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WO2007026032A1 - Reacteur chimique permettant de realiser l'alcoolyse supercritique de tout type de graisses et d'huiles avec differents types d'alcools - Google Patents

Reacteur chimique permettant de realiser l'alcoolyse supercritique de tout type de graisses et d'huiles avec differents types d'alcools Download PDF

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Publication number
WO2007026032A1
WO2007026032A1 PCT/ES2005/070126 ES2005070126W WO2007026032A1 WO 2007026032 A1 WO2007026032 A1 WO 2007026032A1 ES 2005070126 W ES2005070126 W ES 2005070126W WO 2007026032 A1 WO2007026032 A1 WO 2007026032A1
Authority
WO
WIPO (PCT)
Prior art keywords
oils
fats
types
alcohols
reactor
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/ES2005/070126
Other languages
English (en)
Spanish (es)
Inventor
Mauro Ariel Knudsen
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.)
Integral Bioenergies Systems SL
Original Assignee
Integral Bioenergies Systems SL
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 Integral Bioenergies Systems SL filed Critical Integral Bioenergies Systems SL
Priority to PCT/ES2005/070126 priority Critical patent/WO2007026032A1/fr
Publication of WO2007026032A1 publication Critical patent/WO2007026032A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
    • 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
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/008—Processes carried out under supercritical conditions
    • 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
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/02—Feed or outlet devices therefor
    • 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
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • B01J3/042—Pressure vessels, e.g. autoclaves in the form of a tube
    • 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
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2219/00108—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/0013—Controlling the temperature by direct heating or cooling by condensation of reactants
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00132—Controlling the temperature using electric heating or cooling elements
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00132—Controlling the temperature using electric heating or cooling elements
    • B01J2219/00135—Electric resistance heaters
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • B01J2219/00777—Baffles attached to the reactor wall horizontal
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the present invention consists of a chemical reactor in which the alcoholysis of all types of oils and fats is produced in an efficient way, and different types of alcohols can be used for this.
  • the object of the present invention is a reactor suitable for the physical and chemical transformation of all types of oils and fats in esters, in which light alcohols are used, without requiring the presence of chemical catalysts, in which glycerins are obtained in different concentrations as a by-product of the reaction.
  • Oils and fats in general are known as triglycerides, and have a structure in which three fatty acids (esters) are linked to a glyceride (heavy alcohol).
  • the transesterification of these molecules means breaking their primary structure, separating glycerol from the three fatty acids, and these fatty acids, in turn, bind with a lighter alcohol.
  • esters These fatty acids bound with light alcohols are called esters and have a wide range of uses. STATE OF THE ART
  • Reactors for acid esterification using acid catalysts Reactors for biological transesterification using biological agents such as enzymes applied together with different solvents.
  • Acid-base processes which consists of a partial acid esterification of the free fatty acids existing in the raw material and a subsequent basic transesterification that acts on the remaining triglycerides;
  • - Processes under the aqueous method which uses a saturated solution of water-basic catalyst to increase the speed of obtaining methoxides to subsequently transesterify in alkaline form.
  • Good conversion rates can be achieved with basic catalysis production chemical reactors when virgin oils or fats are available, achieving conversion rates of up to 98%.
  • Oil or fat preparation can be by means of acid esterification or by saponification of free fatty acids and their subsequent separation; - Transesterification by any of the aforementioned methods;
  • esters and glycerins There are two major technical problems to be solved in the production of esters and glycerins, which are: - Simplification of the processing of oils with a high amount of free fatty acids (acidity) in the different oils, which destroy the alkaline catalyst and require a greater quantity. of processes and supplies; such as acid esterification and biological transesterification. This translates into plants with a greater number of processes and facilities, and consequently higher production costs.
  • a subject of the present invention is a chemical reactor that carries out a process by which the use of catalysts is unnecessary by means of supercritical alcoholysis, which produces a large change in the physicochemical variables of the alcohol used in the reaction.
