WO2010065872A1 - Transformation de biomasse à l'aide d’un catalyseur basique solide - Google Patents

Transformation de biomasse à l'aide d’un catalyseur basique solide Download PDF

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Publication number
WO2010065872A1
WO2010065872A1 PCT/US2009/066803 US2009066803W WO2010065872A1 WO 2010065872 A1 WO2010065872 A1 WO 2010065872A1 US 2009066803 W US2009066803 W US 2009066803W WO 2010065872 A1 WO2010065872 A1 WO 2010065872A1
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WO
WIPO (PCT)
Prior art keywords
solid
anyone
base catalyst
biomass
solid particulate
Prior art date
Application number
PCT/US2009/066803
Other languages
English (en)
Inventor
Paul O'connor
Steve Yanik
Robert Bartek
Original Assignee
Kior Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kior Inc. filed Critical Kior Inc.
Publication of WO2010065872A1 publication Critical patent/WO2010065872A1/fr

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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
    • C10G1/08—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
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives

Definitions

  • the invention relates generally to the conversion of biomass to a bio-oil in the presence of a solid base catalyst, and more particularly to the conversion of a solid biomass material comprising ligno-cellulose.
  • Solid base catalyzed processes have been proposed for a variety of chemical reactions of organic compounds. Most commonly solid base catalysts have been proposed for isomerization of olefins, hydrogenation reactions and de-hydrogenation reactions. It has also been suggested that solid base catalysts can be used for addition reactions and cyclization reactions.
  • US Patent 4,987,1 14 to Suzukamo et al. discloses a method for preparing an alumina catalyst doped with earth alkaline metals.
  • US Patent 5,097,088 to Fukao et al. discloses a process for preparing an alkyl- substituted hydrocarbon.
  • the process comprises reacting an alkylaromatic hydrocarbon with an olefin in the presence of a solid base catalyst.
  • the solid base is an alumina doped with both an alkali metal and an earth alkaline metal.
  • US Patent 7,341 ,973 to Flego et al. discloses a solid base catalyst consisting of an amorphous material obtained from a silica or alumina gel containing an alkaline, earth alkaline or transition metal. The catalyst is shown to be useful in double bond migration reactions.
  • Solid acid catalysts in particular acidic zeolites, are used in catalytic cracking of mineral oil fractions. Specifically H-ZSM-5 is the catalyst of choice for fluid catalytic cracking (FCC) processes.
  • This approach has two important disadvantages. It requires a two-step process pyrolysis to form a bio-oil, and upgrading of the bio-oil Moreover, the bio-oil is thermally unstable and forms copious amounts of coke in the upgrading reaction. Even after upgrading the quality of the bio-oil is poor.
  • the catalyst preferably is inexpensive, easily separable from the reaction products, and stable enough to withstand high temperatures as may be needed to removed deposited coke in a regeneration step.
  • the present invention addresses these problems by providing a process for converting a solid paniculate biomass to a bio-oil, said process comprising the step of heating the solid particulate biomass in the presence of a solid particulate basic catalyst.
  • Another aspect of the invention comprises a method for pretreating the solid biomass prior to the conversion in the presence of the solid base catalyst.
  • the use of solid base catalysts in the catalytic pyrolysis of solid biomass material offers a number of advantages.
  • the catalyst can be used during the pyrolysis step itself.
  • the resulting bio- oil is of better quality than that obtained with non-catalytic processes or processes using an acid catalyst.
  • the resulting bio-oil in certain cases, is of good enough quality that it can be blended with mineral oil fractions, such as vacuum gas oil (VGO) without requiring further upgrading.
  • VGO vacuum gas oil
  • the catalyst can be readily separated from the liquid and gaseous reaction products. This offers a major advantage as compared to prior art processes in which the biomass is soaked with a solution of an alkali and/or earth alkaline metal.
  • the solid base catalyst is thermally stable. It is inevitable that coke is formed during the pyrolysis of solid biomass material. The coke is deposited onto the catalyst particles. The preferred method of removing the coke is burning it off in a regenerator. A typical regenerator temperature is in the range of 600 to 700 DC. For economic reasons it is important that the catalyst be able to withstand these temperatures, so that the catalyst can be re-used in the process after regeneration.
  • solid base catalysts are inexpensive.
  • alumina- based solid catalysts are considerably less expensive than the solid acid zeolites.
  • a more expensive solid base catalyst such as a basic zeolite or a hydrotalcite, in order to optimize another process parameter, such as conversion yield or coke yield.
