WO2020058898A1 - Préparation d'acides gras à partir d'huiles - Google Patents

Préparation d'acides gras à partir d'huiles Download PDF

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Publication number
WO2020058898A1
WO2020058898A1 PCT/IB2019/057908 IB2019057908W WO2020058898A1 WO 2020058898 A1 WO2020058898 A1 WO 2020058898A1 IB 2019057908 W IB2019057908 W IB 2019057908W WO 2020058898 A1 WO2020058898 A1 WO 2020058898A1
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WO
WIPO (PCT)
Prior art keywords
fatty acid
chloride
short chain
stream
chain fatty
Prior art date
Application number
PCT/IB2019/057908
Other languages
English (en)
Inventor
Vinodkumar Vasudevan
Abdullah Saad AL-DUGHAITHER
Somak PAUL
Mohammad ALQUDHYBI
Ganesh S BHAT
Jefrey Pagsisihan ANONUEVO
Original Assignee
Sabic Global Technologies B.V.
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 Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2020058898A1 publication Critical patent/WO2020058898A1/fr

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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
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/005—Splitting up mixtures of fatty acids into their constituents
    • 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
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
    • 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
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C11C1/10—Refining by distillation
    • C11C1/103—Refining by distillation after or with the addition of chemicals

Definitions

  • oils and/or fats can be subjected to splitting to release fatty acids.
  • splitting processes include hydrolysis by pressure splitting and enzymatic splitting.
  • the fatty acids can contain impurities, such as unsplit or incompletely split glycerides, for example, monoglycerides, diglycerides, or a combination comprising at least one of the foregoing, color bodies, steroid alcohols, and phosphatides.
  • U.S. Patent No. 7,560,579 relates to a process for preparing fatty acids derived from oils and/or fats with a phosphorus content below 200 ppm in good yield and with good color and color stability, which process comprises the steps of (A) hydrolytic splitting of degummed oils and/or fats, (B) at least one thermal pre-treatment of a composition comprising crude fatty acids, and (C) high vacuum distillation of the thermally pretreated composition comprising crude fatty acids.
  • a process for producing fatty acids comprises: forming a crude fatty acid product by splitting a feedstream comprising oils and/or fats in a splitting column; fractioning the crude fatty acid product into a short chain fatty acid stream, a long chain fatty acid stream, and a residual product stream in a fractionating column; exposing the short chain fatty acid stream to an acid chloride wherein impurities present in the short chain fatty acid stream are converted to substances having a higher molecular weight than the impurities; and distilling the short chain fatty acid stream forming a free fatty acid in a distillation column.
  • FIG. 1 is a schematic view of a reactor configuration used in the process disclosed herein.
  • the method can include fractioning a crude fatty acid product formed by splitting a feedstream including oils, fats, or a combination comprising at least one of the foregoing into a short chain fatty acid stream, a long chain fatty acid stream, and a residual product stream. This can be followed by exposing the short chain fatty acid stream to an acid chloride and distilling a free fatty acid stream from the short chain fatty acid stream.
  • the method can allow for recovery of at least 95% of free fatty acids from the short chain fatty acid stream, for example, at least 96%, for example, at least 98% of free fatty acids from the short chain fatty acid stream.
  • the process for preparing fatty acids derived from oils or fats in good yield and with good color and thermal stability can include splitting of degummed oils and/or fats to provide a crude fatty acid product.
  • Oils and fats that can be split include crude or refined vegetable oils and fats and crude, for example, degummed vegetable oils and fats, such as coconut oil, palm oil, palm kernel oil, sunflower oil, soybean oil, rapeseed oil, high erucic rapeseed oil, castor oil, linseed oil, safflower oil, com oil, cottonseed oil, groundnut oil, canola oil, or a combination comprising at least one of the foregoing.
  • Desirable splitting processes to release crude fatty acids from oils and fats include, but are not limited to, hydrolytic splitting processes such as thermal high pressure splitting and enzymatic splitting.
  • the splitting process can make use of a pressure splitter to which the fat or oil can be introduced at one end and water introduced at the opposite end thereof in a countercurrent flow patter.
  • the crude fatty acid product obtained by pressure splitting fats and oils can include about 95 to about 99 weight percent (wt.%) of free fatty acids, based on the total weight of the crude fatty acid product, and about 1-5 wt.% of impurities, such as unsplit glycerides, color bodies, steroid alcohols, and phosphatides.
  • the crude fatty acid product can contain impurities, such as, unsplit or incompletely split glycerides, for example, monoglycerides, diglycerides, or a combination comprising at least one of the foregoing, color bodies, steroid alcohols, and phosphatides.
  • the crude fatty acid product can be split into fractions of C 6- s fatty acids, Cs-io fatty acids, C12-14 fatty acids, C16-18 fatty acids, and residues in a fractionating column.
