WO2010112641A1 - Procédé de production de biocarburants par catalyse hétérogène utilisant un zincate métallique en tant que précurseur de catalyseurs solides - Google Patents

Procédé de production de biocarburants par catalyse hétérogène utilisant un zincate métallique en tant que précurseur de catalyseurs solides Download PDF

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WO2010112641A1
WO2010112641A1 PCT/ES2010/000141 ES2010000141W WO2010112641A1 WO 2010112641 A1 WO2010112641 A1 WO 2010112641A1 ES 2010000141 W ES2010000141 W ES 2010000141W WO 2010112641 A1 WO2010112641 A1 WO 2010112641A1
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Prior art keywords
precursor
transesterification
reaction
carried out
activation
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PCT/ES2010/000141
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English (en)
Spanish (es)
Inventor
Pedro Jésus MAIRELES TORRES
Jose Santamaría González
Ramon Moreno Tost
Juan Miguel Rubio Cabellero
Josefa María MERIDA ROBLES
Enriique Rodriguez Castellon
Antonio Jimenez Lopez
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Universidad De Malaga
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Publication of WO2010112641A1 publication Critical patent/WO2010112641A1/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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B01J35/30—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
    • 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
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • 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
    • 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
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • 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
    • 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 describes the use of solid catalysts, obtained by calcining a ccommuno of an alkaline earth metal or a divalent transition metal, for the production of biofuels, and in particular biodiesel, by transesterification under mild conditions of temperature and atmospheric pressure , of vegetable or animal oils or fats, with low molecular weight alcohols.
  • the biodiesel is formed by a mixture of fatty acid esters obtained by transesterification of triglycerides present in vegetable oils and animal fats with low molecular weight alcohols (mainly methanol or ethanol).
  • biodiesel slightly increases the emissions of nitrogen oxides, although this inconvenience can be mitigated with a specific adjustment of the injection or by the use of specific catalysts for selective removal of NOx after post-combustion, and raises viscosity problems at low temperatures, which can be solved by the use of additives.
  • the transesterification process involves reacting triglycerides, major components of vegetable fats (vegetable oils) and animals (tallow), with methanol or ethanol.
  • Triglycerides are lipids formed by esterification of the three hydroxyl groups of a glycerin molecule with three fatty acid molecules saturated or unsaturated.
  • the transesterification process results in the generation of fatty acid ethyl esters (FAEE, Fatty Acid Ethyl Ester in English) or fatty acid methyl esters (FAME, Fatty Acid Methyl Ester in English), respectively.
  • FEE Fatty Acid Ethyl Ester in English
  • FAME Fatty Acid Methyl Ester in English
  • the overall reaction between one mole of triglyceride and three of methanol leads to one mole of glycerin and three moles of FAME. Said reaction can be carried out both in the absence and in the presence of catalyst. In any case, the formation of DMARD is normally favored by using an excess amount of alcohol with respect to the stoichiometric ratio.
  • the reaction between triglycerides and methanol, which are immiscible, is accelerated by strong agitation, as it facilitates contact between these two phases.
  • the transesterification reaction can be carried out in the absence of catalyst and stirring, using methanol under supercritical conditions (temperatures above 239.5 ° C and pressures above 81 bar; US6187939, US6288251).
  • these drastic reaction conditions involve the use of specific, high-cost equipment, which greatly limits their use for the treatment of low-quality cheap fats (high acidity and high water content).
  • the use of catalysts is a widespread practice, so that the speed of reaction is sufficiently high and high yields in biodiesel are obtained quickly, distinguishing homogeneous and heterogeneous catalytic processes, as well as solid and liquid catalysts.
  • the catalyst used in this homogeneous process cannot be reused, since it is lost in the neutralization and washing stages.
  • the use of a solid catalyst, in a heterogeneous catalytic process reduces the problems associated with homogeneous catalysis, since the solid catalyst can be separated from the reaction medium by simple physical procedures (filtration and / or centrifugation).
  • solid catalysts that have been proposed for triglyceride transesterification reactions, which can be classified as acidic, basic and enzymatic.
  • active acid catalysts are mesoporous silicas functionalized with sulfonic groups (US7122688), carbons derived from polysaccharides functionalized with sulphonic groups [Green Chem. 9 (2007) 434] and vanadium pentoxide (EP2000522), although the latter catalyst is active at 225 0 C and pressures between 35 and 60 Kg / cm 2 .
  • IFP Iron Oxide Powder
