.
  • Non-limiting examples of suitable SPHDO catalysts can include but are not limited to supported or unsupported transition metal nitrides, supported or unsupported transition metal carbides, or combinations thereof.
  • transition metal nitrides include but are not limited to VN; Mo 2 N, TiN, and combinations thereof.
  • transition metal carbides include but are not limited to WC, Mo 2 C, VC, and combinations thereof.
  • the acidity can be one important factor in determining effectiveness.
  • SPHDO catalyst support materials can be non-acidic such that the reaction kinetics of the catalytic stabilization reactions are controlling over non-catalytic repolymerization and coking reactions. As temperatures increase, the non-catalytic coking reactions tend to become controlling.
  • CoMo/Al 2 O 3 SPHDO non-acidic catalysts typically have a maximum operating temperature of about 300 0 C before non- catalytic coking reactions become controlling which leads to poisoning of the catalyst.
  • Other SPHDO catalysts and temperature conditions may vary. However, at least some minor repolymerization reactions can be desirable as such species in minor amounts can act as catalytic promoters for the desirable SPHDO oxygen-group elimination reactions.
  • Noble metal-containing catalysts are generally more active and selective for SPHDO than standard HDO catalysts. Another important advantage of these catalysts is their ability to perform selective direct elimination of entire methoxy groups resulting in compounds containing only one atom of oxygen (phenols) as a main product. Furthermore, such catalysts can be less active for unwanted reactions, e.g., coking and aromatic ring hydrogenation. More highly active catalysts can perform acceptably well in a lower temperature range where coking reactions proceed more slowly. Also, application of active coal or SiO 2 as an SPHDO catalyst support can provide reduced coking. As a general guideline, the SPHDO catalyst and support material can be non-acidic and being substantially free of acidic sites sufficient to avoid poisoning by coking at the specified operating temperatures.
  • an enhanced catalytic lignin conversion process such as an enhanced lignin-to-gasoline (ELTG) process; an enhanced lignin-to-aromatic ethers (ELTE) process; and an integrated lignin-to-liquid fuels process (ILTF).
  • ELTG enhanced lignin-to-gasoline
  • ELTE enhanced lignin-to-aromatic ethers
  • ILTF integrated lignin-to-liquid fuels process
  • FIG. 1 A flow diagram of the proposed the enhanced lignin conversion process for production of aromatic gasoline and gasoline additives, in a three-stage procedure is presented in FIG. 1.
  • a lignin feed is subjected to base- catalyzed depolymerization (BCD) to from a partially depolymerized product.
  • BCD base- catalyzed depolymerization
  • the partially depolymerized BCD product can be subjected to a low temperature stabilization/partial hydrodeoxygenation (SPHDO) process.
  • SPHDO low temperature stabilization/partial hydrodeoxygenation
  • the SPHDO product can be hydroprocessed to obtain a bio-fuels product including aromatic-rich gasoline and a higher molecular weight fraction.
  • the specific bio-fuel product composition can strongly depend on the HPR processing conditions.
  • the latter fraction can be optionally subjected to exhaustive aromatic ring hydrogenation to obtain valuable naphthenic kerosene (NK).
  • NK naphthenic ke
  • a lignin material can be dissolved in an aqueous base- catalyst solution.
  • typical reaction temperatures can range from about 230 0 C to about 350 0 C.
  • autogenic pressure of from about 1000 to about 2300 psig can be useful.
  • the BCD reaction can generally be operated at a lignin material feed rate in liquid hourly space velocity (LHSV) of about 0.5 to about 6.0 hr "1 .
  • LHSV liquid hourly space velocity
  • Alkali and alkaline earth metal hydroxides can be used as base catalysts.
  • suitable base catalysts can include NaOH, KOH neat, Ca(OH) 2 , Mg(OH) 2 , and mixtures thereof.
  • the preferred liquid medium is water; however, methanol and/or ethanol can also be used, as well as combinations of water, methanol, and/or ethanol.
