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WO2004099115A1 - Procede d'extraction et d'esterification catalytique d'acides gras se trouvant dans l'ecume des eaux usees - Google Patents

Procede d'extraction et d'esterification catalytique d'acides gras se trouvant dans l'ecume des eaux usees Download PDF

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Publication number
WO2004099115A1
WO2004099115A1 PCT/BR2004/000058 BR2004000058W WO2004099115A1 WO 2004099115 A1 WO2004099115 A1 WO 2004099115A1 BR 2004000058 W BR2004000058 W BR 2004000058W WO 2004099115 A1 WO2004099115 A1 WO 2004099115A1
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WO
WIPO (PCT)
Prior art keywords
acid
esterification
fatty
fatty acids
scum
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.)
Ceased
Application number
PCT/BR2004/000058
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English (en)
Inventor
Donato Alexandre Gomes Aranda
Marcos Vinicios Marques Fagundes
Luciano Basto Oliveira
Eduardo De Castro Vieira
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.)
Coordenacao dos Programas de Pos Graduacao de Engenharia da UFRJ
Original Assignee
Coordenacao dos Programas de Pos Graduacao de Engenharia da UFRJ
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Publication of WO2004099115A1 publication Critical patent/WO2004099115A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

  • Field of the Invention is related to the esterification process of the fatty acids found in the "sewage scum", namely the surface phase of sewage rich in fatty matter. By dry weight, this oily phase consists of over 80% carboxy acids with 2 - 24 carbon atoms deriving from the decomposition process of different triglycerides and soaps in sewage. Through this invention, these fatty acids are extracted from the scum and esterified with methanol or ethanol through the use of acid catalysts in this process.
  • Background of the Invention Sewage may be defined as a dilute aqueous solution formed by organic and inorganic substances, either dissolved or in suspension.
  • the total fats potential contained in Brazilian sewage may reach some 2.10 6 tons/year, on the basis that each person generates about 250 liters of sewage a day containing 30 - 80 grams of fat.
  • bio- diesel consisting of fatty acid esters, which is an alternative fuel obtained from renewable biological sources such as vegetable oils and animal fats.
  • fatty acid esters which is an alternative fuel obtained from renewable biological sources such as vegetable oils and animal fats.
  • biodiesel is an environmentally clean fuel as it reduces emissions of atmospheric pollutants and particulate matter, in addition to being bio-degradable and atoxic. With physical and chemical properties similar to those of petro-diesel, biodiesel may be used directly in engines with no major mechanical modifications or outlays on maintenance.
  • the pre-esterification of free fatty acids using homogenous acid catalysis has the disadvantage that it is difficult to remove the catalyst residues from the pre- esterified matter.
  • the catalyst is normally removed through washing the mixture with methanol, which is separated from the oil phase through extraction by a solvent that does not blend with the oil, normally glycerin.
  • methanol a solvent that does not blend with the oil, normally glycerin.
  • bio-catalysts enzyme
  • Foglia et al . US patent 5,713,965
  • This invention covers the process of extracting fatty acids from sewage scum, using a catalytic esterification process and presenting the optimum reaction condition ranges in terms of temperature, pressure, space- time and reagent concentrations for the efficient transformation of the fatty acids in the sewage scum into methyl or ethyl esters.
  • This invention also covers the use of solid acid site-based catalysts in the alcohols esterification process for free fatty acids in sewage scum.
  • Figure 1 presents a flow sheet for the bio-diesel production process based on fatty acids extracted from scum. This sequence involves the following items of equipment: 1-pump, 2-centrifuge, 3-press-filter, 4-extractor, 5-esterification reactor, and 6-distillation column to recycle surplus alcohol and solvents.
  • Figures 2 and 4 give the conversion graphs (%) x reaction time ( in) for the esterification reaction of the fatty acids extracted from scum.
  • Table 5 presents some physical and chemical properties of the methyl ester obtained through the procedure described in Example 1. The trials were carried out according to the ASTM standards described in the table .
  • the purposes of this invention include a process for extraction followed by the esterification of free fatty acids in sewage scum and the use of solid acid catalysts in this process.
  • the scum collected at sewage treatment stations has a high water content level.
  • the water dilutes the reagents, slowing the reaction speed.
  • the water is a product of the esterification reaction, with thermodynamic effects on the chemical balance lowering the process yield.
