WO2019125317A2 - Procédé de production de biodiesel (ester méthylique) conforme à la norme en14214 à partir d'huiles et de graisses à forte teneur en acides gras libres, d'acides gras, d'huiles contenant de l'acide sulfurique, qui sont des sous-produits de raffinage des huiles - Google Patents

Procédé de production de biodiesel (ester méthylique) conforme à la norme en14214 à partir d'huiles et de graisses à forte teneur en acides gras libres, d'acides gras, d'huiles contenant de l'acide sulfurique, qui sont des sous-produits de raffinage des huiles Download PDF

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Publication number
WO2019125317A2
WO2019125317A2 PCT/TR2018/050245 TR2018050245W WO2019125317A2 WO 2019125317 A2 WO2019125317 A2 WO 2019125317A2 TR 2018050245 W TR2018050245 W TR 2018050245W WO 2019125317 A2 WO2019125317 A2 WO 2019125317A2
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WO
WIPO (PCT)
Prior art keywords
oils
methyl ester
acid oils
biodiesel
byproduct
Prior art date
Application number
PCT/TR2018/050245
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English (en)
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WO2019125317A3 (fr
Inventor
Emre Aksoy
Mazlum Aksoy
Original Assignee
Maysa Yağ Sanayi̇ Anoni̇m Şi̇rketi̇
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Application filed by Maysa Yağ Sanayi̇ Anoni̇m Şi̇rketi̇ filed Critical Maysa Yağ Sanayi̇ Anoni̇m Şi̇rketi̇
Publication of WO2019125317A2 publication Critical patent/WO2019125317A2/fr
Publication of WO2019125317A3 publication Critical patent/WO2019125317A3/fr