  • a continuous stirred-tank reactor CSTR
  • any reactor which reduces or eliminates accumulation of precipitates can be used, e.g., any agitated reactor, and the like. Precipitates can appear in connection with reduction in the base catalyst concentration during the BCD process and can also cause reactor plugging.
  • the primary solid/liquid portion of the BCD reaction product can be precipitated by acidification with CO 2 and/or other acidic species such as, but not limited to, hydrochloric acid, sulfuric acid, phosphoric acid, and the like. As an added benefit, washing with phosphoric acid can also result in a fertilizer by-product.
  • the precipitated BCD product can then be washed and dried.
  • the remaining non-precipitated BCD water-soluble product mostly benzenepolyols such as benzenediol
  • the extracted water soluble BCD product can be used as a source of valuable bio-chemicals as is.
  • the dry BCD product can be diluted at a temperature range of about 100 0 C to about 150 0 C with any number of liquid vehicles such as self-produced, selected fractions of SPHDO and/or HPR products.
  • Insoluble high-molecular weight components can be separated by filtration or centrifugation and desalted. These insoluble components can be used as feed in the SPHDO process.
  • a suitable desalting treatment similar to those applied in crude oil treatment can be useful to prevent corrosion and catalyst poisoning effects by sodium and calcium salts occluded in the solid BCD product.
  • diluted ether-extracted low-molecular weight fraction of the BCD product can be used as feed in the SPHDO process.
  • the partially depolymerized lignin BCD product or its ether extract after it is diluted with a part of the fraction of the self-produced phenolic and/or high boiling alkylaromatic product, can be subjected to a low temperature stabilization/partial hydrodeoxygenation (SPHDO) process.
  • SPHDO low temperature stabilization/partial hydrodeoxygenation
  • This process can include the conversion of unstable methoxyphenols and benzenediols to a stable phenolic product on catalysts such as those discussed herein such as CoMo catalysts supported on alumina and active carbon.
  • These catalysts can also be used in the basic form, as well as those modified by neutralization of the support surface acidity (alumina) and/or introduction of additional noble metal promoters such as Pt, Pd, Ru, and RIi.
  • An important element of carbon-supported catalyst is the low cost of the carbon support and the ability of recovering the precious metals from spent catalysts by simply burning off the carbon, rather than more expensive refining or recovery processes.
  • the currently preferred processing conditions for the SPHDO reaction are a temperature from about 200 0 C to about 300 0 C, a residence time of about 5 to about 15 minutes, and H 2 pressure from about 500 to about 2000 psig.
  • HPR hydroprocessing
  • the HPR reaction runs with the BCD-SPHDO product as feed can be carried out in a single step procedure, or as a sequence of separate HDO and HCR reactions to obtain an aromatic-rich product, consisting mostly of C 7 - Cu alkylbenzenes.
  • HDO CoMoZAl 2 O 3
  • HCR CoMo/Al 2 O 3 -SiO 2 which can be amorphous or crystallized, i.e. zeolite
  • HDO MMo/ ⁇ -Al 2 O 3
  • HCR MMo/Al 2 O 3 -SiO 2
  • M Ru, Re, Cr or Fe (and combinations with Co)
  • HDO catalysts can be chosen based on low hydrogenation activity and HCR catalysts based on optimizing acidity and low hydrogenation activity. Aromatic ring hydrogenation during these reactions should be minimized by careful choice of the catalyst and associated temperatures. For example, using Ni in an HDO catalyst is highly active but also tends to result in high yields of cyclohexane and other hydrogenated products.
  • HDO catalysts can be neutral, slightly acidic or even slightly basic with substantially neutral being preferred.
  • the HDO catalysts can be chosen to allow exhaustive hydrodeoxygenation without poisoning by coking.
  • HCR (or MH) catalysts-support materials are generally acidic or strongly acidic sufficient to provide cracking without also causing excessive coking.
