[go: up one dir, main page]

WO2010068748A1 - Thermoconversion catalytique sélective d'une biomasse et biocarburants - Google Patents

Thermoconversion catalytique sélective d'une biomasse et biocarburants Download PDF

Info

Publication number
WO2010068748A1
WO2010068748A1 PCT/US2009/067488 US2009067488W WO2010068748A1 WO 2010068748 A1 WO2010068748 A1 WO 2010068748A1 US 2009067488 W US2009067488 W US 2009067488W WO 2010068748 A1 WO2010068748 A1 WO 2010068748A1
Authority
WO
WIPO (PCT)
Prior art keywords
biomass
bio
solid
catalyst
carried out
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.)
Ceased
Application number
PCT/US2009/067488
Other languages
English (en)
Inventor
Michael Brady
Dennis Stamires
Paul O'connor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inaeris Technologies LLC
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 WO2010068748A1 publication Critical patent/WO2010068748A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • the invention relates generally to a two-step process for preparing a biooil from solid biomass, and more particularly to a process using a basic catalyst in the first step and an acidic catalyst in the second step.
  • flaming and smoldering combustion processes relate to pyrolysis processes, wherein the flaming combustion involves the gas phase oxidation of the pyrolysis products, and smoldering combustion involves the combustion of residues remaining alter evaporation of the volatile components.
  • Gray, R., et al. in their work used a wood-derived material that was pyrolized in a fluidized bed reactor operated in a nitrogen atmosphere at different temperatures. (See Ind. Eng. Chem. Process Dev., Vol. 24, No. 3 (1985) 646-65) They acid-treated the samples as well as ion exchanged them with a calcium salt. They measured the yield of gases, aqueous and tar (oily) products, at three different pyrolysis temperatures. Both the acid-treated and calcium exchanged samples gave higher tar yields (organic, volatile compounds) than the untreated samples, which gave increased yields of water, char, and gases.
  • Varhegyi, G ., et at have studied the pyrolytic devolatilization of cellulose and sugar cane bagasse. (See Energy & Fuels (1988) 8, 267-272) The samples were impregnated with MgCb, NaCl, FeSO,*, and Z ' nCk catalysts. ITie authors used a sophisticated experimental equipment arrangement by combining the Thermo- gravimetric and Mass Spectrometry mstruments, and operating in a continuous simultaneous mode. In general, their data show substantial changes in yields and product distribution, as well as lowering the temperature of the weight-maximum loss peaks, as a result of catalyst impregnation.
  • the salts used for the impregnation included Na 2 CO 3 , K 2 CO 3 , ZnC ⁇ 3 , NaCl, KCl, ZnCfe, HCl, NaOH, and were used to treat 13 natural biomass materials plus severaJ synthetic samples. (See Fuel (1995), Vol. 74, No. 12, 1814-1816)
  • Fahmi, R., et al reported on the effect of alkali metals present or added to two kinds of grasses and two kinds of wood on their catalytic pyrolysis.
  • R. Fahmi et al Fuel, 86 (2007) 1560-1569
  • D.S. Scott et al J. Anal. Appl. Pyrolysis, 54 (2001 )169-176
  • DJ. Nowakowski et al Fuel 86 (2007) 2389-2402
  • Acid treatments were used to remove the indigenous metals from the samples, which were milled to below 500 ⁇ m particle size.
  • High resolution DTG measurements showed the individual peaks for the decomposition of heraicellulose (about 500 K) and the higher temperature (598 K) corresponded to the cellulose component decomposition, which is more thermally stable as it is crystalline, whereas the hemicellulose (semi-crystalline) is less thermally stable.
  • the intensity of the individual peaks provided relative quantitative estimates of the concentration of the individual components in the biomass samples. For example, the acid pretreatment of Festuca grass resulted in a 900% increase in the yield of levoglucosan during pyrolysis.
  • U.S. Patent No. 3,926,947 describes a process in which cellulosic waste materials such as paper and newsprint are treated with an acidic fire retardant that enhances the yield of certain bio-oils during pyrolysis.
  • the fire retardanls claimed were: phosphoric acid, ammonium phosphates, ammonium sulphate, and zinc sulphate, which were impregnated on the biomass before subjected to pyrolysis.
  • U.S. Patent No. 5,807,952 teaches a process for converting lignins to phenolic compounds by pyrolyzing the lignin in the presence of a strong base like KOH.
  • the lignin and potassium hydroxide powders were mixed and placed into a single stage quench reactor heated to 600°C. Vapors were analyzed with a mass spectrometer.