  • Another negative aspect of the water is its interaction with the catalyst acid sites, minimizing this effect. Consequently, as much water as possible should be removed before the reaction.
  • Conventional filtering ⁇ equipment such as a press filter may be used for this purpose.
  • a centrifuge is also recommended to remove the water.
  • apolar solvent either organic or not.
  • organic apolar solvents may be used, such as pentane, hexane or heptane, or even solvents in super-critical conditions such as C0 2 , ethane or propane.
  • polar solvents with the esters is not advisable, due to simultaneous interaction with the remaining water content.
  • an upper phase is attained, containing the fatty matter.
  • the lower phase contains the waste waters.
  • the surplus solvent should be recycled through a flash in a distillation unity. A certain amount of solvent is kept for carrying the solubilized fatty matter to the esterification reactor, boosting the reaction yield.
  • the esterification reaction may occur in the presence of a homogeneous or heterogeneous catalyst.
  • acid catalysts are used for esterifying blends of fatty scum acids. These fatty acids may be esterified with methyl or ethyl alcohol.
  • alcohol/fatty acid mol ratios of 3 to 15 should be used, preferably working between 6 and 12.
  • a catalyst is required that triggers the esterification reaction of the fatty acids at the lowest possible temperatures, in order to ensure that the reaction is economically feasible with no heat breakdown of the reagents.
  • This process involves temperatures in a range of 40°C - 200°C, preferably using a range of 60°C - 170°C.
  • High pressure promotes the reaction, although it is not vital.
  • the reaction temperature range described above means that in some cases the process pressure is necessarily larger than atmospheric pressure.
  • the reactions involve liquid phase components and possibly active sites located inside the solid catalyst particles and consequently subject to mass-transfer constraints.
  • High-speed stirring is required at levels sufficient to minimize this problem. Stirring speeds ranging between 400 and 1,500 RPM are appropriate for this purpose.
  • any catalyst with heat stability and Br ⁇ nsted and/or Lewis acidity under the reaction conditions may be used.
  • the catalysts listed below are used: Sulfated zirconia (sulfur content of 3% - 6%) with a surface area of 30 - 200 m 2 /g, pre-calcined between 300°C and 800°C;
  • Zirconia promoted with tungsten (tungsten level of 5% - 15%) , with a surface area of 70 - 200 m 2 /g, pre-calcined at 300°C - 800"C;
  • the fatty acid esterification process using heterogeneous catalysts may be run on a batch basis, in a continuous reactor, as well as in fixed bed reactors.
  • the spatial time in terms of the fatty acids is 1 - 30 minutes, preferably limited to 3 - 20 minutes.
  • the catalysts When using heterogeneous catalysts, the catalysts are removed after the reaction through simple filtering, or maintained through a fixed bed.
  • neutralization of the medium is required after the reaction. This neutralization produces a salt that should be removed by washing.
  • calcium carbonate and sodium carbonate solutions are used, with the possibility of also using controlled amounts of sodium hydroxide or potassium hydroxide, or even ammonia bubbled directly into the solution.
  • the solvent used for extraction in the reaction medium is recovered, in addition to retrieving surplus alcohol.
  • the sequence depends on the solvent vapor pressures and the alcohols used. Vacuum evaporation is recommended, in order to minimize heat decomposition or parallel reactions.
  • esters formed should be dried through heating (vacuum or not) . Esters with high purity levels may then be obtained through vacuum distillation. This stage may be skipped, depending on the bio-diesel specifications .
  • Figure 1 gives a schematic process flow sheet. The items of equipment listed are: 1-pump, 2-extractor, 3-press filter, 4-flash vessel, 5-reactor, 6-distillation column.
  • Figure 2 presents a chromatogram of the methyl esters obtained through the esterification of fatty acids contained in sewage scum.
  • C ⁇ 6 refers to the palmitic acid ester
  • C ⁇ refers to the heptadecanoic acid ester
  • Ci ⁇ refers to the stearic, oleic, linoleic and linolenic acid esters
  • C n -OH refers to the hydroxy fattyesters.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention a trait à un procédé d'estérification d'acides gras se trouvant dans l'écume des eaux usées, notamment la phase superficielle des eaux usées riche en matière grasse, ces acides gras étant extraits de l'écume et estérifiés par des catalyseurs acides et des réactifs tels que le méthanol ou l'éthanol.
PCT/BR2004/000058 2003-05-06 2004-04-29 Procede d'extraction et d'esterification catalytique d'acides gras se trouvant dans l'ecume des eaux usees Ceased WO2004099115A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0301254-9 2003-05-06
BR0301254A BR0301254B1 (pt) 2003-05-06 2003-05-06 ôprocesso para extração e esterificação catalítica dos ácidos graxos presentes na escuma de esgotoö.