  • Higher molecular weight fraction components such as alkylated naphthalenes, alkylated tetralines, alkylated indanes, alkylated biphenyls and polyalkylated benzenes of the BCD-SPHDO-HPR product (b.p. > 205 0 C) can be optionally subjected to exhaustive hydrogenation, yielding high- value naphthenic kerosene as shown in Stage III of FIG. 1.
  • the BCD and SPHDO stages of the ELTE process can be nearly the same as presented for the ELTG process of FIG. 1.
  • the BCD-SPHDO product can be subjected to subsequent mild hydrocracking and etherification with methanol.
  • the BCD-SPHDO of lignin results in a high-yield but incomplete depolymerization of the feed's polymeric structure.
  • the main product consisting of monocyclic phenols
  • a mild hydrocracking procedure for the crude BCD product designated as an MH procedure
  • solid superacid catalysts is shown in FIG. 2 as Stage III.
  • This supplemental MH treatment can effectively depolymerize the lignin by selective C - C cleavage of residual intermediate oligomers to produce the desirable monomeric phenols.
  • processing conditions for the MH treatment can vary, the currently preferred processing conditions are a reaction temperature from about 200 °C to about 400 0 C, a residence time from about 5 to about 30 minutes, and a pressure (H 2 ) from about 1,000 to about 1,800 psig.
  • suitable strongly acidic catalysts for MH treatment step can include PtAVO 4 2" /ZrO 2 , heteropolyacids and their salts (supported and unsupported), FeCl 3 " 6H 2 O, and the like.
  • a mixture of light monomeric phenols in the BCD- SPHDO product can be subjected to etherification with methanol.
  • the etherification reaction can be performed at a reactor temperature from about 200 °C to about 400 0 C and an autogenous pressure from about 100 to about 2000 psig.
  • Suitable catalysts can include, but are not limited to, supported heteropolyacids or their salts, potassium benzoate, Cs-P/SiO 2 , S0 4 2 7Mn0 x /Al 2 0 3 , SO 4 2 7MoO x /Al 2 O 3 , SO 4 2 7WO X /A1 2 O 3 , S ⁇ 4 2 7CrO x /Al 2 O 3 , S0 4 2 7Ce0 x /Al 2 0 3 , and the like.
  • methanol can be used as the etherification agent. Any flow reactor system which allows for continuous drying of the recycled reaction mixture can be used.
  • the ELTG process of the present invention provides a number of benefits over previously available processes.
  • the majority portion of oxygen present in the BCD-SPHDO product can be preserved which eliminates the need for costly further hydrodeoxygenation steps.
  • oxygen remains incorporated in a major portion of the final, high-octane alkoxybenzene gasoline components. Therefore, there is substantially no need for outside oxygen-containing additives, as recommended by the Clean Air Act amendment.
  • the final total ELTG product, including hydrocarbons is expected to have octane numbers of about 130. As a result, these products can be conveniently used as a blending additive (e.g. to petroleum-derived gasolines having lower octane numbers) to generate premium reformulated gasolines possessing greatly improved combustion characteristics.
  • ILTF Integrated Lignin-to-Liquid Fuels
  • the ELTG and ELTE processes can be integrated into a single process.
  • the final ILTF products derived from such an integrated process can include the products of each of the ELTG and ELTE processes such as alkylbenzene gasoline, aromatic ether gasoline additives, and naphthenic kerosene.
  • a base catalyzed depolymerization reaction can be used to produce a partially depolymerized lignin product.
  • the base catalyzed depolymerization reaction can be performed with substantially only water as the solvent and reaction medium.
  • a low temperature stabilization/partial hydrodeoxygenation (SPHDO) process and (optional) fractionation of C 6 - C 9 alkylphenols from the SPHDO product can be performed.