  • U.S. Patent No. 5,395,455 describes a process for producing anhydrosugars from lignin and cellulose containing biomass by pyrolysis, using a strong acid prctreatr ⁇ ent of the biomass before pyrolysis. Besides claiming the acid-removal of the natural minerals from the biomass, the patent also claims that certain anions, such as sulphate, sulphite or nitrate, can be added to the acid-treated biomass by impregnation. Further, after the strong acid-treatment (digestion) of the biomass, soluble organic material can be separated and the residue then pyrolyzed. [0034] Thus, there is a particular need for providing an improved process for the catalytic conversion of solid biomass to bio-crude, followed by the catalytic upgrading of bio-crude to bio-oil.
  • the present invention addresses these problems by providing a process for the conversion of solid biomass, said process comprising the steps of;
  • Another aspect of the invention comprises a method for the conversion of solid biomass as described above wherein the ash content of the biomass is reduced prior to step (i).
  • Category A involves inorganic materials which enhance the decomposition of the raw biomass, which may act as catalysts involving C-O and C-steam reactions.
  • Such basic catalysts that increase the rate of the solid raw biomass conversion will be referred to herein as Primary Catalysts, and include the Alkaline and Alkaline Earth salts, oxides, hydroxides, carbonates, hydroxyi-carbo ⁇ ates, etc.
  • Category B involves acidic inorganic materials that interact with the evolving organic gases and liquid products, which are produced in-situ from the thermolysis of biomass.
  • These kinds of acidic catalysts are referred to as Secondary Catalysts, some of which are similar to those used in cracking heavy petroleum feedstocks.
  • Examples of the Secondary Catalysts include solid jtuper-aeids, fluorinated transition metal oxides (i.e., F-doped aluminum oxides), acidic zeolites, acidic clays, alumina-titania, silica-alumina composites with or without zeolites, and so on.
  • the Primary Catalyst must be allowed to react effectively and selectively with the solid raw biomass first, while subsequently the produced organic gases and liquids are allowed to react with the Secondary Catalyst before they undergo further interactions between themselves, with the solid biomass or with the char.
  • US Patent 3,926,947 the disclosures of which are incorporated herein by reference, teaches the use of acidic salts, applied to cellulosic materials by impregnation, using solutions of phosphoric acid, ammonium phosphate, zinc sulphate and zinc phosphate.
  • Other acidic rlre-retardants have been applied to cellulosic materials before being subjected to pyrolysis or gasification processes. Such applications are referred to as chemical pretreatr ⁇ ents.
  • inorganic catalysts that have been applied to biomass by impregnation from solutions, include the chloride and sulphate salts of zinc, magnesium, sodium and iron. Such applications are referred to as chemical pretreatments.
  • Still another category of solid acidic catalysts primarily siHcon-aluminates, specifically known FCC-type catalysts, non-zeolite FCC, FCC-Additives and catalysts containing ZSM zeolites, or MCM zeolites, have been used as particulate physical mixtures in pyrolytic and gasification conversion reactions. Such applications using different particulate components of biomass and catalysts, are referral to as physical mixtures.
  • Impregnation and demineralization of different types of biomass are described by W. DeGroot, et al in the J. Analytical & Applied Pyrolysis (1989) 16, 117-126), where salts of zinc and potassium chlorides as well as potassium and zinc carbonates were impregnated on biomass, and the resulting volatiles, gas, liquid and char, were measured.
  • potassium carbonate was demonstrated to be an effective catalyst for biomass gasification reactions as it lowers the gasification temperature, increases the gasification rates, increases gas yields and increases the heat content of the fuel gas produced.
  • Flash pyrolysis in fluidized bed experiments were conducted for maxinming the organic liquid yield from biotnass using lime and a nickel hydrogenation catalyst.
  • the solid lime particles were mixed with woody sawdust and the physical mixture pyrolyzed at different temperatures.
  • the addition of lime resulted in a lower temperature decomposition for maximum liquid yield and an increase of light hydrocarbon yields.
  • the lime catalyst produced liquid organic products (tar) which contained higher carbon and less oxygen contents.
  • a simplified model of the various decomposition, cross-interactions and product formation pathways involves a primary and a secondary stage.
  • Primary Stage primary liquids and primary char are being formed.
  • secondary stage primary liquids transform into tar, secondary char, and light pyrolysis products.
  • These light hydrocarbon products which include acids, esters, aldehydes and ketones act as catalysts to further auto-catalyze the breakdown of the primary liquids to lighter products.
  • This invention describes a two-step process that enhances the production of pyrolysis oils and improves their quality in terms of containing less oxygen, more carbon, being less acidic and having lower molecular weight.