  • the use of solid base catalysts offers the option of using relatively inexpensive materials.
  • the invention provides a process for converting a solid particulate biomass to a bio-oil, said process comprising the step of heating the solid particulate biomass in the presence of a solid particulate basic catalyst.
  • the step of heating the solid paniculate biomass in the presence of a solid particulate basic catalyst will be referred to herein as the "pyrolysis step”.
  • the pyrolysis step may be carried out in any of a number of reactors. Suitable examples include cyclone reactors, fluid bed reactors, and ablative reactors. It is possible, and often preferable, to give the catalyst particles a secondary role as heat carrier particles. That is, the catalyst particles are preheated, prior to contacting them with the solid biomass particles, so that the catalyst particles provide at least part of the heat for the endothermic pyrolysis reaction. Suitably, the catalyst particles may be pre-heated in the regenerator, using the heat developed by burning off the coke deposits.
  • This second heat carrier material may be an inert material, such as sand.
  • the hot catalyst particles still contain a small amount of coke, e.g. 1 -3 wt%.
  • the coke increases the heat capacity of the catalyst particles, and acts as a reducing agent to the biomass.
  • the presence of coke on the catalyst tends to improve the quality of the bio-oil produced in the reaction.
  • Circulating fluidized bed reactors are well known in fluid catalytic cracking (FCC) of mineral oil fractions. It has been found that FCC reactors are particularly suitable for the pyrolysis step of the process of the present invention.
  • Any solid base is in principle suitable as a solid base catalyst in the process of the present invention.
  • Suitable examples include silica; alumina; layered hydroxy oxide; hydrotalcite; a hydrotalcite-like material; an anionic clay; a cationic clay; a metal oxide; a metal hydroxide; a metal carbonate; a basic zeolite, alumino phosphates; or a combination thereof.
  • alumina is a specifically preferred solid base material for use in the catalyst for the process of the present invention.
  • Alumina is sufficiently basic to be used as-is.
  • the basic characteristics of alumina can be enhanced by doping alumina with an alkali metal, an earth alkaline metal, or a combination thereof.
  • Silica by itself is not catalytic, but can be made into a solid base catalyst by doping with an alkali metal and/or an earth alkaline metal.
  • Doping of alumina or silica may be accomplished with any of a number of processes known in the art. Examples include the processes disclosed in Patent 4,71 1 ,873 to Suzukamo et al.; US Patent 4,987,1 14 to Suzukamo et al.; US Patent 5,097,088 to Fukao et al.; and US Patent 7,341 ,973 to Flego et al., the disclosures of each of which being incorporated herein by reference.
  • the solid base catalyst preferably has a particle size in the range of from 20 ⁇ m to 2000 ⁇ m, preferably from 30 ⁇ m to 800 ⁇ m.
  • the particles preferably have a spherical shape.
  • the solid particulate biomass material may be pretreated with an alkaline material.
  • the alkaline material may be the same material as the solid base catalyst, or may be a different material. Preferably the alkaline material is different from the solid base catalyst.
  • alkaline materials include alkali metals and earth alkaline metals, in particular Na, K, or a combination thereof.
  • the Na or K may be in the form of its carbonate or its hydroxide.
  • the pretreatment may comprise subjecting the solid particulate biomass to impregnation with a solution containing the alkaline material, or to mechanical treatment in the presence of the alkaline material.
  • mechanical treatment include milling, grinding, kneading, or a combination thereof.
  • biomass material is suitable for use in the present invention.
  • biomass materials comprising cellulose, in particular ligno-cellulosic materials.
  • biomass materials that cannot themselves be used as food, and do not compete with food harvests for arable acreage.
  • Preferred sources of biomass include aquatic plants, such as algae; energy crops such as switch grass and fast-growing trees (willow, poplar, eucalyptus); agricultural wastes (straw, com stover; bagasse); and forestry wastes (bark, branches, saw dust, wood chips).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé de transformation catalytique de biomasse solide qui consiste notamment à chauffer la biomasse particulaire solide en présence d'un catalyseur basique solide. La réaction catalytique peut être réalisée dans un réacteur cyclone, un réacteur à lit fluidisé ou un réacteur ablatif. L'alumine et l'alumine dopée constituent des catalyseurs basiques solides particulièrement appropriés.
PCT/US2009/066803 2008-12-05 2009-12-04 Transformation de biomasse à l'aide d’un catalyseur basique solide WO2010065872A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12007108P 2008-12-05 2008-12-05
US61/120,071 2008-12-05

