WO2009073938A1 - Procédé pour transformer du glycérol et/ou de la biomasse en produits de plus grande valeur ajoutée - Google Patents

Procédé pour transformer du glycérol et/ou de la biomasse en produits de plus grande valeur ajoutée Download PDF

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Publication number
WO2009073938A1
WO2009073938A1 PCT/BR2008/000013 BR2008000013W WO2009073938A1 WO 2009073938 A1 WO2009073938 A1 WO 2009073938A1 BR 2008000013 W BR2008000013 W BR 2008000013W WO 2009073938 A1 WO2009073938 A1 WO 2009073938A1
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WO
WIPO (PCT)
Prior art keywords
fact
biomass
pursuant
products
glycerol
Prior art date
Application number
PCT/BR2008/000013
Other languages
English (en)
Inventor
Nunes Pessoa Márcio
Cláudia Danielle CARVALHO DE SOUSA
José BARBOSA DUARTE
Original Assignee
Sentex Industrial Ltda.
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 Sentex Industrial Ltda. filed Critical Sentex Industrial Ltda.
Publication of WO2009073938A1 publication Critical patent/WO2009073938A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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
    • C10G2400/22—Higher olefins
    • 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

Definitions

  • the present invention consists in a process of transformation of glycerol and/or biomass by heterogenic catalysis aiming the production of olefins and/or fuel and/or organic intermediates for polymer synthesis.
  • the glycerol used in the catalytic process is, usually, the raw glycerol resultant from the alcoholysis of grease raw materials, which is converted into products of higher value added.
  • Such process can be extended to any kind of dry biomass.
  • the products obtained which can be alcohols and/or aldehydes and/or alkanes and/or olefins, vary with the conditions of the process and catalyzer selected among the developed in the present invention.
  • the raw glycerin is made of glycerol, water and impurities, among which are: alcohols, esters, fatty acids and catalyzers. These are considered glycerin contaminants and unable its use for traditional purposes, like pharmaceutical, hygiene and food products, and other industrial purposes that they are conditioned to, each one, an specific degree of purity.
  • glycerin In order glycerin can be employed, it is necessary to purify the raw glycerin, which has been traditionally made by vacuum distillation. However, it does not create new purposes for the biodiesel sub-product, in order to absorb this supply excess that increases day after day.
  • glycerol is a kind of monomer of the majority of the natural polyols, including starch, cellulose, hemicelluloses and other carbohydrate polymers. This way, processes used for glycerol can be adequately adapted for the use of biomass containing basically cellulose and hemicelluloses. In a symmetrical way, glycerol can be considered a "methanol trimer".
  • the American patent US 4788369 describes how gasoline can be obtained from methanol using a continuous process, in a fixed bed, with acid crystalline catalyzer as, for example, ZSM-5.
  • MTO acid crystalline catalyzer
  • an alcohol can be converted into hydrocarbons.
  • the oil refinement industry uses additives made of the zeolite MFI, also known as ZSM-5, to produce olefins during the catalytic cracking process of the oil during the FCC process. These olefins, as ethylene and propylene, are high value raw materials for Petrochemical.
  • the acrolein Through chemical pathways from propylene it is obtained: the acrolein, the acrylic acid, acrylonitrile used as intermediate for acrylate polymers, and also polypropylenes.
  • the production of these olefins implies in the expenditure of part of the gasoline that could be obtained in the FCC process.
  • the international patent application WO 95/16723 reports the obtainment of glycerol polymers from the glycerol, 2,2-dimetil-1 ,3-dioxolan-4-methanol, glycidol glycerol carbonate, with a clay type hydrotalcite in temperature of 180 to 25O 0 C. Differently from the process that will be presented here, the polymerization is inhibited by the presence of ZSM-5 mixed with hydrotalcite, in order to obtain a higher fraction of lights.
  • the American patent US 5387720 describes a process for use of acid catalyzers, for example the acid zeolite ZSM-5, for acrolein production, by glycerol dehydration.
  • the temperature of this process goes from 180 to 340 0 C.
  • the acid ZSM-5 promotes the generation of alcohols and aldehydes that function as intermediates for the condensation/cleavage step for the creation of the final product.
  • One of the purposes of the present invention is to promote the transformation of glycerol and/or biomass into products of higher added value, aiming the creation of a new chemical pathway for the production of olefins and/or biofuel. More specifically, this transformation occurs in a process that uses solid acid and/or crystalline basic and/or amorphous catalyzers specially synthesized for this purpose, like zeolites, hydrotalcite and niobia.
  • the present invention refers to a process that allows the use of glycerol and/or biomass as raw materials for production of olefins and other light gases, and also paraffin and aromatics, under process conditions in fluidized bed.
  • This process occurs through a catalytic reaction with different solid materials, which can have basic or acid catalytic activity.
  • the solid materials used in the catalytic reaction can contain: aluminum oxides, magnesium oxides, silicon oxides, sodium oxides and calcium oxides and were synthesized as such for the fabrication of catalyzers used in the glycerin dehydration and polymerization reaction.
  • These solids can be: crystalline as zeolites like MFI, LTA and MOR and/or lamellar aluminum magnesium oxides, like hydrotalcite and/or amorphous solids like Niobia HY® and calcium oxide.
  • the crystalline materials were adequately mixed with ligands, inerts and peptizing and/or chelating agents in order to obtain catalyzers with size, porosity, texture and catalytic activity characteristics adequate for its use in this process of heterogenic catalysis.
  • Fixed and fluidized bed reactors were used with temperature of the process varying from 170 to 380 0 C, preferentially between 250 and 280 0 C.
  • the work pressure may vary between 60mmHg of vacuum and 11400mmHg of positive pressure, preferentially between vacuum and lOOmmHg.
  • the process can be made under inert atmosphere with nitrogen flux or in the presence of air.
  • the reactor can be operated in batch, continuous or semi-continuous regime, with the catalyzer presenting a percentage between 0.05 and 40% w/w in relation to the biomass.
  • the time of reaction for the process to occur in an efficient manner vary between 0.5 and 5hs.
  • Example 1 The examples below present the variations of the process.
  • a catalyzer predominantly composed of magnesium and aluminum oxide like hydrotalcite was used in a stuffing column connected to a saturator.
  • a mass of 30Og of glycerol was heated and the glycerin vapor came in contact with the catalytic bed previously heated between 250 and 32O 0 C, containing 10OmL of catalyzer mixed with inert silicon.
  • the device was kept under vacuum of 50 and 80mmHg and the gaseous and condensable material obtained was adequately trapped.
  • the material was previously mixed, and then heated in a reactor with agitation and linked to a distillation column with reflow. The reacted material was separated by vacuum distillation, under a temperature that vary between 220 and 280 0 C.
  • a catalyzer predominantly composed of acid ZSM-5 was extrused with alumine Catapal® and Niobia® in the presence of an adequate peptizer like citric acid, acetic acid or nitric acid, preferentially citric acid.
  • This material was used in a stuffing column connected to a saturator.
  • a mass of 30Og of glycerol was heated and the glycerin vapor came in contact with the catalytic bed previously heated between 250 and 32O 0 C, containing 10OmL of catalyzer mixed with inert silicon.
  • the device was kept under vacuum of 50 and 80mmHg and the gaseous and condensable material obtained was adequately trapped.
  • a mass of 300g of glycerol was reacted with a catalyzer composed only of acid ZSM-5.
  • a distillation column with reflow connected to the reactor promoted the removal of part of the reaction products.
  • the distilled material was reacted with calcium oxide, and the bottom material was separated from the catalyzer by filtration.
  • Example 7 A mass of 30Og of glycerol was heated between 200 and 34O 0 C, preferentially between 280 and 310 0 C, under autogenic pressure between 6 to 8,827mmHg with an amount between 1 and 10%w/w of a mix previously prepared of sodium bicarbonate, sodium carbonate and citric acid, during a period between 30 minutes and 2hs.
  • the material obtained this way presented biphasic and was separated by decantation.
  • the ones proficient in arts will value immediately the important benefits resulting from the use of the present invention. Variations in the ways to concretize the inventive concept here exemplified must be understood as inside the spirit of the invention and the annexed claims.