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Classifications

    • 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
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • 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
    • 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 relates to a process which enables to produce biodiesel in EN14214 norm from high FFA oils&fats [%5-l00 FFA], fatty acids, sulfuric acid oils [%5-l00] which are byproducts of refining of oils.
  • Biodiesel refers to diesel fuels based on vegetable or animal oils with long chain alkyl (ethyl, methyl) esters. The synthesis of these fuels is generally realized by chemically reacting vegetable and animal oils with an alcohol. Biodiesel fuels are based on recycling oils or waste oils to be used in diesel engines; they can be used by mixing with petrodiesel in different ratios as well as they can be used alone. The biodiesel having high boiling point and low vapor pressure has much higher ignition temperature (>130 °C) relative to petrodiesel (64 °C) and gasoline (-45 °C).
  • biodiesel is manufactured by transesterification of a vegetable or animal oil source.
  • the raw oil is transformed into desired esters by means of liquid transesterification.
  • the free fatty acids of the oil are transformed into soapstock and removed from the process, or they can be esterified in presence of an acidic catalyst (in presence of methanol and for the production of biodiesel).
  • Biodiesel obtained as a result of esterification process exhibits combustion features similar to petrodiesel, being different from the vegetable oil, and it can replace vegetable oil in many applications for this reason.
  • Biodiesel subjected to transesterification comprises a mixture of mono-alkyl esters of long chain fatty acids.
  • the acidity degree indicates the amount of "oleic acid” in 100 grams of oil.
  • Oleic acid is a fatty acid, and usually found in animal and vegetable oils in natural ways.
  • Fatty acid is a carboxylic acid which may be saturated or unsaturated and which has a long aliphatic chain.
  • Oils are comprised of glycerin and fatty acids. While fat is suitable for use as food when the amount of free fatty acid is low, when this amount increases, its bitterness increases and it can be used in different fields rather than the food.
  • biodiesel methyl ester
  • oils with low-fatty acids from raw oils
  • waste frying oils with base catalyst from waste frying oils
  • production is performed by means of base catalyst after acid catalyst reaction from fatty acids.
  • Turkish Patent Document no TR2008/01480 an application known in the state of the art, discloses raw vegetable oils comprising free fatty acids to be used in biodiesel production, and a process for removing acid from frying oils.
  • the present invention relates to a process for removing acid from vegetable oils with high free fatty acid or used frying oils to be used in the production of biodiesel.
  • free fatty acid part is removed from the oil and separated completely as waste, and whole product cannot be recycled.
  • International Patent document no W02007113530 an application known in the state of the art, discloses a biodiesel production method. Within the scope of this method, the crude oil, which is slightly higher in acidity, is blended with the other crude oil with lower acidity, and then the fatty acid is separated and the product is neutralized and the remaining product is converted into biodiesel.
  • Malaysian Patent document no MY163535 an application known in the state of the art, discloses a biodiesel preparation method. This process is carried out with acid catalyst.
  • Malaysian Patent document no MY156279 an application known in the state of the art, discloses a method developed in order to produce biodiesel from oils with high free fatty acid content. This process is carried out with calcined bismuth vanadyl phosphate catalyst.
  • Cida patent document no CN105647656 an application known in the state of the art, discloses a biodiesel and glycerin production method from sources with high free fatty acids. Within the scope of this method, distillation is being carried out, including reactive distillation of stream rich in fatty acid alkyl ester. This process is not developed for products with high impurity; it is a method where fatty acids are used. Tar byproduct cannot be converted into energy.
  • the objective of the invention is the production of biodiesel in EN14214 norm from oils with high fatty acids, sulfuric acid oils which are byproduct of refining of fatty acids and oils by utilizing raw materials with lower cost by means of managing sulfur and other impurity parameters in the process.
  • Another objective of the invention is to recover oils with high fatty acids having high sulfur and other impurity ratios which have great effect on environment and health, and sulfuric acid oils which are the byproduct of refining of high fatty acids and oils into economy.
  • the inventive method which enables to produce biodiesel in EN14214 norm from high FFA oils&fats [%5-l00 FFA], fatty acids, sulfuric acid oils [%5-l00] which are byproducts of refining of oils, comprises the steps of
  • oils with high fatty acids, fatty acids and sulfuric acid oils which are byproduct of refining of oils into a stainless steel neutralization reactor suitable for vacuum and high temperature
  • tar which is obtained as byproduct besides distilled methyl ester is used in order to be transformed into energy after disintegration and adsorbent filtration.
  • the inventive method for producing biodiesel (methyl ester) in EN14214 norm from high fatty acid oils, sulfuric acid oils which are byproduct of fatty acids and oils is primarily comprised of three main process steps: neutralization, methylation, distillation: 1) Neutralization
  • High fatty acid oils, fatty acids and sulfuric acid oils which are byproduct of refining of oils are used as raw material.
  • the raw material is transferred into a stainless steel neutralization reactor suitable for vacuum and high temperature, and antioxidant is added into the oils in order to prevent oxidation.
  • the raw material is first neutralized with base and then the neutralization reaction is carried out in the absence of catalyst at a temperature range of 150-250 °C, at a stirring speed of 30-60 rpm, under reflux and a vacuum of 2-300 mbar by using tempered water in condensing exchangers for 3-12 hours when the mixer is in upwards position.
  • the reaction is carried out until the free fatty acid (FFA) is neutralized.
  • the product is removed from the vacuum by cooling and sent to the neutralized oil tank.
  • FFA free fatty acid
  • the neutral oil is taken into the methylation (transesterification) reactor in order to be converted into methyl ester.
  • Solution of methanol in ratio of 10-40% of the oil by weight and sodium methylate in ratio of 1-10% are added into the reactor.
  • the sodium methylate solution is obtained readily, or prepared by dissolving solid NaOH in methanol.
  • the methylation (transesterification) reaction is carried out at a reactor temperature of 50-65 0 C, in a mixing rotation of 30-60 rpm, under reflux and 1 atm of nitrogen, while maintaining the mixer in the downward direction for 0.5-2 hours.
  • the unreacted methanol is rectified at the end of the reaction under vacuum.
  • the product is washed with water after the rectification and the reactor is left for decantation.
  • the methyl ester is cooled to remove the streyl glucosides therein and passed through the separator in order to be separated, and then taken into methyl ester tank by being clarified under 10000- 15000G force.
  • Antioxidant is added into the methyl ester, and it is cleared from impurities by being degassed by being sprayed under vacuum of 2-50 mbar at temperature of l00-l75°C.
  • the methyl ester is distilled and condensed in stainless steel equipment/piping under a vacuum of 2-50 mbar at a temperature range of 200-260 °C.
  • Distilled methyl ester is obtained in accordance with EN 14214 norm.
  • Distilled methyl ester is preserved with the addition of antioxidant and CFPP under nitrogen. Tar which is obtained as byproduct besides distilled methyl ester is used by being converting into energy after soap disintegration process and adsorbent filtration at a temperature range of 60-90°C.
  • Methyl esters produced from fatty acids can also be used without distillation on ground that they are compatible with EN14214.
  • raw materials with lower cost are utilized with the production of biodiesel (methyl ester) in EN14214 norm from high fatty acid oils, acid oils and sulfuric acid oils which are byproduct of refining of oils, and these products affecting the environment are recovered into economy.
  • the byproducts of the said process are also transformed into energy.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne un procédé qui permet de produire du biodiesel conforme à la norme EN14214 à partir d'huiles et de matières grasses à forte teneur en acides gras libres [5 à 100 % d'acides gras libres], d'acides gras, d'huiles contenant de l'acide sulfurique [5 à 100 %] qui sont des sous-produits de raffinage des huiles. L'objectif de la présente invention est d'utiliser des matières premières peu coûteuses pour la production de biodiesel conforme à la norme EN14214 à partir d'huiles et et de matières grasses à forte teneur en acides gras libres [5 à 100 % d'acides gras libres], d'acides gras, d'huiles contenant de l'acide sulfurique [5 à 100 %] qui sont des sous-produits de raffinage des huiles, et de recycler ces produits, qui ont une incidence sur l'environnement/la santé, dans l'économie.
PCT/TR2018/050245 2017-12-19 2018-05-17 Procédé de production de biodiesel (ester méthylique) conforme à la norme en14214 à partir d'huiles et de graisses à forte teneur en acides gras libres, d'acides gras, d'huiles contenant de l'acide sulfurique, qui sont des sous-produits de raffinage des huiles WO2019125317A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2017/20807 2017-12-19
TR2017/20807A TR201720807A1 (tr) 2017-12-19 2017-12-19 Yüksek asi̇tli̇ yağlardan (high ffa oils&fats), yağ asi̇tleri̇nden (fatty acid), yağlarin rafi̇nasyon yan ürünü sülfürlü asi̇tli̇ yağlardan (acidoil) en14214 normunda bi̇yodi̇zel (meti̇l ester) üreti̇m yöntemi̇

