WO2007062825A1 - Procede de production d'esters a partir d'huiles vegetales ou de graisses animales, utilisant des catalyseurs a base de composes de vanadium - Google Patents

Procede de production d'esters a partir d'huiles vegetales ou de graisses animales, utilisant des catalyseurs a base de composes de vanadium Download PDF

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Publication number
WO2007062825A1
WO2007062825A1 PCT/EP2006/011456 EP2006011456W WO2007062825A1 WO 2007062825 A1 WO2007062825 A1 WO 2007062825A1 EP 2006011456 W EP2006011456 W EP 2006011456W WO 2007062825 A1 WO2007062825 A1 WO 2007062825A1
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WIPO (PCT)
Prior art keywords
catalyst
reaction
vanadyl phosphate
vegetable oils
glycerin
Prior art date
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PCT/EP2006/011456
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English (en)
Inventor
Elio Santacesaria
Giuseppe Minutillo
Martino Di Serio
Pasquale Patrono
Fulvia Pinzari
Marianna Ledda
Riccardo Tesser
Dante Siano
Mario Nastasi
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Aser S.R.L.
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Publication of WO2007062825A1 publication Critical patent/WO2007062825A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • 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 relates to a method for producing esters from vegetable oils and animal fats, particularly for producing biodiesel, which uses homogeneous, heterogeneous, supported or unsupported catalysts based on vanadium compounds to produce esters by reaction between vegetable oils or animal fats and aliphatic alcohols.
  • Biodiesel used as fuel in diesel engines, is constituted by a mixture of esters of fatty acids obtained by transesterification reaction of vegetable oils and animal fats with methanol or ethanol and subsequent separation from glycerin.
  • the transesterification reaction for producing biodiesel is performed generally by using as catalysts bases of alkaline metals such as for example
  • Barium hydroxide dissolves, producing an essentially homogeneous catalyst, while calcium oxide produces suspensions [3]. Suspensions of CaO make it difficult to separate the ester and glycerin phases.
  • heterogeneous catalysts constituted by vanadyl phosphate dihydrate are active in partial oxidation reactions of hydrocarbons [8, 9]. Vanadyl phosphates substituted with an M 3+ cation and supported on titania and silica have been tested in the partial oxidation reaction of propane [10]. These catalysts, in addition to having substantial redox properties, also have interesting Bronsted and Lewis acid properties.
  • the aim of the present invention is to provide a method which allows to produce biodiesel at lower costs than known methods.
  • An object of the present invention is to provide a method which has additional economical advantages, allowing to produce the byproduct of biodiesel, glycerin, with a higher degree of purity and therefore with a higher market price.
  • Another object of the present invention is to provide a method in which the formation of surfactant species in solution, which slow the step for separation of glycerin and biodiesel by facilitating the formation of emulsions, is limited, avoiding the need to neutralize the products and further avoiding the need for an operation for separating the glycerin from the residues of the catalyst.
  • An additional object of the present invention is to provide a method which can be performed with good yields even in the presence of a high concentration of free fatty acids (>1%).
  • Catalysts constituted by supported or unsupported vanadyl phosphate dihydrate (VOP4-2H 2 O) or by a mixed solid having the general formula
  • the method according to the present invention comprises in particular, among its stages, the stage of mixing vegetable oils or animal fats with an aliphatic alcohol, placing the mixture in contact with the catalyst, and then heating to the reaction temperature.
  • the inventors of the present invention have found catalysts which comprise vanadyl phosphate dihydrate
  • the catalyst used in the method according to the present invention may be unsupported or supported, for example supported on titania, silica or alumina.
  • the reaction stage of the method according to the present invention comprises the steps of:
  • the alcohol used can be for example an aliphatic monoalcohol, in particular an aliphatic monoalcohol containing 1 to 5 atoms of carbon, for example methanol or ethanol.
  • the method according to the present invention can be performed at a temperature which is suitable for the reaction, for example at a temperature from 100 to 250 0 C, in particular at a temperature around 180 0 C.
  • the alcohol/vegetable oil or animal fat weight ratio used in the method according to the present invention ranges for example from 0.5 to 5. Moreover, in one embodiment of the method according to the present invention, the reaction occurs in the presence of free fatty acids, even in high concentrations, for example higher than 1%.
  • the reaction can occur discontinuously or continuously.
  • the heterogeneous catalysts can be separated by filtration, the unreacted aliphatic alcohol can be separated by distillation, and the glycerin phase can be separated by decantation from the ester phase.
  • the method according to the present invention can also comprise an additional stage for transesterification of the unreacted glycerides which are present in the ester phase.
  • the reaction can be performed discontinuously or in continuous agitated or fixed-bed reactors.
  • the catalysts used in the method according to the present invention are characterized by the use of VOPO 4 as a precursor.
  • the method according to the present invention allows a reduction in cost and allows to work in continuous plants.
  • the following Examples are suitable for illustrating the invention and must not be considered as limiting its scope. All the reagents used were supplied by FLUKA, except for the soybean oil, supplied by Casa Olearia Italiana S.p.A. (Monopoli, Italy).