Publications (1)

Publication Number Publication Date
WO2004099115A1 true WO2004099115A1 (fr) 2004-11-18

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PCT/BR2004/000058 Ceased WO2004099115A1 (fr) 2003-05-06 2004-04-29 Procede d'extraction et d'esterification catalytique d'acides gras se trouvant dans l'ecume des eaux usees

Country Status (2)

Country Link
BR (1) BR0301254B1 (fr)
WO (1) WO2004099115A1 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010010118A1 (fr) * 2008-07-22 2010-01-28 Yellow Diesel B.V. Catalyseur de zircone sulfatée, sa production par fusion des précurseurs et son utilisation pour l'estérification d'acides gras avec des alcools
DE102008060902A1 (de) 2008-12-09 2010-06-10 Grace Gmbh & Co. Kg Verfahren zur Herstellung von Biodiesel
US7790044B2 (en) * 2006-04-04 2010-09-07 Nowa Technology, Inc. Method and apparatus for separation of chemical materials from feces
JP2011507695A (ja) * 2007-12-27 2011-03-10 エルジー・ケム・リミテッド ジルコニウム化合物を含むエステル化触媒組成物およびこれを用いたエステル化合物の製造方法
US7915474B2 (en) 2009-04-01 2011-03-29 Earth Renewal Group, Llc Aqueous phase oxidation process
US7951988B2 (en) 2009-04-01 2011-05-31 Earth Renewal Group, Llc Aqueous phase oxidation process
WO2011085461A1 (fr) * 2010-01-18 2011-07-21 Marcos Vinicios Marques Fagundes Procédé pour désémulsification et estérification intégrée d'acides gras et de leurs dérivés au moyen de réactifs résiduels et récupération simultanée d'alcool et élimination d'eau
CN101358138B (zh) * 2008-09-23 2011-08-24 浙江大学 一种生物质油提质的方法
US8115047B2 (en) 2009-04-01 2012-02-14 Earth Renewal Group, Llc Aqueous phase oxidation process
US8168847B2 (en) 2009-04-01 2012-05-01 Earth Renewal Group, Llc Aqueous phase oxidation process
EP2481733A1 (fr) * 2011-01-28 2012-08-01 Süd-Chemie AG Procédé pour la fabrication d'esters de l'acide 2,5-furandicarboxylique
US8481800B2 (en) 2009-04-01 2013-07-09 Earth Renewal Group, Llc Aqueous phase oxidation process
CN103923685A (zh) * 2014-05-09 2014-07-16 北京师范大学 一种利用活性污泥制备生物柴油的方法
CN103936091A (zh) * 2013-12-26 2014-07-23 重庆宜化化工有限公司 一种淡液蒸馏工艺方法
US9611158B2 (en) 2009-04-01 2017-04-04 Earth Renewal Group, Llc Waste treatment process
CN106867566A (zh) * 2017-03-15 2017-06-20 北京师范大学 一种提高剩余污泥制备生物柴油产量的方法
RU2813102C1 (ru) * 2022-12-06 2024-02-06 Общество с ограниченной ответственностью "Центр разработки низкоуглеродных технологий" (ООО "ЦРНТ") Способ получения сложных эфиров карбоновых кислот
WO2024123205A1 (fr) * 2022-12-06 2024-06-13 Общество С Ограниченной Ответственностью "Центр Разработки Низкоуглеродных Технологий" Procédé de production d'esters complexes d'acides carboxyliques

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990008127A1 (fr) * 1989-01-17 1990-07-26 Davy Mckee (London) Limited Procede et appareil
US6399800B1 (en) * 1999-09-22 2002-06-04 The United States Of America As Represented By The Secretary Of Agriculture Process for the production of fatty acid alkyl esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990008127A1 (fr) * 1989-01-17 1990-07-26 Davy Mckee (London) Limited Procede et appareil
US6399800B1 (en) * 1999-09-22 2002-06-04 The United States Of America As Represented By The Secretary Of Agriculture Process for the production of fatty acid alkyl esters