Publications (2)

Publication Number Publication Date
WO2019125317A2 true WO2019125317A2 (fr) 2019-06-27
WO2019125317A3 WO2019125317A3 (fr) 2019-08-08

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PCT/TR2018/050245 WO2019125317A2 (fr) 2017-12-19 2018-05-17 Procédé de production de biodiesel (ester méthylique) conforme à la norme en14214 à partir d'huiles et de graisses à forte teneur en acides gras libres, d'acides gras, d'huiles contenant de l'acide sulfurique, qui sont des sous-produits de raffinage des huiles

Country Status (2)

Country Link
TR (1) TR201720807A1 (fr)
WO (1) WO2019125317A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112945675A (zh) * 2021-03-16 2021-06-11 山东非金属材料研究所 一种油中氮含量标准物质的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPR946201A0 (en) * 2001-12-13 2002-01-24 Jott Australia Pty. Ltd. Process for production of fatty acid esters
RU2379332C1 (ru) * 2004-10-20 2010-01-20 Каунсил Оф Сайентифик Энд Индастриал Рисерч Усовершенствованный способ получения метилового эфира жирной кислоты (биодизеля) путем переэтерификации триглицеридов масла
US20080282606A1 (en) * 2007-04-16 2008-11-20 Plaza John P System and process for producing biodiesel
TR200703297A2 (tr) * 2007-05-15 2007-11-21 Keski̇nler Bülent Bitkisel yağlardan serbest yağ asitlerinin uzaklaştırılması için bir proses
US8709109B2 (en) * 2009-01-12 2014-04-29 Arisdyne Systems Incorporated Process for improved biodiesel fuel
US9085547B2 (en) * 2011-04-14 2015-07-21 Alfa Laval Corporate Ab Process for autocatalytic esterification of fatty acids

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112945675A (zh) * 2021-03-16 2021-06-11 山东非金属材料研究所 一种油中氮含量标准物质的制备方法

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TR201720807A1 (tr) 2019-07-22
WO2019125317A3 (fr) 2019-08-08

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