WO2010011123A1 - Procédé de production d'un ester d'alkyle - Google Patents

Procédé de production d'un ester d'alkyle Download PDF

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Publication number
WO2010011123A1
WO2010011123A1 PCT/MY2008/000074 MY2008000074W WO2010011123A1 WO 2010011123 A1 WO2010011123 A1 WO 2010011123A1 MY 2008000074 W MY2008000074 W MY 2008000074W WO 2010011123 A1 WO2010011123 A1 WO 2010011123A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
entrainer
fatty acid
free fatty
oil
Prior art date
Application number
PCT/MY2008/000074
Other languages
English (en)
Inventor
Sze Wai Low
Original Assignee
Sze Wai Low
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 Sze Wai Low filed Critical Sze Wai Low
Priority to PCT/MY2008/000074 priority Critical patent/WO2010011123A1/fr
Publication of WO2010011123A1 publication Critical patent/WO2010011123A1/fr

Links

Classifications

    • 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
    • C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • 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

  • Alkyl esters make from natural lipid or vegetable oil, commonly known as biodiese! are now a viable alternative as fuel for diesel engines.
  • the alkyl ester know better as biodiesel are knows to have better properties that petroleum diesel such as reduction of particulate output, hydrocarbon pollutants and improve lubrication of diesel engine when used as a fuel or mixed with petroleum diesel.
  • biodiesel are manufacture from virgin vegetable oils and this is true for almost all the biodiesel plants in the world.
  • the usage of biodiesel was found to have contributed towards increase in the price of vegetable oil by as much as three fold for the past 3 years. This was partly attributed to biodiesel production and it use as an accepted alternative fuel for commercial diesel.
  • the current biodiesel plant uses 1 st generation technologies such as liquid acid and base process. These processes were limited by incomplete esterification of all the free fatty acid in the feedstock oil and hence cannot use lower grade low cost, but high free fatty acid oil for biodiesel production without large economical and environmental problems.
  • the disadvantages include long purification methods, relative long reaction times, contamination and separation difficulties, high energy cost as well as requiring much more methanol to be recovery from the waste stream plus much higher capital cost. This is due to the process sensitivity to even small quantity of water making it expensive to purify aqueous methanol to high level of purity and excessive salt deposition.
  • the final biodiesel product can also be bleached and filtered to acceptable color if required.
  • the final biodiesel product can also be distilled to provide colorless biodiesel.
  • Catalysts can be added to speed up the reaction. Catalysts that could be used are alkali metal oxides and salts such as potassium and sodium hydroxide or it salts such as potassium acetate or tin compound.
  • a Volatile entrainer that is immiscible with water was introduced into the mixture in the proportion of 1-30% of the lipid volume.
  • the entrainer is then feed to optional water absorbent 10 such as molecular sieve and feedback either directs to the reactor 2 or preheats to vapor form, o)
  • the vapor form have the advantage to separate the entrainer vapor from organic portion such as fatty acid that co distill over with the entrainer when the pressure is set low enough, p)
  • This co distilled fatty acid also act as entrainer to drive off liquid water and the fatty acid removal enable very low level of fatty acid remaining in the reactor such as 0.1 to 0.01%
  • low water solubility entrainer such as cyclohexane, propyl acetate, octanol, toluene, hexane and petroleum diesel is preferred.
  • Diesel as a volatile entrainer is especially useful, as it need not be taken out of the final product, thus removing a production step to remove the entrainer.
  • diesel does have relatively higher water content both in emulsion form and in dissolved form. The water in the diesel is reduced by two methods, a) lowering the entrainer temperature by designing a counter flow condenser to get the lowest diesel temperature and using hydrophobic filter to remove suspended colloidal water.
  • Free Fatty acid that distilled over, x) The resultant glycerides are then subject to alkaline catalyzed tranesterification process to form alkyl ester and glycerin as a byproduct, using known process in the art.
  • y) The glycerin from this step is semi-purified by neutralization and decolorized using the normal procedure knows in the art such as acid treatment, distillation and bleaching.
  • the glycerin generated in this second step of the process can be recycle for use in the first step to form glycerides from fatty acid, aa) It is understood that any alcohol can be used in the second step of the process.
  • the reaction scheme particular the first step of the reaction scheme may be performed with a catalyst.
  • Contemplated catalysts include but not limited to organotin compounds (eg dibutyltin oxide), organo titanium compound (e.g. tetrabutly titanate), alkali acetates, earth alkali acetate, lewis acid, alkali carbonate, alkali oxide and combination thereof.
  • the reactor was initially heated to 190 deg C where the mixture starts to evaporate and temperature slowly rises to 270 deg C within 1 hour.
  • the entrainer evaporates and the water of reaction was removed by the entrainer vapor at the same time.
  • the vapor mixture was condensed, and the water forms a lower layer, which was drained.
  • the diesel condensed was send thru a hydrophobic filter to remove the colloid water in suspension and the diesel is then fed back to the reactor thru the bottom of the reactor.
  • the reaction proceed rapidly and reached 99% conversion within 1 hour, measure from the time temp reach 190deg C
  • the sample tested before and after the above from step 1 was found with approx 95% and 1% free fatty acid respectively.
  • the product from step 1 was reacted with alkaline methanol 200 Litres and 6kg of sodium hydroxide under reflux. The product was allowed to settle for 2 hours and the glycerin separated. The resultant methyl ester was washed and dried. The final product contains approx 93% methyl ester and approx 5-7% diesel that have not been evaporated off.
  • the oil is reacted with alkaline methanol 200 ml with 6gm sodium hydroxide for 1 hour in a reflux condition.
  • the reacted products are allowed to settle for 2 hours and glycerin was separated out.
  • the methyl ester formed was washed and dry to form biodiesel of high quality with 0 to 1% propyl acetate still in the product.
  • Most of the trace propyl acetate was removed together with the methanol during distillation to remove the methanol from the alkyl ester.
  • Propyl acetate was an acceptable impurity as it 100% hydrocarbon.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de traitement d'un acide gras libre, provenant de sources d'huile végétale et d'huile animale bon marché, en esters d'alkyle avec les avantages suivants : a) la vitesse de réaction est beaucoup plus grande que celle de l'invention précédente ; réaction complète en 1 à 2 heures. b) Diminution des stocks de sels, de savons et de déchets aqueux ou même une élimination totale des déchets. c) Diminution de l'utilisation d’énergie. Une option ne nécessite pas de vide pour effectuer cette opération et diminue de ce fait les coûts d'entretien ainsi que de fonctionnement. d) Le procédé ne nécessite pas de méthanol au premier stade du procédé et élimine la nécessité d'effectuer une distillation fractionnée avec les coûts d'entretien et de fonctionnement associés. Ces avantages, et d'autres, sont obtenus en convertissant les acides gras végétaux ou animaux exempts de source d'huile en glycérides dans la première étape et en convertissant dans la seconde étape les glycérides créés, conjointement avec l'huile originale, en ester d'alkyle d'acide gras qui est communément appelé biodiesel. L'huile convertie dans la première étape peut être un monoglycéride, un diglycéride ou un triglycéride ou un mélange de ceux-ci. Elle peut être soit de source animale soit de source végétale. L'huile convertie est ensuite mise en réaction avec du méthanol afin de former du biodiesel et de la glycérine par le biais d'un procédé connu dans l'art tel qu'en utilisant un catalyseur alcalin. La présente invention diffère des inventions précédentes par l'utilisation d'un entraîneur destiné à éliminer l'eau de la réaction et permettant ainsi un temps de réaction beaucoup plus rapide. L'invention diffère également des autres en ce que l'huile est préalablement traitée afin d'éliminer l'oxygène dissous de sorte que l'opération peut être effectuée à une température beaucoup plus élevée sans qu'une oxydation ait lieu et dégrade l'huile. Cette étape est facultative si l'huile et ses mélanges de composants ont une teneur en oxygène dissous extrêmement faible et aucun composant organique ou produit dégommé qui se décomposerait à la température de la réaction formant ainsi de la gomme dans le réacteur.
PCT/MY2008/000074 2008-07-22 2008-07-22 Procédé de production d'un ester d'alkyle WO2010011123A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/MY2008/000074 WO2010011123A1 (fr) 2008-07-22 2008-07-22 Procédé de production d'un ester d'alkyle