  • the catalyst in the First Step, to achieve optimal thermoconversion of the biomass, the catalyst must be uniformly distributed on the surface or penetrated into the individual biomass particles. Impregnations, from solutions or from catalyst slurries, assisted with shear mechanical mixing, is much more effective in distributing homogenously the catalyst on the surface of the individual biomass products than, for exampl ⁇ j by simply mixing the biomass with the solid catalysts, or by co-milling the bioraass with the catalyst.
  • the basic catalyst effectively interacts with the biomass, which is acidic in nature, as both components exist in intimate contact while the biomass decomposes with the assistance of the basic catalyst In simple terms, this can be envisioned as an "acid-base” reaction. Still further, while the basic catalyst is part of the "Biomass-Catalyst” composite, the light organic gases and tars produced in the flash pyrolysis are removed and thus have a lesser exposure towards the basic catalyst- biomass composite, thus minimizing the cross and the back-reactions with the basic catalyst part of the biomass-catalyst composite particle.
  • Another beneficial Junction that the basic catalyst serves is to neutralize the acids produced during the thermolysis of the biomass, which acids act as catalysts in reactions between the products and between the products and biomass.
  • acidic neutralizations caused by the basic catalyst increase the pH of the tars, so the tars having a higher pH are more suitable to be treated with an acidic type of cracking catalyst to be converted to light hydrocarbon products.
  • Another mode of operating the First-Step of Ae process involves using fine powders of the basic-catalyst and homogenously mixing the powder with the fine particles of biomass while heating the biomass to cause a softening of the biomass surface sufficient to allow the basic-catalyst particles to adhere to the biomass particles.
  • This procedure does not use water, only die two fine particle powders are bonded together. This procedure is useful when water solutions or slurries of the basic-salt catalysts are not desirable. Steaming may optionally be used to facilitate the adhering process of the two solid particles.
  • Still another mode of operation of this invention involves contacting the biomass in the pyrolysis reactor with the fl ⁇ idized bed of the heat carrier which contains a basic catalysl.
  • Said basic catalyst may function also as a heat carrier and may consist of oxides, hydroxides, hydroxycarbonates, carbonates of the alkaline and alkaline earth metals, and mixtures thereof.
  • the purpose of the Second-Step is to catalyticaUy crack die freshly, instantly in-situ-generated tar with an acidic cracking type of catalyst before the tar components cross interact between themselves, and with the remnants of the biomass to form heavier organic compounds (tars) or chars.
  • Another objective of the second-step is, to the extent that it is physicaHy/rDCchanicaUy possible, to keep separate (with minimum superimposition), the reactions of the acidic catalyst with the nascent tars from the devolatilization of the biomass-cataJyst composite.
  • the second-step of the process can be conducted in a separate reactor connected in line with the pyrolysis reactor.
  • the overall objective of this invention has two functions: (a) to selectively promote, first, the solid biomass-basic catalyst reaction and second by (b) promoting the tar/vapors-acidic catalyst reaction, while at the same time minimizing the overlapping and competing cross interactions between these two functions (a) and (b).
  • the overall process is flexible and provides a means to selectively optimize product yields and quality.
  • the acidic catalyst can be used in the second-step of the process, whereas in the first-step, a pretreated biomass can be used.
  • pretreated biomass material examples include:
  • Biomass that has been torrefied /toasted and contacted with a basic catalyst are torrefied /toasted and contacted with a basic catalyst.
  • Calcium compounds applied to biomass in contrast to the salts of alkali metals from Group I of the Periodic Table, do not lower the bio oil yields, and produce maximum yields at lower biomass decomposition temperatures, as do all other metals.
  • the use of calcium compounds i.e., lime, limestone, dolomite, etc.
  • the biomass (tar) produced contains less oxygen and higher amounts of carbon.
  • the calcium catalyst is finely and uniformly applied to biomass particles, which is accomplished by applying a fine spray of the slurry to the small particle of biomass while it is being vigorously agitated or fluidized. Impregnation of the biomass small particles with slurries containing well dispersed in colloidal form the calcium compounds is another method of placing the calcium catalyst in intimate contact with the biomass before pyrolysis, as a first-step processing. Also, this can be accomplished in a kneader with spraying capability.