  • the method according to the invention consists in mixing vegetable oils or animal fats with an aliphatic alcohol, preferably methanol. The reaction mixture is then heated to the reaction temperature and placed in contact with the catalyst.
  • the catalyst constituted by vanadyl phosphate dihydrate, having the formula VOPO 4 -2H 2 O, was prepared by following the method described by Ladwig et al. [11], by refluxing for 16 h a suspension Of V 2 O 5 in diluted phosphoric acid.
  • Example 2 Preparation of catalysts of supported VOPO 4 (here referenced as VOPZTiO 2 , VOPZSiO 2 , VOPZAl 2 O 3 ).
  • the heterogeneous catalysts of supported VOPO 4 were prepared by anchoring the vanadyl phosphate dihydrate on supports having a high specific area: TiO 2 anatase (Eurotitania, specific area 125 m 2 g '1 ), SiO 2 (Sigma, specific area 200 m 2 g 1 ), or ⁇ -Al 2 O 3 (CK-300 Akzo, specific area 190 m 2 g "1 ) by means of the wet impregnation method.
  • the anchoring reaction was performed in a water medium.
  • Example 3 Preparation of catalysts constituted by M 3+ monosubstituted compounds of vanadyl phosphate having the general formula [M(H 2 O)J X VOL X POWH 2 O (here referenced as AlVOP, GaVOP, FeVOP, CrVOP).
  • the M 3+ monosubstituted compounds of vanadyl phosphate having the general formula [M(H 2 O)] x VOi -x PO 4 *2H 2 O, where M is a trivalent cation such as Al, Ga, Fe and Cr and x 0.18-0.25, were prepared by adding to the suspension of V 2 O 5 in phosphoric acid in countercurrent the appropriate amount of trivalent metallic salt as indicated in detail in the references [15-18]. The characteristics of the resulting solids are given in table 2.
  • Example 4 Tests for transesterification of oil without catalyst.
  • the reactor was placed in a forced ventilation oven and subjected to the following temperature program: 14 minutes at 5O 0 C, heating at
  • Example 5 Tests for transesterification of acid oil without catalyst.
  • Example 6 Tests for transesterification of oil with vanadyl phosphate dihydrate catalyst (VOPO 4 2H 2 O) (in the absence or presence of free fatty acids).
  • VOPO 4 2H 2 O vanadyl phosphate dihydrate catalyst
  • the test in the absence of free acidity was performed by loading a small steel reactor with 2 g of soybean oil, 0.9 g of methanol, and 0.1 g of catalyst.
  • the test in the presence of free acidity was performed by loading a small steel reactor with 2 g of soybean oil acidified with oleic acid (acid oil 10% by weight), 0.9 g of methanol, and 0.1 g of catalyst.
  • the catalyst was kept at 500 0 C for 2 hours before use.
  • the reactors were placed in a forced ventilation oven and subjected to the following temperature program: 14 minutes at 50 0 C, heating at 20°C/min up to 180 0 C; the reactors were kept at this temperature for 60 minutes. The reactors were then cooled rapidly to ambient temperature.
  • Example 7 Tests for trans esterification of oil with heterogeneous catalysts of VOPO 4 , supported (here referenced as VOPZTiO 2 , VOPZSiO 2 , VOPZAl 2 O 3 ).
  • the tests were carried out by loading small steel reactors with 2 g of soybean oil, 0.9 g of methanol, and 0.1 g of catalyst.
  • the catalysts were kept at 500 0 C for 2 hours before use.
  • the reactors were placed in a forced ventilation oven and subjected to the following temperature program: 14 minutes at 50 0 C, heating at 20°C/min to 180 0 C; the reactors were kept at this temperature for 60 minutes. The reactors were then cooled rapidly to ambient temperature.
  • Example 8 Tests for transesterification of oil with heterogeneous catalysts constituted by Ad 3+ monosubstituted compounds of vanadyl phosphate having the general formula [M(H 2 O)] x VOi. x PO 4 *2H 2 ⁇ (here designated as
  • AlVOP, GaVOP, FeVOP, CrVOP AlVOP, AlVOP, GaVOP, FeVOP, CrVOP.
  • the catalytic activity of the heterogeneous catalysts listed in Table 2 was verified. The tests were carried out by loading small steel reactors with 2 g of soybean oil, 0.9 g of methanol and 0.1 g of catalyst.
  • the catalysts were kept at 500 0 C for 2 hours.
  • the reactors were placed in a forced ventilation oven and subjected to the following temperature program: 14 minutes at 50 0 C 5 heating at 20°C/min to 180 0 C; the reactors were kept at this temperature for 60 minutes. The reactors were then cooled rapidly to ambient temperature.
  • the AlVOP solid was placed in contact 1, 2 times with methanol at
  • Tests in the presence of free acidity were carried out by loading a small steel reactor with 2 g of soybean oil acidified with oleic acid (acid oil 10.5% by weight), 0.9 g of methanol, 0.1 g of catalyst.
  • the catalyst was kept at 500 0 C for 2 hours before use.
  • the reactors were placed in a forced ventilation oven and subjected to the following temperature program: 14 minutes at 50 0 C, heating at 20°C/min up to 180 0 C; the reactors were kept at this temperature for 60 minutes. The reactors were then cooled rapidly to ambient temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention porte sur un procédé de production d'esters d'acides gras et de glycérine comportant les étapes suivantes: réaction d'huiles végétales et/ou de graisses animales avec de l'alcool aliphatique en présence d'un catalyseur supporté ou non, de vanadyl phosphate dihydrate, ou de composés M3+ monosubstitués de vanadyl phosphate, de formule générale [M(H2O)]xVO1-xPO4*2H2O dans laquelle: M est un cation trivalent tel que Al, Ga, Fe et Cr, et x = 0.18-0.25, pour obtenir des esters d'acides gras et de glycérine; séparation de l'alcool n'ayant pas réagi; et séparation des esters d'acides gras de la glycérine.
PCT/EP2006/011456 2005-12-01 2006-11-29 Procede de production d'esters a partir d'huiles vegetales ou de graisses animales, utilisant des catalyseurs a base de composes de vanadium WO2007062825A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT002303A ITMI20052303A1 (it) 2005-12-01 2005-12-01 Processo per la produzione di esteri da oli vegetali o grassi animali con l'impiego di catalizzatori a base di composti di vanadio
ITMI2005A002303 2005-12-01