  • a mixture of zinc and calcium oxides prepared by precipitation of the corresponding nitrates and subsequent calcination at 600-900 0 C has also been shown to be active in the transesterification of palm kernel oil with methanol, but to obtain higher FAME contents than 94% after 1 hour of reaction at 60 0 C, require the use of 10% by weight of activated catalyst at 700 0 C and a methanokaceite molar ratio of 30: 1 [Appl. Catal. A: Gen. 341 (2008) 77-85].
  • Other metal oxides that have also shown their usefulness as solid catalysts are those based on mixed oxides of V and P [Appl. Catal. A: Gen. 320 (2007) 1] and Fe-Zn [Appl. Catal. A: Gen. 314 (2006) 148].
  • lipases as biocatalysts (enzymatic catalysts) for the transesterification of triglycerides with alcohols (US7473791) has been proposed.
  • the solid catalyst must be able to be reused and eliminate the homogeneous contribution to the catalytic process of transesterification of triglycerides with low molecular weight alcohols, associated with the existence of solubilized basic species in the reaction medium.
  • the invention object of the present patent application implies, in addition to the advantages already mentioned in relation to heterogeneous catalysis compared to homogeneous processes, a series of technical advantages that provide a solution to technical problems not solved by the alternatives that constitute the state of the technique: 1 - Simplicity, reproducibility and easy escalation of the synthesis. '-
  • the precursor of the active catalyst is stable in air.
  • the decomposition or activation temperature of the catalyst is lower than that of other basic solid catalysts.
  • the present invention proposes a heterogeneous method of obtaining biofuels, particularly biodiesel, by catalytic transesterification using a metallic ccommune, particularly an alkaline earth metal or a divalent transition metal, as a precursor to active solid catalysts.
  • the thermal activation of the metallic cyero used as a precursor can be carried out in a wide range of temperatures.
  • the amount of precursor that can be used, and consequently of the resulting catalyst, so that the process is efficient, is also variable.
  • the oils or fats that can be used as a substrate are also diverse, as well as their degree of acidity or their water content. Acceptable reaction conditions are also variable without the process being efficient.
  • the nature of the precursor, the resulting catalyst, and the process conditions allow catalyst recycling and reuse of the precursor.
  • Figure 1 X-ray diffractograms obtained after treating calcium cyere dihydrate at different temperatures. From top to bottom: room temperature, from 100 to 800 0 C at intervals of 100 0 C, and after cooling to room temperature.
  • biodiesel is defined as a mixture of esters of low molecular weight alcohols, preferably methanol or ethanol, with fatty acids.
  • the preferred embodiment of the present invention involves the use of calcium ccommune dihydrate as a precursor of the active solid catalyst.
  • the kinetics of the transesterification process is enhanced by the use of a 4% precursor weight, 12: 1 methanol radical oil ratios and 1000 rpm stirring speed, reaching 95% FAME yields after 45 minutes of reaction.
  • the catalysts obtained by thermal activation of calcium c institutionse dihydrate are particularly active in the transesterification of sunflower and soybean oil with methanol, causing the formation of methyl esters of fatty acids present in these oils (FAME).
  • FAME methyl esters of fatty acids present in these oils
  • Calcium c Marie dihydrate is stable in air against water and carbon dioxide;
  • the catalysts obtained can be recycled, since calcium and zinc oxides are the raw materials for the synthesis of calcium ccommune dihydrate; the catalyst obtained by activation at 400 0 C can be used for at least three catalytic cycles an hour, with yields FAME over 85% when 4% is used in weight zincate dihydrate calcium molar ratio metanohaceite 12: 1 .
  • a series of non-limiting examples are described below, which show the flexibility and advantages of the present invention, and especially the use of this precursor for obtaining an active catalyst in the transesterification of vegetable oils with methanol, for the production of biodiesel.
  • EXAMPLE Ij Reaction of catalytic transesterification of triglycerides to obtain biodiesel with catalysts obtained by heat treatment of calcium cyere dihydrate, with percentages by weight between 1 and 4% of precursor.
  • the basic heterogeneous transesterification reaction of triglycerides contained in sunflower oil begins with a catalyst activation stage.
  • the previously weighed catalyst is activated in an inert atmosphere of helium (other gases can be used, although avoiding the use of air, since the carbon dioxide present in it could react with the catalyst at high temperature), in a tubular furnace (they can used alternative devices) at the temperature of 400 0 C, using a heating rate of 20 ° C / min, and remaining one hour (shorter times result in less active catalysts) at the temperature of 400 0 C.
  • the thermal-differential and thermogravimetric analysis of calcium c institutions reflects, between room temperature and 1000 0 C, a total weight loss of 26.3%, associated with the elimination of hydroxyl groups (dehydroxylation process) and hydration water (dehydration process ). Thus a load of 4% by weight of precursor corresponds to approximately 3% by weight of catalyst.