  • the chemical reactor proposed for supercritical alcoholysis subjects the two main components of the chemical reaction, fatty acids (oils and fats of any type) and alcohol, to extreme pressure and temperature conditions, or supercritical conditions for alcohol used. Therefore, the two problems mentioned above are solved thereby:
  • the reactor has the following advantages: High speed, since the reaction time in the process carried out in this reactor is about 20 minutes, compared to the 90 minutes required in the aforementioned conventional processes, Greater simplicity of operation, since only two inputs are involved liquids,
  • a chemical reactor for supercritical alcoholysis of all types of fats and oils with various types of alcohols comprising: at least one oil supply tank 1 to be treated; at least one tank 7 for supplying a light alcohol; supply lines for oil or fat to be treated 5 and light alcohol 8; at least one oil or grease feed pump 6; - at least one light alcohol feed pump 9; at least one tubular reaction vessel 11; at least one tank or lung for depressurizing the effluents 14; heat exchangers 2 and 4 of effluents and tributaries; a heating medium for tributaries 10 and 12; - flow regulating valves 13;
  • the injection pumps are located in the initial part of the reactor in the direction of the tributaries.
  • the oil injector pump (6) receives the raw material from the heat exchangers (2 and 4) in countercurrent, which heats the oil and cools the reaction products.
  • Both fats or oils and alcohols are injected directly into the reactor at the same time; by means of the heating means (10) the tributaries are heated and by means of the pumping means the pressure is raised to a supercritical point.
  • an oil tank (1) is observed in the figure, said oil being the main tributary and product that we must process.
  • the oil through supply lines (3 and 5) to an oil supply pump (6).
  • a tank (7) of a light alcohol methyl, ethyl, propyl, butyric alcohol (7), said alcohol being the one that has to react with each of the esters or fatty acids that make up the oils , to form light chains.
  • the alcohol is led through the corresponding supply line 8 to the alcohol supply pump 9.
  • the reaction occurs within the tubes of the reactor 11.
  • the temperature is maintained by heating means 12 distributed along the tubes of the reactor.
  • heat exchangers 2 and 4 are placed, preferably in countercurrent, so that the oil, and possibly also the alcohol, take part of the heat that the effluents have.
  • the disintegration reaction of the triglycerides and the combination of the resulting esters with the supplied light alcohol takes place in a chemical reactor, where conditions of pressure and temperature high enough to make the reaction under these conditions occur spontaneously, varying the pressure and temperature values respectively depending on the composition of the oils used and the type of alcohol used.
  • the products are then passed through exchanger 2 to finish cooling the mixture and then the esters and glycerin can be separated by decantation in a separate container and evacuated by means of an outlet line 15.
  • the new catalyst-free alcoholysis technology has fewer processing stages, does not require the provision of steam and boilers, processing times are much shorter; and thanks to these advantages, it is possible that plants are very compact (they can fit whole in a 20 'or 40' container) and with a capacity many times less, they are also economically viable, just like an industrial plant. In this way, small plants can be installed for individual producers, thus avoiding all the logistics of collecting and transporting oils to an industrial plant. The same happens with production, which if it is small can be consumed in its entirety in one place, avoiding all the logistics of fuel distribution. We believe that this is an important factor since additional costs in the raw material and fuel are avoided, as well as additional consumption of fuels and energy.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne un réacteur chimique qui permet de réaliser l'alcoolyse supercritique de tous types de graisses et d'huiles avec différents types d'alcools. Ce réacteur chimique comprend un réservoir (1) d'alimentation d'huile à traiter, un réservoir (7) d'administration d'un alcool léger, des lignes d'alimentation (5, 8) des affluents, des pompes d'alimentation (6, 9), un réservoir de dépressurisation (14), des échangeurs thermiques (2, 4) permettant de tirer un profit optimal de l'énergie, des milieux de réchauffement (10, 12) des affluents, un récipient tubulaire de réaction (11) et des soupapes (13) de régulation du débit.
PCT/ES2005/070126 2005-09-01 2005-09-01 Reacteur chimique permettant de realiser l'alcoolyse supercritique de tout type de graisses et d'huiles avec differents types d'alcools Ceased WO2007026032A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/ES2005/070126 WO2007026032A1 (fr) 2005-09-01 2005-09-01 Reacteur chimique permettant de realiser l'alcoolyse supercritique de tout type de graisses et d'huiles avec differents types d'alcools