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2000522A1 (fr) * 2007-05-30 2008-12-10 Petroleo Brasileiro S.A. Petrobras Procédé pour la production de biodiesel à partir d'huiles végétales et de matières grasses, et hétérogènes
WO2008113730A3 (fr) * 2007-03-16 2008-12-24 Basf Se Pyrophosphate de vanadyle polynaire
WO2008113728A3 (fr) * 2007-03-16 2008-12-24 Basf Se Phosphate polynaire d'oxyde métallique
WO2008113729A3 (fr) * 2007-03-16 2008-12-24 Basf Se Phosphate polynaire d'oxyde de vanadium et de métal
WO2008113731A3 (fr) * 2007-03-16 2009-01-15 Basf Se Phosphate polynaire d'oxyde métallique
WO2009007234A1 (fr) * 2007-07-09 2009-01-15 Aser S.R.L. Nouveau procédé de fabrication d'esters à partir d'huiles végétales et/ou de graisses animales à l'aide de catalyseurs hétérogènes, en particulier en présence d'acidité libre et d'eau
WO2012088546A1 (fr) * 2010-12-24 2012-06-28 Sapphire Energy, Inc. Production de produits aromatiques à partir de ressources renouvelables

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005021697A1 (fr) * 2003-08-29 2005-03-10 Nippon Shokubai Co., Ltd. Procede de production d'alkyl esters d'acide gras et/ou de glycerine et composition renfermant lesdits esters

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005021697A1 (fr) * 2003-08-29 2005-03-10 Nippon Shokubai Co., Ltd. Procede de production d'alkyl esters d'acide gras et/ou de glycerine et composition renfermant lesdits esters

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARENGO S ET AL: "Propane partial oxidation over M<3+>-substituted vanadyl phosphates dispersed on titania and silica", APPLIED CATALYSIS A: GENERAL, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 230, no. 1-2, 30 April 2002 (2002-04-30), pages 219 - 231, XP004347108, ISSN: 0926-860X *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008113730A3 (fr) * 2007-03-16 2008-12-24 Basf Se Pyrophosphate de vanadyle polynaire
WO2008113728A3 (fr) * 2007-03-16 2008-12-24 Basf Se Phosphate polynaire d'oxyde métallique
WO2008113729A3 (fr) * 2007-03-16 2008-12-24 Basf Se Phosphate polynaire d'oxyde de vanadium et de métal
WO2008113731A3 (fr) * 2007-03-16 2009-01-15 Basf Se Phosphate polynaire d'oxyde métallique
EP2000522A1 (fr) * 2007-05-30 2008-12-10 Petroleo Brasileiro S.A. Petrobras Procédé pour la production de biodiesel à partir d'huiles végétales et de matières grasses, et hétérogènes
WO2009007234A1 (fr) * 2007-07-09 2009-01-15 Aser S.R.L. Nouveau procédé de fabrication d'esters à partir d'huiles végétales et/ou de graisses animales à l'aide de catalyseurs hétérogènes, en particulier en présence d'acidité libre et d'eau
WO2012088546A1 (fr) * 2010-12-24 2012-06-28 Sapphire Energy, Inc. Production de produits aromatiques à partir de ressources renouvelables
CN103384714A (zh) * 2010-12-24 2013-11-06 蓝宝石能源公司 由可再生资源制备芳族化合物

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