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7790044B2 (en) * 2006-04-04 2010-09-07 Nowa Technology, Inc. Method and apparatus for separation of chemical materials from feces
EP2231327A4 (fr) * 2007-12-27 2011-09-28 Lg Chemical Ltd Composition catalysante comprenant des composés de zirconium destinés à créer une réaction d'estérification, et méthode de préparation de composés d'ester
JP2011507695A (ja) * 2007-12-27 2011-03-10 エルジー・ケム・リミテッド ジルコニウム化合物を含むエステル化触媒組成物およびこれを用いたエステル化合物の製造方法
EP2153893A1 (fr) * 2008-07-22 2010-02-17 Yellow Diesel B.V. Catalysateurs à base d'oxyde de zirconium sulfaté. Procédé de preparation contenant une etape de fusion des precurseurs et utilisation du catalyseur pour l'esterification d'acides gras avec des alcools.
WO2010010118A1 (fr) * 2008-07-22 2010-01-28 Yellow Diesel B.V. Catalyseur de zircone sulfatée, sa production par fusion des précurseurs et son utilisation pour l'estérification d'acides gras avec des alcools
CN101358138B (zh) * 2008-09-23 2011-08-24 浙江大学 一种生物质油提质的方法
DE102008060902A1 (de) 2008-12-09 2010-06-10 Grace Gmbh & Co. Kg Verfahren zur Herstellung von Biodiesel
US7915474B2 (en) 2009-04-01 2011-03-29 Earth Renewal Group, Llc Aqueous phase oxidation process
US9611158B2 (en) 2009-04-01 2017-04-04 Earth Renewal Group, Llc Waste treatment process
US8115047B2 (en) 2009-04-01 2012-02-14 Earth Renewal Group, Llc Aqueous phase oxidation process
US8168847B2 (en) 2009-04-01 2012-05-01 Earth Renewal Group, Llc Aqueous phase oxidation process
US7951988B2 (en) 2009-04-01 2011-05-31 Earth Renewal Group, Llc Aqueous phase oxidation process
US9902632B2 (en) 2009-04-01 2018-02-27 Earth Renewal Group, Llc Waste treatment method
US8481800B2 (en) 2009-04-01 2013-07-09 Earth Renewal Group, Llc Aqueous phase oxidation process
WO2011085461A1 (fr) * 2010-01-18 2011-07-21 Marcos Vinicios Marques Fagundes Procédé pour désémulsification et estérification intégrée d'acides gras et de leurs dérivés au moyen de réactifs résiduels et récupération simultanée d'alcool et élimination d'eau
EP2481733A1 (fr) * 2011-01-28 2012-08-01 Süd-Chemie AG Procédé pour la fabrication d'esters de l'acide 2,5-furandicarboxylique
WO2012101015A1 (fr) * 2011-01-28 2012-08-02 Süd-Chemie AG Procédé de fabrication d'esters de l'acide 2,5-furandicarboxylique
CN103936091A (zh) * 2013-12-26 2014-07-23 重庆宜化化工有限公司 一种淡液蒸馏工艺方法
CN103936091B (zh) * 2013-12-26 2015-09-02 重庆宜化化工有限公司 一种淡液蒸馏工艺方法
CN103923685B (zh) * 2014-05-09 2016-03-16 北京师范大学 一种利用活性污泥制备生物柴油的方法
CN103923685A (zh) * 2014-05-09 2014-07-16 北京师范大学 一种利用活性污泥制备生物柴油的方法
CN106867566A (zh) * 2017-03-15 2017-06-20 北京师范大学 一种提高剩余污泥制备生物柴油产量的方法
RU2813102C1 (ru) * 2022-12-06 2024-02-06 Общество с ограниченной ответственностью "Центр разработки низкоуглеродных технологий" (ООО "ЦРНТ") Способ получения сложных эфиров карбоновых кислот
WO2024123205A1 (fr) * 2022-12-06 2024-06-13 Общество С Ограниченной Ответственностью "Центр Разработки Низкоуглеродных Технологий" Procédé de production d'esters complexes d'acides carboxyliques

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Publication number Publication date
BR0301254A (pt) 2005-10-04
BR0301254B1 (pt) 2012-05-02

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