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2005/070126 WO2007026032A1 (fr) 2005-09-01 2005-09-01 Reacteur chimique permettant de realiser l'alcoolyse supercritique de tout type de graisses et d'huiles avec differents types d'alcools

Publications (1)

Publication Number Publication Date
WO2007026032A1 true WO2007026032A1 (fr) 2007-03-08

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PCT/ES2005/070126 Ceased WO2007026032A1 (fr) 2005-09-01 2005-09-01 Reacteur chimique permettant de realiser l'alcoolyse supercritique de tout type de graisses et d'huiles avec differents types d'alcools

Country Status (1)

Country Link
WO (1) WO2007026032A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008155436A2 (fr) 2007-06-19 2008-12-24 Beeb Bioenergias, S.A. Installation pour la production de biodiesel
ES2313840A1 (es) * 2007-06-19 2009-03-01 Guillermo Perez Celada Instalacion para la produccion de biodiesel.
EP2857483A1 (fr) 2013-10-03 2015-04-08 Supercritical Ideas, SL Instalation et procédé pour obtenir des esters des acides graises
CN112007942B (zh) * 2020-10-19 2021-01-01 四川北控聚慧物联网科技有限公司 一种基于工业物联网的餐厨垃圾处理自动化控制方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0985654A1 (fr) * 1998-09-09 2000-03-15 Sumitomo Chemical Company Limited Méthode de préparation d'esters d'acide gras et combustible comprenant des esters d'acide gras
EP1061120A1 (fr) * 1998-10-06 2000-12-20 Lonford Development Limited Preparation d'esters d'alkyle d'acides gras a partir de graisses et d'huiles
JP2001031991A (ja) * 1999-07-23 2001-02-06 Sumitomo Chem Co Ltd 脂肪酸エステルとグリセリンの連続的製造方法および連続的製造装置
EP1215275A1 (fr) * 2000-12-15 2002-06-19 Sumitomo Chemical Company Limited Procédé de préparation d'esters d'acides gras à partir de graines ou fruits
EP1298192A1 (fr) * 2001-09-28 2003-04-02 Sumitomo Chemical Company Limited Méthode et appareil pour la production d'esters de corps gras
JP2004182966A (ja) * 2002-10-07 2004-07-02 Kimura Chem Plants Co Ltd 脂肪酸エステルの製造装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0985654A1 (fr) * 1998-09-09 2000-03-15 Sumitomo Chemical Company Limited Méthode de préparation d'esters d'acide gras et combustible comprenant des esters d'acide gras
EP1061120A1 (fr) * 1998-10-06 2000-12-20 Lonford Development Limited Preparation d'esters d'alkyle d'acides gras a partir de graisses et d'huiles
JP2001031991A (ja) * 1999-07-23 2001-02-06 Sumitomo Chem Co Ltd 脂肪酸エステルとグリセリンの連続的製造方法および連続的製造装置
EP1215275A1 (fr) * 2000-12-15 2002-06-19 Sumitomo Chemical Company Limited Procédé de préparation d'esters d'acides gras à partir de graines ou fruits
EP1298192A1 (fr) * 2001-09-28 2003-04-02 Sumitomo Chemical Company Limited Méthode et appareil pour la production d'esters de corps gras
JP2004182966A (ja) * 2002-10-07 2004-07-02 Kimura Chem Plants Co Ltd 脂肪酸エステルの製造装置

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DATABASE WPI Week 200124, Derwent World Patents Index; AN 2001-229949, XP002333210 *
DATABASE WPI Week 200445, Derwent World Patents Index; AN 2004-473067, XP003009352 *
DIASAKOU M. ET AL.: "Kinetics of the non-catalytic transesterification of soybean oil", FUEL, vol. 77, no. 12, 1998, pages 1297 - 1302, XP004287070 *
SAKA S. ET AL.: "Biodiesel fuel from rapeseed oil as prepared in supercritical methanol", FUEL, vol. 80, 2001, pages 225 - 231, XP004286376 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008155436A2 (fr) 2007-06-19 2008-12-24 Beeb Bioenergias, S.A. Installation pour la production de biodiesel
WO2008155436A3 (fr) * 2007-06-19 2009-02-26 Beeb Bioenergias S A Installation pour la production de biodiesel
ES2313840A1 (es) * 2007-06-19 2009-03-01 Guillermo Perez Celada Instalacion para la produccion de biodiesel.
ES2313840B1 (es) * 2007-06-19 2009-12-29 Guillermo Perez Celada Instalacion para la produccion de biodiesel.
EP2857483A1 (fr) 2013-10-03 2015-04-08 Supercritical Ideas, SL Instalation et procédé pour obtenir des esters des acides graises
WO2015049573A1 (fr) 2013-10-03 2015-04-09 Supercritical Ideas, Sl Installation et procédé de production d'esters d'acides gras utilisables comme carburant
CN112007942B (zh) * 2020-10-19 2021-01-01 四川北控聚慧物联网科技有限公司 一种基于工业物联网的餐厨垃圾处理自动化控制方法

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