  • the pretreated biomass with calcium-bearing catalyst can be pyrolyzed in a fashion that the acidic catalyst preferably is introduced to the pyrolysis reactor after the biomass has been thermolyzed, as, for example, in the dilute phase of the fluidized bed or in a second, in-line reactor, such as the stripper.
  • This second-step processing is designed to achieve further upgrading of the bio oils (tars).
  • the process of the invention optimizes both the yield and the quality of bio- oil obtained in the pyrolytic conversion of solid biomass by providing a basic catalyst for catalyzing the conversion of the solid biomass to a liquid conversion product, and an acidic catalyst for upgrading the liquid conversion product,
  • bio- crude the liquid conversion product
  • bio-oil the upgraded bio-crude
  • the basic catalyst and the acidic catalyst are both present during the bioroass conversion reaction. If both catalysts are solid, chemical interaction of the t-wo catalyst types with each other is minimized.
  • This embodiment has the advantage that the bio-crude components are upgraded in situ, as they are formed.
  • the conversion step and upgrading step are conducted sequentially in the same reactor. Specifically, the solid biomass is initially contacted in the reactor with the basic catalyst alone; after at least part of the conversion to bio-crude has taken place, the acidic catalyst is introduced into the reactor.
  • the latter embodiment can conveniently be carried out in a fluid bed riser.
  • Solid biomass particles and solid base catalyst particles are introduced near the bottom of the riser.
  • the solid acid catalyst is introduced at a higher point in the riser, preferably at or above the mid-point of the riser.
  • the cracking step is carried out in a separate reactor, for example a stripper, a disengager or a cyclone located downstream from a fluid bed riser.
  • a separate reactor for example a stripper, a disengager or a cyclone located downstream from a fluid bed riser.
  • the bio-crude is se/parated from unconverted biomass prior to being subjected to the cracking step.
  • the conversion of the solid biomass may be carried out at a temperature in the range of from 400 to 550 0 C.
  • the cracking of the bio-crude to bio-oil may be carried out at a lower temperature , for example in the range of from 350 to 450 °C. If the two steps are carried out in a riser, this can be accomplished by quenching the reaction mixture with cold acidic catalyst
  • the solid biomass material and the basic catalyst are mixed in the reactor.
  • the basic catalyst can be used as a heat carrier, providing all or part of the heat for the endothermic conversion reaction.
  • the solid biomass and the basic catalyst are contacted with each other prior to entering the reactor.
  • This pre-contaeting may take place just prior to entering the reactor, or it may be done in a separate pretreatifying step.
  • the pretreatment step desirably comprises mechanical treatment, such as co-milling, co-grinding or co-kneading of the solid biomass and the basic catalyst.
  • An important aspect of the process of the invention is the high quality of the bio-oil produced by it.
  • An important parameter for gauging the quality of a bio-oil is the Total Acid Number, or TAN, defined as the amount of KOH, in mg, required to neutralize 1 g of the bio-oil.
  • TAN Total Acid Number
  • the bio-oils produced by the process of the present invention generally have a TAN of less than 40.
  • the process can be optimized, for example by pre-treating the biomass, and/or by a judicious choice of reaction temperatures, to produce bio-oils having a TAN of less than 20.
  • minerals naturally present in the solid biomass may interfere with the catalytic process. It is desirable to use biomass feedstocks for the process having an ash content of less than 5 wt%, preferably less than 2 wt%. This can be accomplished by selecting a biomass source having a naturally low level of ash, or by subjecting the biomass feedstock to an ash removal step. For example, indigenous salts can be effectively removed by extraction with an aqueous liquid.
  • the extraction step may comprise swelling the biomass with the aqueous liquid, and removing at least part of the aqueous liquid (which contains dissolved minerals from the biomass) by mechanical action.
  • suitable mechanical action include pressing in a filter press or in a kneader.
  • the basic catalyst comprises a cation from Group I or Group II of the Periodic Table of the Elements.
  • the cation preferably is added in the form of its oxide, hydroxide, carbonate, or a combination thereof.
  • Preferred cations from Group 1 of the Periodic Table are Na and K.
  • a preferred cation from Group II of the Periodic Table is Ca.
  • Suitable examples of Ca- containing basic catalysts include lime and dolomite.
  • the acidic catalyst preferably comprises a solid acid.
  • Suitable examples of solid acids include the acidic zeolites, such as HZSM zeolites, and H-Mordenites.

