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US20100163793A1 - Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same - Google Patents

Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same Download PDF

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Publication number
US20100163793A1
US20100163793A1 US12/588,678 US58867809A US2010163793A1 US 20100163793 A1 US20100163793 A1 US 20100163793A1 US 58867809 A US58867809 A US 58867809A US 2010163793 A1 US2010163793 A1 US 2010163793A1
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US
United States
Prior art keywords
solid
heterogeneous catalysts
catalysts
apatite
accordance
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.)
Abandoned
Application number
US12/588,678
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English (en)
Inventor
Marcio de Figueiredo Portilho
Alexander Rangel Bastos
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.)
Petroleo Brasileiro SA Petrobras
Original Assignee
Petroleo Brasileiro SA Petrobras
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 Petroleo Brasileiro SA Petrobras filed Critical Petroleo Brasileiro SA Petrobras
Assigned to PETROLEO BRASILEIRO S.A.- PETROBRAS reassignment PETROLEO BRASILEIRO S.A.- PETROBRAS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BASTOS, ALEXANDER RANGEL, PORTILHO, MARCIO DE FIGUEIREDO
Publication of US20100163793A1 publication Critical patent/US20100163793A1/en
Priority to US14/057,252 priority Critical patent/US8853436B2/en
Abandoned legal-status Critical Current

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Classifications

    • 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
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
    • 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
    • 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

  • This invention belongs to the field of catalysts for the transesterification of triglycerides, for the production of fatty acid glycerin and esters. More specifically, the invention describes solid catalysts for heterogeneous transesterification of triglycerides present in oils and fats and preparatory methods for the production of same.
  • the solid catalysts of this invention are sufficiently magnetic to use in the production of biodiesel from vegetable oils and fats, not only because they work in a similar fashion as state of the art catalysts, but also because of the low cost of the raw materials used in its production.
  • Transesterfication or alcoholization appeared to be a significantly advantageous industrial procedure to make it feasible to obtain fuel from triglycerides, present in vegetable oils and fats. Methanol was used, or alternatively ethanol, in the presence of homogeneous alkaline catalysts to generate long chain esters and glycerin.
  • homogeneous catalysts to generate long chain esters and glycerin.
  • transesterfication using homogeneous catalysts introduces problems. Normally, the catalyst must be removed through complicated separation processes which increase the price of the final products.
  • alkaline catalysts cause saponification of the free fatty acid esters present in oils, which requires the products to be washed with enormous amounts of water and causing a reduction in the ester production.
  • the impurity of the products obtained as well as burning of fuel generates considerable amounts of formaldehyde, acrylaldehyde, the metallic salts of formic acid and carbonates, in addition to pollutants cause damage to pistons and engines.
  • U.S. Pat. No. 5,908,946 describes a process to produce fuel from vegetable or animal oils, using a heterogeneous catalyst to carry out the alcoholization.
  • the catalyst includes a mixture of zinc and aluminum oxides. The process also produces pure glycerin.
  • Patent WO 2005/021697 A1 describes a method to produce glycerin and long chain esters, suitable for use in biodiesel, both having a high level of purity.
  • Transesterification with alcohol is carried out from oils and fats using a heterogeneous catalyst that may include an oxide, an alkaline metal and at least one metal element selected from among groups 4 and 5 of the periodical table of chemical elements, associated with H, Ti, and Nb or Ta.
  • This invention describes preparatory methods using solid catalysts and the formulation of these catalysts for the production of fatty acid esters, glycerin, and specifically, biodiesel through the heterogeneous transesterification reaction of triglycerides present in vegetable oils and fats, such as soy, cotton seed, canola, castor, peanut oils and animal fats.
  • a conversion of 100% is obtained using catalysts prepared using the procedures described in this invention.
  • the purity of the products, such as biodiesel and glycerin, in the composition produced is greater than 96.5%.
  • the catalysts of this invention are economically obtained from cheaper raw materials and lower industrial costs of production, making them more attractive for production on a large scale than the catalysts produced by other methods for the same purpose.
  • This invention describes catalysts for the heterogeneous transesterfication of triglycerides present in vegetable oils and fats.
  • the catalysts consist of:
  • the invention also describes preparatory methods for these catalysts.
  • the invention even describes a composition that includes not less than 98% p/p of fatty acid esters and no more than 4,500 ppm of fatty acids.
  • the purity of the products, such as biodiesel and glycerin, is greater than 96.5%.
  • the catalysts may be used with vegetable oil as well as soy oil, cottonseed oil, canola oil, castor oil, peanut oil, as well as pure or used animal fat.
  • the solid oxide is apatite or a barium oxide.
  • the substrate consists of a solid oxide or a mixture of solid oxides, that confers suitable textural properties to said catalyst and improves its catalytic performance such as for example, an alumina.
  • the apatite catalyst is obtained from the powdered ore of same name, with an enriched phosphorus level, using the traditional treatment for phosphoric acid production.
  • the resulting powder is dried in a kiln at 120° C./16 hr and later heated at 550° C./3 hr.
  • the apatite thus produced has the following elemental composition: Phosphorus, 4.1%; barium, 10.0%; calcium, 6.1%; iron, 9.0%; manganese, 1.3%; aluminum, 11.0%.
  • the barium oxide catalyst is prepared from a mixture containing 80% gamma-aluminum and 20% barium hydroxide octahydrate.
  • the mixture is peptized using the wet point technique with an acetic acid solution of 4% p/p. After that it is dried at 120° C./8 hr and is heated to 550° C./3 hr.
  • the reaction conditions for obtaining biodiesel with the use of these catalysts make use of temperatures lower than 290° C., under self-generated system pressure.
  • the reaction may be carried out using the batch or continuous mode.
  • the catalyst is added to the reagent oil in amounts that fall within the range of 1% p/p and 5% p/p.
  • the heated reaction medium is maintained at the reaction temperature during an interval of time that falls in the range of between 1 and 8 hours. Separation of the catalyst is accomplished by filtration.
  • the alcohol/glycerin mixture is separated from the biodiesel mixture by gravimetric or centrifugal decanting.
  • the biodiesel is washed with water, to remove fine residual catalyst and alcohol particles and then it is dried.
  • transesterification reactions are performed in the reactor in batches of 300 ml, under self-generated system pressure, mechanical mixing at 500 rpm and the oil/alcohol ratio is 1/15 mol/mol and 130 mol/mol, respectively.
  • the product yield is measured by nuclear magnetic carbon 13 resonance (RMN 13 C), the reaction time and the amount of catalyst are shown in each example.
  • Reactions were performed using conventional catalytic solids under the same conditions as the reaction conditions shown in the examples, the yield of which shall be used as a reference for the yield achieved by this invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US12/588,678 2008-12-29 2009-10-23 Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same Abandoned US20100163793A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/057,252 US8853436B2 (en) 2008-12-29 2013-10-18 Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0805625-0A BRPI0805625A2 (pt) 2008-12-29 2008-12-29 catalisadores heterogêneos para a transesterificação de triglicerìdeos e métodos preparatórios dos mesmos
BRPI0805625-0 2008-12-29