  • the short chain, e.g., C 6-i o, fatty acid fraction can contain impurities and can have a relatively high ester value.
  • the short chain fatty acid fraction can be exposed to an acid chloride to convert monoglycerides, diglycerides, or a combination comprising at least one of the foregoing present in the short chain fatty acid fraction to triglycerides (i.e., higher molecular weight glycerides).
  • Exemplary acid chlorides include fatty acid chlorides, such as caproic chloride, capric chloride, pelargonic chloride, caprylic chloride, lauric chloride, myristic chloride, palmitic chloride, isopalmitic chloride, stearic chloride, isostearic chloride, oleic chloride, or a combination comprising at least one of the foregoing.
  • the acid chloride treatment can be performed at a temperature of 150 to l80°C and at atmospheric pressure.
  • Rl and R2 can independently be a C 6 hydrocarbon, a Cs hydrocarbon, or a C 10 hydrocarbon.
  • the acid chloride is not contaminated during the reaction.
  • a free fatty acid stream can be distilled from the short chain fatty acid stream in a distillation column.
  • the distillation can be based on a high vacuum distillation method, for example, thin film evaporation, (centrifugal) molecular distillation, wiped film
  • the distillation temperature can be 100 to l40°C and the distillation pressure can be 1 to 10 mm mercury (Hg) (0.133 to 1.333 kPa).
  • the ester value of the free fatty acid stream can be less than or equal to 1.
  • the ester value corresponds to esters, for example, monoglycerides, diglycerides, triglycerides, or a combination comprising at least one of the foregoing, present in the free fatty acid stream.
  • Ester value is calculated as the difference between saponification value and acid value of the fatty acids.
  • the acid chloride treatment reduces the esters present in the fatty acids and reduces the difference between saponification value and acid value of the fatty acids to less than or equal to 1.
  • esters are present in the free fatty acid stream can be less than 0.5 wt.%.
  • the esters can be present in an amount of 0.5-5 mgKOH/g, which is calculated as the difference in the value of the saponification value and the acid value.
  • Desirable values of ester value of the free fatty acid stream and esters present in the free fatty acid stream can be obtained due to, for example, a boiling point of the free fatty acid stream being less than the boiling point of monoglycerides.
  • Monoglycerides have boiling points less than diglycerides, and diglycerides have boiling points less than triglycerides.
  • a boiling point of the free fatty acid stream can be less than a boiling point of thelimpurities present, in the short chain fatty acid stream.
  • the impurities can include, for example, monoglycerides, diglycerides, or a combination comprising at least one of the foregoing.
  • a difference between the boiling point of the free fatty acid stream and the boiling point of the triglycerides can be at least 30°C, for example, at least 50°C.
  • Table 1 lists boiling points for exemplary free fatty acids, monoglycerides, and diglycerides. Pressure is listed in both Torr (torr) and Pascals (Pa).
  • Additional purification can be avoided, for example, due to a boiling point of the free fatty acid stream being less than the boiling point of monoglycerides.
  • triglycerides formed by conversion of monoglycerides, diglycerides, or a combination comprising at least one of the foregoing present in the short chain fatty acid stream can be recycled to the splitting column in which the feedstream including oils, fats, or a combination comprising at least one of the foregoing is split.
  • Triglycerides that are recycled can either be admixed with newly added oils and/or fats prior to or during the splitting process or collected separately and recycled without admixing with newly added oils and/or fats.
  • a process for producing fatty acids is shown.
  • a feedstream 12 comprising oils and/or fats is sent to a splitting column 20 to form a crude fatty acid product 14.
  • the crude fatty acid product 14 is then sent to a fractionating column 30 to be fractionated into a short chain fatty acid stream 15, a long chain fatty acid stream 16, and a residual product stream 18.
  • the short chain fatty acid stream 15 is exposed to an acid chloride so that impurities present in the short chain fatty acid stream 15 are converted to substances having a higher molecular weight than the impurities.
  • the shorty chain fatty acid stream 15 is sent to a distillation column 40 to form a free fatty acid 22.
  • An ester value of the free fatty acid can be less than or equal to 1.
  • the feedstream can comprise palm kernel oil, coconut oil, vegetable oil, safflower oil, canola oil, sunflower oil, or a combination comprising at least one of the foregoing.
  • the crude fatty acid product can comprise impurities.
  • the impurities can comprise unsplit or incompletely split glycerides, color bodies, steroid alcohols, phosphatides, or a combination comprising at least one of the foregoing.
  • the unsplit or incompletely split glycerides can comprise a monoglyceride, a diglyceride, or a combination comprising at least one of the foregoing.
  • the monoglyceride, diglyceride, or a combination comprising at least one of the foregoing can be converted to a triglyceride.
  • the short chain fatty acid stream can comprise C 6-i o fatty acids, for example, the short chain fatty acid stream can comprise C 6- s fatty acids or Cs-io fatty acids.
