Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/42—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/42—Separation; Purification; Stabilisation; Use of additives
  • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
  • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/48—Separation; Purification; Stabilisation; Use of additives
  • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
  • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07J—STEROIDS
  • C07J51/00—Normal steroids with unmodified cyclopenta(a)hydrophenanthrene skeleton not provided for in groups C07J1/00 - C07J43/00
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07J—STEROIDS
  • C07J75/00—Processes for the preparation of steroids in general
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07J—STEROIDS
  • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
• • 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
  • C11B13/005—Recovery of fats, fatty oils or fatty acids from waste materials of residues of the fabrication of wood-cellulose (in particular tall-oil)
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/62—Carboxylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
  • C12P7/6436—Fatty acid esters
  • C12P7/6445—Glycerides
  • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
  • C12P7/6436—Fatty acid esters
  • C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
• • 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
  • 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 invention refers to a process for obtaining fatty acid alkyl esters, rosin acids and sterols from crude tall oil (CTO) which involves several esterification and distillation steps.
• CTO crude tall oil
• Crude tall oil typically comes from the sulphate process employed in the manufacture of cellulose from wood. More particularly, the spent black liquor from the pulping process is concentrated until sodium salts (soaps) of various acids separate out and are skimmed off. The salts are acidified or decomposed with sulphuric acid so as to provide the crude tall oil.
• Crude tall oil is refined mainly by vacuum distillation processes to separate the various compounds almost completely into rosin and fatty acid fractions.
• the current technology is based in distillation where the acids are fractionated in several columns. Using a first column to separate the more volatile fatty acids and rosin acids, from the less volatile materials, which include many of the unsaponifiable and neutral materials such as sterols and their esters. A second column is commonly designed to separate the more volatile fatty acids from the less volatile rosin acids. This process usually ends up with a bottom that is currently called “pitch”, where sterols, heavy hydrocarbons, wax alcohols are the main substances. Commercially, only fatty and rosin acids are produced. Pitch usually is used as a fuel.
• a method of separating sterols from crude tall oil, wherein the sterols are not destroyed in the process, would be a useful invention in the chemical preparation industry. Therefore, the objective of this invention is to find an economic process to separate the three main crude tall oil (CTO) components, fatty acids or their esters, rosin acids, and sterols, to get these commercially valuable products.
• CTO crude tall oil
• the present invention therefore provides a new process for obtaining fatty acid alkyl esters, rosin acids and sterols from crude tall oil (CTO), which is characterised by the following steps:
• step (a) of the process the fatty acids are converted into their respective C 1 -C 4 alkyl esters, preferably into their methyl esters.
• the major advantage of this step lies in the low boiling point of the esters thus obtained, which makes it easy to separate them from the other fractions. This is preferably done in a single esterification step due to the selective enzymatic or chemical reaction between fatty and rosin acids, with means that usually only the fatty acids are converted into their respective esters.
• the esterification can be conducted by means of acidic catalysts, like for example methane sulfonic acid at temperatures of 120 to 150° C., or enzymes, like for example Novozym CaLB (Novo) at temperatures of 20 to 50° C., depending on the activity optimum of the micro-organisms. Usually, the enzymatic reaction takes a significantly longer time.
• the esterification can be carried out under pressure.
• step (b) the fatty acid esters thus obtained are separated from the remaining CTO by means of distillation, short path distillation or fractionation, employing milder conditions compared to the acid distillation.
• the fatty acid alkyl esters preferably fatty acid methyl esters, are thereby advantageously obtained without rosin acids contamination and leaving less fatty acids in the bottom stream.
• the distillation is preferably carried out by means of a wiped film evaporator which is usually conducted at a reduced pressure of 0.01 to 10 mmHg and a temperature of 190 to 240° C.
• boric acid H 3 BO 3
• H 3 BO 3 boric acid
• the esterification is conducted a temperature of 200 to 230° C.
• the borate esters step can be applied to separate tocopherols and sterols from the fatty acids portion in the soy bean vegetable oil distillate (VOD), and also to separate sterols and high molecular alcohols in the sugar cane waxes.
• the first stream fatty acid methyl esters, is used to produce methyl dimerate, a raw material used to make polyamides as described in the U.S. Pat. No. 6,281,373.
• the second stream, the rosin acids is used to produce adhesives and other conventional products.
• the third stream can be used as high sterols feed in the existent purification sterols processes.
• This example illustrates for comparison purpose a wiped film evaporator (WFE) distillation of crude tall oil (CTO) in the same wiped film evaporator equipment used to develop the entire process, without selective enzymatic or chemical esterification of fatty acid and without transforming all free sterols into sterols borate triesters.
• WFE wiped film evaporator
• the CTO contained 4.7% b.w. sterol, of which only 9.0% b.w. was already present as sterol esters.
• the WFE was operated at 1 mm Hg, with a initial residue temperature of 190° C.
• the residue fraction (residue 1) leaving the bottom of the WFE represented 64.0% b.w. of the CTO feed.
• the residue 1 contained 38.0% b.w. rosin acids, 40.0 b.w. % of TOFA.
• the WFE was operated at 1 mm Hg, with a initial residue 1 temperature of 240° C.
• the residue fraction (residue 2) leaving the bottom of the WFE represented 15.0% b.w. of the residue 1 feed.
• the residue 2 contained 40% b.w. rosin acids, and 6% b.w. total sterol.
• the sterol yield in this process was 25% b.w., which means that 75% b.w. of the sterols were degradated or distilled off together with the rosins and fatty acids.
• This inventive example describes the use of an selective chemical esterification of fatty acid from crude tall oil followed by the wiped film evaporator (WFE) to separate the fatty acids as methyl esters from the remaining heavy products.
• WFE wiped film evaporator
• WFE wiped film evaporator
• the product was distilled in the WFE which was operated at 1 mm Hg, with a initial residue temperature of 190° C.
• the residue 1 leaving the bottom of the WFE represented 54.0% b.w. of the CTO feed.
• the residue 1 contained 8.8% b.w. total sterols.
• the sterols yield in this first fractionation represented 99.4% b.w.
• the remaining 0.6% b.w. of the sterol were evaporated along with the volatile portion of the CTO. Thermal degradation reactions were minimal.
• residue 1 5.0 g of boric acid (0.08 moles ) obtained from Aldrich Chemical Co., the sample were added.
• the sample was transferred into a 2-liter, 3-necked round bottom flask and reacted for 4 h at 220° C. to convert all the free sterols into esters.
• the product was distilled through a WFE operating at 1 mm Hg, with a residue temperature of 240° C.
• the residue 2 fraction leaving the bottom of the WFE represented 35.0% b.w. of the residue 1 feed having 21% b.w. of sterols.
• Thermal degradation products were 6.0% b.w. of the total.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Health & Medical Sciences (AREA)
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• General Chemical & Material Sciences (AREA)
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• Biochemistry (AREA)
• Bioinformatics & Cheminformatics (AREA)
• General Engineering & Computer Science (AREA)
• Genetics & Genomics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Steroid Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Fats And Perfumes (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2003
  • 2003-02-21 CA CA 2514700 patent/CA2514700A1/en not_active Abandoned
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