Related Child Applications (1)

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US14/057,252 Division US8853436B2 (en) 2008-12-29 2013-10-18 Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same

Publications (1)

Publication Number Publication Date
US20100163793A1 true US20100163793A1 (en) 2010-07-01

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US12/588,678 Abandoned US20100163793A1 (en) 2008-12-29 2009-10-23 Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same
US14/057,252 Active US8853436B2 (en) 2008-12-29 2013-10-18 Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same

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Country Status (4)

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US (2) US20100163793A1 (es)
EP (1) EP2201999A3 (es)
AR (1) AR074236A1 (es)
BR (1) BRPI0805625A2 (es)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140046082A1 (en) * 2008-12-29 2014-02-13 Petroleo Brasileiro S.A.- Petrobras Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same
KR101459334B1 (ko) * 2013-12-04 2014-11-10 희성촉매 주식회사 지방산 알킬 에스테르 제조용 촉매
CN109289828A (zh) * 2018-11-18 2019-02-01 邵阳天堂助剂化工有限公司 一种焙烧态水铝钙石催化合成脂肪酸甲酯的方法

Citations (9)

* Cited by examiner, † Cited by third party
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US5075275A (en) * 1989-07-06 1991-12-24 Mazda Motor Corporation Catalyst for purification of exhaust gases
US5908946A (en) * 1996-08-08 1999-06-01 Institut Francais Du Petrole Process for the production of esters from vegetable oils or animal oils alcohols
US5958829A (en) * 1992-02-14 1999-09-28 Degussa-Huls Aktiengesellschaft Coating dispersion for exhaust gas catalysts
US6350421B1 (en) * 1998-08-24 2002-02-26 Dmc2 Degussa Metals Catalysts Cerdec Ag Nitrogen oxide storage material and nitrogen oxide storing catalyst prepared therefrom
US20020042342A1 (en) * 2000-08-19 2002-04-11 Lothar Mussmann Oxygen storage material based on cerium oxide, a process for its preparation and its use
US20040102655A1 (en) * 2002-11-25 2004-05-27 Shelue Liang Preparation of cyclopentenoes
US20050014237A1 (en) * 2003-07-16 2005-01-20 Inmok Lee Method for producing fats or oils
US20060257982A1 (en) * 2005-05-13 2006-11-16 Archer-Daniels-Midland Company Method for producing fats or oils
WO2007086496A1 (ja) * 2006-01-30 2007-08-02 Showa Denko K.K. α,β-不飽和エーテルの製造方法