  • the acid chloride can comprise a fatty acid chloride, for example, the fatty acid chloride can comprise caproic chloride, capric chloride, pelargonic chloride, caprylic chloride, lauric chloride, myristic chloride, palmitic chloride, isopalmitic chloride, stearic chloride, isostearic chloride, oleic chloride, or a combination comprising at least one of the foregoing.
  • the fatty acid chloride can comprise caproic chloride, capric chloride, pelargonic chloride, caprylic chloride, lauric chloride, myristic chloride, palmitic chloride, isopalmitic chloride, stearic chloride, isostearic chloride, oleic chloride, or a combination comprising at least one of the foregoing.
  • the free fatty acid can be distilled under vacuum.
  • a boiling point of the free fatty acid can be less than a boiling point of the impurities present in the short chain fatty acid stream.
  • the boiling point of the free fatty acid can be less than the boiling point of a monoglyceride, diglyceride, or triglyceride.
  • the boiling point of the free fatty acid can be 30°C to 50°C, for example, at least 30°C, for example, at least 50°C, less than the boiling point of a triglyceride.
  • At least 95% of free fatty acid can be recovered from the short chain fatty acid stream, for example, at least 96%, for example, at least 98%.
  • a process for producing fatty acids comprising: forming a crude fatty acid product by splitting a feedstream comprising oils and/or fats in a splitting column; fractioning the crude fatty acid product into a short chain fatty acid stream, a long chain fatty acid stream, and a residual product stream in a fractionating column; exposing the short chain fatty acid stream to an acid chloride wherein impurities present in the short chain fatty acid stream are converted to substances having a higher molecular weight than the impurities; and distilling the short chain fatty acid stream forming a free fatty acid in a distillation column.
  • Aspect 2 The process of Aspect 1, wherein an ester value of the free fatty acid is less than or equal to 1.
  • Aspect 3 The process of Aspect 1 or Aspect 2, wherein the feedstream comprises palm kernel oil, coconut oil, vegetable oil, safflower oil, canola oil, sunflower oil, or a combination comprising at least one of the foregoing.
  • Aspect 4 The process of any of Aspects 1-3, wherein the crude fatty acid product comprises impurities.
  • Aspect 5 The process of Aspect 4, wherein the impurities comprise unsplit or incompletely split glycerides, color bodies, steroid alcohols, phosphatides, or a combination comprising at least one of the foregoing.
  • Aspect 6 The process of Aspect 5, wherein the unsplit or incompletely split glycerides comprise a monoglyceride, a diglyceride, or a combination comprising at least one of the foregoing.
  • Aspect 7 The process of Aspect 6, wherein the monoglyceride, diglyceride, or a combination comprising at least one of the foregoing is converted to a triglyceride.
  • Aspect 8 The process of any of the preceding aspects, wherein the short chain fatty acid stream comprises C 6-i o fatty acids, preferably, wherein the short chain fatty acid stream comprises C 6 -Cs fatty acids or Cs-io fatty acids.
  • Aspect 9 The process of any of the preceding aspects, wherein acid chloride comprises a fatty acid chloride, preferably, wherein the fatty acid chloride comprises caproic chloride, capric chloride, pelargonic chloride, caprylic chloride, lauric chloride, myristic chloride, palmitic chloride, isopalmitic chloride, stearic chloride, isostearic chloride, oleic chloride, or a combination comprising at least one of the foregoing.
  • the fatty acid chloride comprises caproic chloride, capric chloride, pelargonic chloride, caprylic chloride, lauric chloride, myristic chloride, palmitic chloride, isopalmitic chloride, stearic chloride, isostearic chloride, oleic chloride, or a combination comprising at least one of the foregoing.
  • Aspect 10 The process of any of the preceding aspects, further comprising distilling the free fatty acid under vacuum.
  • Aspect 11 The process of any of the preceding aspects, wherein a boiling point of the free fatty acid is less than a boiling point of the impurities present in the short chain fatty acid stream.
  • Aspect 12 The process of Aspect 11, wherein the boiling point of the free fatty acid is less than the boiling point of a monoglyceride, diglyceride, or triglyceride.
  • Aspect 13 The process of Aspect 11, wherein the boiling point of the free fatty acid is at least 30°C, preferably at least 50°C, less than the boiling point of a
  • Aspect 14 The process of any of the preceding aspects, wherein at least 95% of free fatty acid are recovered from the short chain fatty acid stream, preferably, at least 96%, more preferably, at least 98%.
  • Aspect 15 The process of any of Aspects 7-14, further comprising recycling the triglyceride converted from the monoglyceride, diglyceride, or a combination comprising at least one of the foregoing to the splitting column
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
  • the phrases“crude fatty acids” and“crude fatty acid product” refer to free fatty acids that are contaminated with one or more impurities, such as, unsplit or incompletely split glycerides (like monoglycerides, diglycerides, or a combination comprising at least one of the foregoing), color bodies, steroid alcohols, and phosphatides.
  • the phrases“free fatty acids” and“fatty acids” refer to aliphatic monocarboxylic acids having varying degrees of unsaturation and that are derivable from glycerides (the esters of glycerol with the aliphatic monocarboxylic acids).