Landscapes

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

Abstract

La présente invention concerne un procédé de conversion catalytique d'une biomasse solide en biocarburant. Dans une première étape, la biomasse solide est convertie en un produit biologique brut en présence d'un catalyseur basique. Dans une seconde étape, le produit biologique brut est soumis à un craquage catalytique en présence d'un catalyseur acide. La première étape et la seconde étape peuvent être effectuées simultanément ou de manière séquentielle. Le procédé produit un biocarburant de qualité élevée, comme le démontre son faible indice d'acidité totale (TAN).
PCT/US2009/067488 2008-12-10 2009-12-10 Thermoconversion catalytique sélective d'une biomasse et biocarburants Ceased WO2010068748A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12123408P 2008-12-10 2008-12-10
US61/121,234 2008-12-10

Publications (1)

Publication Number Publication Date
WO2010068748A1 true WO2010068748A1 (fr) 2010-06-17

Family

ID=42243066

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/067488 Ceased WO2010068748A1 (fr) 2008-12-10 2009-12-10 Thermoconversion catalytique sélective d'une biomasse et biocarburants

Country Status (1)

Country Link
WO (1) WO2010068748A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120055077A1 (en) * 2010-09-02 2012-03-08 Savage Phillip E Method of producing an upgraded bio-oil
WO2012128055A1 (fr) * 2011-03-22 2012-09-27 昭和電工株式会社 Procédé de prétraitement de matériaux de base pour réaction hydrolytique d'une biomasse végétale et procédé de saccharification de la biomasse végétale
CN103124712A (zh) * 2010-07-23 2013-05-29 科伊奥股份有限公司 多级生物质转化
EP2595915B1 (fr) * 2010-07-19 2019-01-02 KiOR, Inc. Procédé de pyrolyse de biomasse
CN116064167A (zh) * 2021-10-30 2023-05-05 中国石油化工股份有限公司 一种生物质制合成气的方法和系统

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064018A (en) * 1976-06-25 1977-12-20 Occidental Petroleum Corporation Internally circulating fast fluidized bed flash pyrolysis reactor
US4266083A (en) * 1979-06-08 1981-05-05 The Rust Engineering Company Biomass liquefaction process
US5233109A (en) * 1989-11-06 1993-08-03 National University Of Singapore Production of synthetic crude petroleum
US5599510A (en) * 1991-12-31 1997-02-04 Amoco Corporation Catalytic wall reactors and use of catalytic wall reactors for methane coupling and hydrocarbon cracking reactions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064018A (en) * 1976-06-25 1977-12-20 Occidental Petroleum Corporation Internally circulating fast fluidized bed flash pyrolysis reactor
US4266083A (en) * 1979-06-08 1981-05-05 The Rust Engineering Company Biomass liquefaction process
US5233109A (en) * 1989-11-06 1993-08-03 National University Of Singapore Production of synthetic crude petroleum
US5599510A (en) * 1991-12-31 1997-02-04 Amoco Corporation Catalytic wall reactors and use of catalytic wall reactors for methane coupling and hydrocarbon cracking reactions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2595915B1 (fr) * 2010-07-19 2019-01-02 KiOR, Inc. Procédé de pyrolyse de biomasse
CN103124712A (zh) * 2010-07-23 2013-05-29 科伊奥股份有限公司 多级生物质转化
EP2595941A4 (fr) * 2010-07-23 2014-07-30 Kior Inc Conversion de biomasse à étapes multiples
US9394487B2 (en) 2010-07-23 2016-07-19 Inaeris Technologies, Llc Multi-stage biomass conversion
US20120055077A1 (en) * 2010-09-02 2012-03-08 Savage Phillip E Method of producing an upgraded bio-oil
WO2012128055A1 (fr) * 2011-03-22 2012-09-27 昭和電工株式会社 Procédé de prétraitement de matériaux de base pour réaction hydrolytique d'une biomasse végétale et procédé de saccharification de la biomasse végétale
CN103442816A (zh) * 2011-03-22 2013-12-11 昭和电工株式会社 植物性生物质的水解反应用原料的前处理方法和植物性生物质的糖化方法
US9284614B2 (en) 2011-03-22 2016-03-15 Showa Denko K.K. Pre-treatment method for plant biomass hydrolysis reaction raw materials and plant biomass saccharification method
JP5943489B2 (ja) * 2011-03-22 2016-07-05 昭和電工株式会社 植物性バイオマスの加水分解反応用原料の前処理方法及び植物性バイオマスの糖化方法
CN116064167A (zh) * 2021-10-30 2023-05-05 中国石油化工股份有限公司 一种生物质制合成气的方法和系统