  • the calcium precursor and the catalyst obtained after thermal activation at 400 0 C is determined by atomic absorption technique (ICP-AA). The values found were 19.9 and 25.1% CaO for the precursor, before and after activation, which are very close to the respective theoretical values of 18.2 and 25.6%. Chemical analysis indicates that calcium cuouse dihydrate has no potassium in its chemical composition.
  • the zincate dihydrate calcium is transformed into a mixture of zinc oxide and calcium oxide , as confirmed by the X-ray diffraction data.
  • One of the most relevant aspects of the catalyst obtained at 400 0 C is its high specific surface area (76.7 m ⁇ g "1 ) and pore volume (0.144 crn ⁇ g " 1 ).
  • the pore size distribution is relatively narrow, centered around 4.3 nm, which allows triglyceride molecules to access the catalyst's basic sites.
  • the materials used in the transesterification reaction are basically: sunflower oil, methanol and catalyst.
  • the reaction is carried out in a discontinuous reactor of complete mixing under N 2 atmosphere, with reflux, magnetic stirring and at the temperature of 60 0 C. This temperature is achieved by a silicone bath heated by a heating plate.
  • the complete mixing batch reactor has three mouths and a gas inlet.
  • the central mouth is connected to a cooling system, to keep the volume of methanol constant inside the reactor.
  • One of the mouths located at the ends is used in the aliquot extraction process for later analysis, while on the other the reactor temperature is controlled by a thermometer.
  • the system is in continuous agitation, to obtain optimum contact between phases, by means of a magnetic stirrer whose speed range is from 100 rpm to 1000 rpm.
  • Sunflower oil 25 g
  • the catalyst is introduced into the reactor without cutting off the helium current to prevent the entry of air and therefore of CO 2 .
  • the methanol (16.5 ce) is poured and the reactor is sealed. Magnetic stirring allows the contact of the two immiscible phases (methanol and oil).
  • the assembly of the complete mixing batch reactor is confined within a gas extraction hood, to prevent possible problems caused by methanol leaks in the assembly.
  • the separation process consists of a stage of extraction, filtration, neutralization and decantation.
  • the extraction step is to obtain a sample aliquot (1.5 ml) of the reaction medium, by means of a syringe.
  • the filtration step is then carried out by means of a microfilter, in order to remove the catalyst particles present.
  • the neutralization step is based on the addition of 1 ml of the 0.1 M solution of HCl, to neutralize the remaining basic catalyst residues. Subsequently we reach the stage of decantation, adding 1.5 ml of dichloromethane and vigorous stirring to the sample. Two phases are obtained: an organic phase (ester phase) and an aqueous phase (alcoholic phase).
  • the ester phase also contains dichloromethane and traces of methanol that must be removed before analyzing the biodiesel phase. For this, the solution is maintained for 5 hours in a sand bath at a temperature of 90 0 C. The samples were analyzed by high performance liquid chromatography.
  • HPLC HPLC with a JASCO device equipped with a quaternary gradient pump (PU-2089), an ultraviolet detector (MD-2015), an automatic injector (AS-2055) and a column oven (co-2065).
  • the column used was PHENOMENEX LUNA Cl 8 (250 mm x 4.6 mm x 5 ⁇ m).
  • the solvents were microfiltered and degassed with helium.
  • the injection volumes in the column were 15 ⁇ L, with a constant column temperature equal to 40 0 C.
  • the purified samples were previously prepared for analysis in the HPLC, dissolving 80 ⁇ l of the sample in 10 ml of the isopropanol / hexane mixture (5: 4 v / v).
  • the triglyceride areas of the unreacted oil have been recorded, as have the areas of methyl esters (biodiesel or FAME) and mono-, diglycerides and free fatty acids.
  • EXAMPLE 2 Reaction of catalytic transesterification of triglycerides to obtain biodiesel with catalysts obtained by activating calcium ccommune dihydrate at different temperatures.
  • This example demonstrates the influence of the activation temperature of calcium cyere dihydrate on the catalytic behavior in the transesterification of sunflower oil with methanol. Temperatures of 350, 400, 500 and 800 0 C were used, a weight percentage of calcium ccommune dihydrate of 1%, methanol: oil molar ratios of 12: 1 and a reaction temperature of 60 0 C. After thermal activation at 350 0 C, the catalyst obtained needs a reaction time of 3 hours to reach a yield of 89% ( Figure 3). However, with temperatures at or above 400 0 C, the values obtained are higher over the entire range of reaction times studied, and two hours yields FAME are over 85%.
  • EXAMPLE 3 Reaction of catalytic transesterification of triglycerides to obtain biodiesel with a catalyst obtained after calcining calcium ccommune dihydrate at 400 0 C. in different reuse cycles.
  • the catalyst obtained after calcining the calcium zincate dihydrate in inert atmosphere at 400 0 C was used in several cycles of reuse.
  • the solid catalyst is separated from the solution (reagents and reaction products) by centrifugation at 7000 rpm for 7 minutes. Then the catalyst obtained in the centrifugation process is reused, but without performing the previous activation stage.
  • the results obtained are shown in Figure 5, where it is observed that this catalyst can be used for at least three 1-hour catalytic cycles, with FAME yields greater than 86%.
  • the catalyst obtained after activating calcium zincate dihydrate 400 0 C has been used to study the influence of the acidity of the oil on the performance of FAME.
  • different amounts of oleic acid C 18 H 34 O 2