Publications (1)

Publication Number Publication Date
WO2010065872A1 true WO2010065872A1 (fr) 2010-06-10

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/066803 WO2010065872A1 (fr) 2008-12-05 2009-12-04 Transformation de biomasse à l'aide d’un catalyseur basique solide

Country Status (1)

Country Link
WO (1) WO2010065872A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102039202A (zh) * 2010-12-15 2011-05-04 东南大学 具有规整孔道的固体碱整体催化剂及制备方法
CN103421529A (zh) * 2012-05-16 2013-12-04 中国科学院化学研究所 一种生物质催化热解的方法及陶瓷固体酸催化剂
WO2014015302A1 (fr) 2012-07-20 2014-01-23 Kior, Inc. Catalyseurs utilisés pour la conversion catalytique thermique de biomasse, et procédés de production et utilisation desdits catalyseurs
WO2014089131A1 (fr) * 2012-12-04 2014-06-12 Research Triangle Institute Compositions catalytiques et applications associées dans la pyrolyse catalytique de biomasse
US9522392B2 (en) 2013-03-15 2016-12-20 Inaeris Technologies, Llc Phosphorous promotion of zeolite-containing catalysts
US10155908B2 (en) 2012-03-07 2018-12-18 Research Triangle Institute Catalyst compositions and use thereof in catalytic biomass pyrolysis

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670613A (en) * 1985-05-08 1987-06-02 Shell Oil Company Process for producing hydrocarbon-containing liquids from biomass
US4987114A (en) * 1988-08-12 1991-01-22 Sumitomo Chemical Company, Limited Solid base and process for producing the same for preparing internal olefins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670613A (en) * 1985-05-08 1987-06-02 Shell Oil Company Process for producing hydrocarbon-containing liquids from biomass
US4987114A (en) * 1988-08-12 1991-01-22 Sumitomo Chemical Company, Limited Solid base and process for producing the same for preparing internal olefins

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102039202A (zh) * 2010-12-15 2011-05-04 东南大学 具有规整孔道的固体碱整体催化剂及制备方法
CN102039202B (zh) * 2010-12-15 2012-09-19 东南大学 具有规整孔道的固体碱整体催化剂及制备方法
US10155908B2 (en) 2012-03-07 2018-12-18 Research Triangle Institute Catalyst compositions and use thereof in catalytic biomass pyrolysis
CN103421529A (zh) * 2012-05-16 2013-12-04 中国科学院化学研究所 一种生物质催化热解的方法及陶瓷固体酸催化剂
CN103421529B (zh) * 2012-05-16 2015-01-21 中国科学院化学研究所 一种生物质催化热解的方法及陶瓷固体酸催化剂
WO2014015302A1 (fr) 2012-07-20 2014-01-23 Kior, Inc. Catalyseurs utilisés pour la conversion catalytique thermique de biomasse, et procédés de production et utilisation desdits catalyseurs
CN104602813A (zh) * 2012-07-20 2015-05-06 Kior股份有限公司 用于生物质的热催化转化的催化剂及其制造与使用的方法
US9518229B2 (en) 2012-07-20 2016-12-13 Inaeris Technologies, Llc Catalysts for thermo-catalytic conversion of biomass, and methods of making and using
WO2014089131A1 (fr) * 2012-12-04 2014-06-12 Research Triangle Institute Compositions catalytiques et applications associées dans la pyrolyse catalytique de biomasse
US9522392B2 (en) 2013-03-15 2016-12-20 Inaeris Technologies, Llc Phosphorous promotion of zeolite-containing catalysts

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