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US2634234A (en) * 1949-07-16 1953-04-07 Eastman Kodak Co Production of monoesters of polyhydric alcohols
US3525599A (en) * 1967-10-25 1970-08-25 Continental Oil Co Barium-containing dispersion
US3806454A (en) * 1971-05-12 1974-04-23 Witco Chemical Corp Process for preparing barium-containing dispersion
JP2537239B2 (ja) * 1987-08-28 1996-09-25 エヌ・イーケムキヤツト 株式会社 耐熱性に優れた内燃機関排気ガス浄化用触媒及びその製造方法
AU2004269265B2 (en) 2003-08-29 2009-11-26 Nippon Shokubai Co., Ltd. Method of production of fatty acid alkyl esters and/or glycerine and fatty acid alkyl ester-containing composition
EP1593732A1 (fr) * 2004-05-03 2005-11-09 Institut Français du Pétrole Procede de transesterification d'huiles vegezales ou animales au moyen de catalyseurs heterogenes a base de zinc ou de bismuth de titane et d'aluminium
EP2043972B8 (en) * 2006-07-23 2020-06-10 Iowa State University Research Foundation, Inc. Biodiesel production using composite catalysts
JP2009262010A (ja) * 2008-04-22 2009-11-12 Univ Nihon バイオディーゼル燃料合成用固体塩基触媒およびその製造方法
BRPI0805625A2 (pt) * 2008-12-29 2010-09-14 Petroleo Brasileiro Sa catalisadores heterogêneos para a transesterificação de triglicerìdeos e métodos preparatórios dos mesmos

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5075275A (en) * 1989-07-06 1991-12-24 Mazda Motor Corporation Catalyst for purification of exhaust gases
US5958829A (en) * 1992-02-14 1999-09-28 Degussa-Huls Aktiengesellschaft Coating dispersion for exhaust gas catalysts
US5908946A (en) * 1996-08-08 1999-06-01 Institut Francais Du Petrole Process for the production of esters from vegetable oils or animal oils alcohols
US6350421B1 (en) * 1998-08-24 2002-02-26 Dmc2 Degussa Metals Catalysts Cerdec Ag Nitrogen oxide storage material and nitrogen oxide storing catalyst prepared therefrom
US20020042342A1 (en) * 2000-08-19 2002-04-11 Lothar Mussmann Oxygen storage material based on cerium oxide, a process for its preparation and its use
US20040102655A1 (en) * 2002-11-25 2004-05-27 Shelue Liang Preparation of cyclopentenoes
US20050014237A1 (en) * 2003-07-16 2005-01-20 Inmok Lee Method for producing fats or oils
US20060257982A1 (en) * 2005-05-13 2006-11-16 Archer-Daniels-Midland Company Method for producing fats or oils
WO2007086496A1 (ja) * 2006-01-30 2007-08-02 Showa Denko K.K. α,β-不飽和エーテルの製造方法
US20090227818A1 (en) * 2006-01-30 2009-09-10 Showa Denko K.K. Method for producing a,beta-unsaturated ether
US7728181B2 (en) * 2006-01-30 2010-06-01 Showa Denko K.K. Method for producing α, β-unsaturated ether

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140046082A1 (en) * 2008-12-29 2014-02-13 Petroleo Brasileiro S.A.- Petrobras Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same
US8853436B2 (en) * 2008-12-29 2014-10-07 Petroleo Brasileiro S.A.-Petrobras Heterogeneous catalysts for transesterification of triglycerides and preparation methods of same
KR101459334B1 (ko) * 2013-12-04 2014-11-10 희성촉매 주식회사 지방산 알킬 에스테르 제조용 촉매
CN109289828A (zh) * 2018-11-18 2019-02-01 邵阳天堂助剂化工有限公司 一种焙烧态水铝钙石催化合成脂肪酸甲酯的方法

Also Published As

Publication number Publication date
EP2201999A2 (en) 2010-06-30
BRPI0805625A2 (pt) 2010-09-14
AR074236A1 (es) 2010-12-29
EP2201999A3 (en) 2011-11-16
US20140046082A1 (en) 2014-02-13
US8853436B2 (en) 2014-10-07

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Owner name: PETROLEO BRASILEIRO S.A.- PETROBRAS,BRAZIL

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PORTILHO, MARCIO DE FIGUEIREDO;BASTOS, ALEXANDER RANGEL;REEL/FRAME:023453/0960

Effective date: 20090811

STCB Information on status: application discontinuation

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