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/MY2008/000074 WO2010011123A1 (fr) 2008-07-22 2008-07-22 Procédé de production d'un ester d'alkyle

Publications (1)

Publication Number Publication Date
WO2010011123A1 true WO2010011123A1 (fr) 2010-01-28

Family

ID=41570468

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/MY2008/000074 WO2010011123A1 (fr) 2008-07-22 2008-07-22 Procédé de production d'un ester d'alkyle

Country Status (1)

Country Link
WO (1) WO2010011123A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITFI20090092A1 (it) * 2009-05-05 2010-11-06 Silo Srl Processo per la preparazione di oli vegetali esterificati per la produzione di biodiesel e di biocarburante per motori per la produzione di energia elettrica.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004103934A2 (fr) * 2003-05-16 2004-12-02 Stepan Company Procede de fabrication d'esters d'alkyle par pression
US20050075509A1 (en) * 2003-08-12 2005-04-07 Luxem Franz J. Method of making alkyl esters using glycerin
US6878837B2 (en) * 2002-04-11 2005-04-12 Institut Francais Du Petrole Process for producing alkyl esters from a vegetable or animal oil and an aliphatic monoalcohol
US20070260077A1 (en) * 2006-05-05 2007-11-08 Tda Research, Inc. Method of making alkyl esters
US20080051593A1 (en) * 2006-08-24 2008-02-28 William Wesley Berry Process of Making Alkyl Esters of Free Fatty Acids

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6878837B2 (en) * 2002-04-11 2005-04-12 Institut Francais Du Petrole Process for producing alkyl esters from a vegetable or animal oil and an aliphatic monoalcohol
WO2004103934A2 (fr) * 2003-05-16 2004-12-02 Stepan Company Procede de fabrication d'esters d'alkyle par pression
US20050075509A1 (en) * 2003-08-12 2005-04-07 Luxem Franz J. Method of making alkyl esters using glycerin
US20070260077A1 (en) * 2006-05-05 2007-11-08 Tda Research, Inc. Method of making alkyl esters
US20080051593A1 (en) * 2006-08-24 2008-02-28 William Wesley Berry Process of Making Alkyl Esters of Free Fatty Acids

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITFI20090092A1 (it) * 2009-05-05 2010-11-06 Silo Srl Processo per la preparazione di oli vegetali esterificati per la produzione di biodiesel e di biocarburante per motori per la produzione di energia elettrica.

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