Similar Documents

Publication Publication Date Title
US8168840B2 (en) Biomass pretreatment process
CA2829205C (fr) Pretraitement de biomasse pour une pyrolyse rapide pour obtenir des liquides
Stephanidis et al. Catalytic upgrading of lignocellulosic biomass pyrolysis vapours: effect of hydrothermal pre-treatment of biomass
Li et al. Investigation on the catalytic behavior of alkali metals and alkaline earth metals on the biomass pyrolysis assisted with real-time monitoring
Yaman et al. Catalytic upgrading of pyrolysis vapours: effect of catalyst support and metal type on phenolic content of bio-oil
RU2715243C2 (ru) Варочные щелоки и их применение
US9175235B2 (en) Torrefaction reduction of coke formation on catalysts used in esterification and cracking of biofuels from pyrolysed lignocellulosic feedstocks
WO2009118363A2 (fr) Huile brute bio à faible indice d'acidité
WO2010068748A1 (fr) Thermoconversion catalytique sélective d'une biomasse et biocarburants
Li et al. Synergistic enhancement of bio-oil quality through hydrochloric or acetic acid-washing pretreatment and catalytic fast pyrolysis of biomass
Wang et al. Pyrolysis mechanism of hemicellulose monosaccharides in different catalytic processes
Dong et al. Review on the progress in the production of aromatic hydrocarbons by co-catalytic pyrolysis of biomass and plastics
Jin et al. Co-processing of pyrolysis vapors with bio-chars for ex-situ upgrading
Singh et al. Catalytic upgrading of biomass pyrolysis vapors for selective production of phenolic monomers over metal oxide modified alumina catalysts
Prabhakara et al. Role of dolomite as an in-situ CO2 sorbent and deoxygenation catalyst in fast pyrolysis of beechwood in a bench scale fluidized bed reactor
Uzun et al. Pyrolysis: A sustainable way from biomass to biofuels and biochar
Aho et al. Catalytic pyrolysis of lignocellulosic biomass
Yang et al. In-situ catalytic upgrading of tar and coke during biomass/coal co-pyrolysis
El-Sayed Chemical products yielded from different pyrolysis processes of rice waste residues: a comprehensive review
Hu et al. Recent advances in the catalytic pyrolysis of biomass
Mhemed et al. Kinetic study of lignocellulosic biomasses pyrolysis using thermogravimetric analysis
Tsvetkov et al. Thermocatalytic Biomass Processing
Kumar et al. Lignocellulose biomass pyrolysis for bio-oil production: biomass pre-treatment methods for production of drop-in fuels
Wang et al. Influence of the Zeolite ZSM-5 on Catalytic Pyrolysis of Biomass via TG-FTIR
Huyghe The role of alkali and earth alkaline metals as intrinsic catalysts in the fast pyrolysis of biomass constituents

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09832531

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09832531

Country of ref document: EP

Kind code of ref document: A1