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  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de transformation de glycérol et/ou de biomasse par catalyse hétérogène visant la production d'oléfines et/ou de combustible et/ou d'intermédiaires organiques pour la synthèse de polymères. En particulier, le glycérol utilisé dans le procédé catalytique est, habituellement, le glycérol brut résultant de l'alcoolyse de matières premières de graisse, qui est converti en produits de plus haute valeur ajoutée.
PCT/BR2008/000013 2007-12-13 2008-01-18 Procédé pour transformer du glycérol et/ou de la biomasse en produits de plus grande valeur ajoutée WO2009073938A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPROT.020070176758 2007-12-13
BRPI0704950-1A BRPI0704950A2 (pt) 2007-12-13 2007-12-13 processo para transformação de glicerol e/ou biomassa em produtos de maior valor agregado

Publications (1)

Publication Number Publication Date
WO2009073938A1 true WO2009073938A1 (fr) 2009-06-18

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ID=40755193

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2008/000013 WO2009073938A1 (fr) 2007-12-13 2008-01-18 Procédé pour transformer du glycérol et/ou de la biomasse en produits de plus grande valeur ajoutée

Country Status (2)

Country Link
BR (1) BRPI0704950A2 (fr)
WO (1) WO2009073938A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274886A (zh) * 2013-03-28 2013-09-04 中国石油大学(北京) 一种甘油转化制烯烃的方法及催化剂
CN107099380A (zh) * 2017-05-25 2017-08-29 上海应用技术大学 一种生物柴油的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4225870A1 (de) * 1992-08-05 1994-02-10 Basf Ag Verfahren zur Herstellung von Glycerincarbonat
EP1580255A1 (fr) * 2004-03-26 2005-09-28 Instytut Chemii Przemyslowe im. Prof. Ignacego Moscickiego Biocarburant pour moteur à allumage par compression et méthode de préparation.
WO2007058556A1 (fr) * 2005-11-21 2007-05-24 Instytut Chemii Przemyslowej Nouveau composant biocarburant et procede d’obtention de nouveaux composants biocarburants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4225870A1 (de) * 1992-08-05 1994-02-10 Basf Ag Verfahren zur Herstellung von Glycerincarbonat
EP1580255A1 (fr) * 2004-03-26 2005-09-28 Instytut Chemii Przemyslowe im. Prof. Ignacego Moscickiego Biocarburant pour moteur à allumage par compression et méthode de préparation.
WO2007058556A1 (fr) * 2005-11-21 2007-05-24 Instytut Chemii Przemyslowej Nouveau composant biocarburant et procede d’obtention de nouveaux composants biocarburants

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274886A (zh) * 2013-03-28 2013-09-04 中国石油大学(北京) 一种甘油转化制烯烃的方法及催化剂
CN103274886B (zh) * 2013-03-28 2015-09-02 中国石油大学(北京) 一种甘油转化制烯烃的方法及催化剂
CN107099380A (zh) * 2017-05-25 2017-08-29 上海应用技术大学 一种生物柴油的制备方法

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BRPI0704950A2 (pt) 2009-12-22

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