  • High- temperature hydroprocessing reactions (HPR) of SPHDO product can yield aromatic-rich gasoline as a primary product. Further, exhaustive hydrogenation of higher molecular weight fraction of the HPR product, containing alkylated naphthalenes, alkylated tetralines, alkylated indanes, alkylated biphenyls and polyalkylated benzenes, yielding high-value naphthenic kerosene.
  • Etherification of C 6 - C 9 alkylphenols from the SPHDO product can be performed to produce aromatic ethers (alkylated alkoxybenzenes). Each of these steps was previously discussed in connection with FIGs. 1 and/or 2.
  • FIG. 3 A flow diagram of the integrated lignin conversion process (ILTF) for production of aromatic gasoline, rocket/jet propellant and aromatic ethers in a multi-stage procedure is presented in FIG. 3.
  • lignin material can be subjected to base- catalyzed depolymerization (BCD) with water, optionally methanol or ethanol, as solvent and reaction medium.
  • BCD base- catalyzed depolymerization
  • the entire partially depolymerized lignin product or its ether extract after being diluted with a part of SPHDO product and/or the high-boiling fraction of the alkylaromatic product, can be subjected to a low temperature stabilization/partial hydrodeoxygenation (SPHDO) process.
  • SPHDO low temperature stabilization/partial hydrodeoxygenation
  • This SPHDO process involves the conversion of unstable methoxyphenols and benzenediols to a more stable phenolic product.
  • the partially hydrodeoxygenated SPHDO product can be subjected to hydroprocessing (HPR) reactions in order to obtain aromatic-rich gasoline.
  • HPR hydroprocessing
  • Higher molecular weight compounds e.g., alkylated naphthalenes, alkylated tetralines, alkylated indanes, alkylated biphenyls and polyalkylated benzenes are produced as a hydroprocessing product.
  • the yields and types of products can be controlled to some extent by the HPR process.
  • the hydroprocessing products can then be optionally subjected to exhaustive catalytic hydrogenation.
  • This hydrogenation step can yield naphthenic kerosene containing a mixture of alkylated decalins, alkylated bicyclohexyls, alkylated hydrindanes, and polyalkylated cyclohexanes.
  • C 6 - C 9 alkylphenols fractionated from the SPHDO product can be used as feed for the etherification process with methanol leading to alkoxyphenols.
  • the integrated ILTF process can lead to production of at least three valuable fuel products, provides an opportunity to perform the overall lignin conversion process in a feasible way, and can improve the overall economy of the process as well as overall economy of projected bio-refineries.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne des procédés de conversion de lignine en produits liquides tels que des biocarburants et des additifs pour carburant. Un procédé de conversion d'un matériau de lignine en biocarburants peut consister à soumettre le matériau de lignine à un réaction de dépolymérisation catalysée basique afin d'obtenir une lignine partiellement dépolymérisée. Cette lignine partiellement dépolymérisée peut ensuite être soumise à une réaction de stabilisation/hydrodéoxygénation partielle afin d'obtenir un produit partiellement hydrodéoxygéné. Suite à l'hydrodéoxygénation partielle, le produit partiellement hydrodéoxygéné peut être soumis à une réaction au cours d'une étape de raffinage afin de former un biocarburant. Chacune des étapes peut être effectuée en une ou plusieurs étapes, en fonction de type de procédé. La fabrication d'un produit intermédiaire partiellement hydrodéoxygéné et la réaction ultérieure permettent de réduire ou d'éliminer de manière significative l'obturation du réacteur et l'encrassement du catalyseur. Plusieurs types de biocarburants utiles tels que des carburants, des additifs pour carburant, et similaires peuvent être fabriqués à partir de matériaux de lignine renouvelables au cours d'un procédé de conversion amélioré.
EP06758980A 2005-05-02 2006-05-02 Procedes de conversion catalytique de lignine en biocarburants Withdrawn EP1888713A4 (fr)

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WO2006119357A2 (fr) 2006-11-09
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