Abstract

La présente invention porte sur l'utilisation de catalyseurs solides, obtenus par calcination d'un zincate d'un métal alcalino-terreux ou d'un métal de transition bivalent, pour la production de biocarburants (biodiesel) par transestérification dans des conditions modérées de température et de pression atmosphérique, d'huiles ou de graisses d'origine végétale ou animale, avec des alcools de faible poids moléculaire. Les avantages, outre ceux propres à la catalyse hétérogène sont: - la simplicité, la reproductibilité et l'échelonnement facile de la synthèse; - le précurseur du catalyseur actif est stable dans l'air; - la température de décomposition ou d'activation du catalyseur est inférieure à celle d'autres catalyseurs solides basiques. La cinétique de la réaction est similaire à la cinétique décrite dans des réactions de catalyse homogène et significativement plus rapide que dans le cas d'autres catalyseurs solides.
PCT/ES2010/000141 2009-04-01 2010-03-27 Procédé de production de biocarburants par catalyse hétérogène utilisant un zincate métallique en tant que précurseur de catalyseurs solides WO2010112641A1 (fr)

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ES200900932A ES2345866B2 (es) 2009-04-01 2009-04-01 Procedimiento de produccion de biocarburantes mediante catalisis heterogenea empleando un cincato metalico como precursor de catalizadores solidos.
ESP200900932 2009-04-01

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012111023A1 (fr) 2011-02-14 2012-08-23 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) Procédé amélioré pour la production d'esters alkyliques d'acide gras (biogazole) à partir d'huiles triglycéridiques au moyen de catalyseurs basiques solides respectueux de l'environnement
WO2016156749A1 (fr) 2015-04-03 2016-10-06 Easyl Procédé de fabrication de cristaux de zincate de calcium, ainsi que ses utilisations

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CHAWALIT NGAMCHARUSSRIVICHAI ET AL.: "Ca and Zn mixed oxide as a heterogeneous base catalyst for transesterification of palm kernthe oil", APPLIED CATALYSIS A: GENERAL, vol. 341, 10 March 2008 (2008-03-10), pages 77 - 85 *
LOPEZ GRANADOS, M. ET AL.: "Biodiesthe from sunflower oil by using activated calcium oxide", APPLIED CATALYSIS B: ENVIRONMENTAL, vol. 73, 9 January 2007 (2007-01-09), pages 317 - 326 *
MARTIN ALONSO, D. ET AL.: "Biodiesthe preparation using Li/CaO catalysts: Activation process and homogeneous contribution", CATALYSIS TODAY, vol. 143, 5 November 2008 (2008-11-05), pages 167 - 171 *
MASATO KOUZU ET AL.: "Calcium dioxide as a solid base catalyst for transesterification of soybean oil and its application to biodiesthe production", FUEL, vol. 87, 20 November 2007 (2007-11-20), pages 2798 - 2806 *
MASATO KOUZU ET AL.: "Heterogeneous catalysis of calcium oxide used for transesterification of soybean oil with refluxing methanol", APPLIED CATALYSIS A: GENERAL, vol. 335, 9 December 2008 (2008-12-09), pages 94 - 99 *
ZHENQIANG YANG ET AL.: "Soybean oil transesterification osee zinc oxide modified with alkali earth metals", FUTHE PROCESSING TECHNOLOGY, vol. 88, 7 May 2007 (2007-05-07), pages 631 - 638 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012111023A1 (fr) 2011-02-14 2012-08-23 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) Procédé amélioré pour la production d'esters alkyliques d'acide gras (biogazole) à partir d'huiles triglycéridiques au moyen de catalyseurs basiques solides respectueux de l'environnement
US9029583B2 (en) 2011-02-14 2015-05-12 Council Of Scientific & Industrial Research Process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
WO2016156749A1 (fr) 2015-04-03 2016-10-06 Easyl Procédé de fabrication de cristaux de zincate de calcium, ainsi que ses utilisations
US10472248B2 (en) 2015-04-03 2019-11-12 Easyl Method for manufacturing calcium zincate crystals, and the uses thereof

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