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

Abstract

L'invention concerne un procédé de production d'acides gras, consistant à : former un produit d'acide gras brut par division d'un flux d'alimentation comprenant des huiles et/ou des graisses dans une colonne de division ; fractionner le produit d'acide gras brut en un flux d'acides gras à chaîne courte, un flux d'acides gras à longue chaîne et un flux de produit résiduel dans une colonne de fractionnement ; soumettre le flux d'acides gras à chaîne courte à l'action d'un chlorure d'acide, les impuretés présentes dans le flux d'acides gras à chaîne courte étant converties en substances présentant un poids moléculaire plus élevé que celui des impuretés ; et distiller le flux d'acides gras à chaîne courte, ce qui forme un acide gras libre dans une colonne de distillation.
PCT/IB2019/057908 2018-09-20 2019-09-19 Préparation d'acides gras à partir d'huiles WO2020058898A1 (fr)

Applications Claiming Priority (2)

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US201862733824P 2018-09-20 2018-09-20
US62/733,824 2018-09-20

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WO2020058898A1 true WO2020058898A1 (fr) 2020-03-26

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5142072A (en) * 1989-12-19 1992-08-25 The Procter & Gamble Company Selective esterification of long chain fatty acid monoglycerides with medium chain fatty acid anhydrides
WO2006108754A1 (fr) * 2005-04-08 2006-10-19 Danisco A/S Le procede de recuperation et d'utilisation de diglycerides
US7560579B2 (en) 2003-07-10 2009-07-14 Oleon N.V. Process for preparing purified fatty acids
US9745541B1 (en) * 2016-09-09 2017-08-29 Inventure Renewables, Inc. Methods for making free fatty acids from soaps using thermal hydrolysis followed by acidification

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5142072A (en) * 1989-12-19 1992-08-25 The Procter & Gamble Company Selective esterification of long chain fatty acid monoglycerides with medium chain fatty acid anhydrides
US7560579B2 (en) 2003-07-10 2009-07-14 Oleon N.V. Process for preparing purified fatty acids
WO2006108754A1 (fr) * 2005-04-08 2006-10-19 Danisco A/S Le procede de recuperation et d'utilisation de diglycerides
US9745541B1 (en) * 2016-09-09 2017-08-29 Inventure Renewables, Inc. Methods for making free fatty acids from soaps using thermal hydrolysis followed by acidification

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