Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
• • 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
  • C11B13/02—Recovery of fats, fatty oils or fatty acids from waste materials from soap stock
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
• • 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
  • C11C1/025—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by saponification and release of fatty acids
• • 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
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D13/00—Making of soap or soap solutions in general; Apparatus therefor
  • C11D13/30—Recovery of soap, e.g. from spent solutions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
• • 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
• • 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 concerns a process for forming a fatty acid, a fatty acid ester or a mixture thereof from a starting material comprising soap, as well as use of the formed mixture.
• Biodiesel is mainly the methyl ester of fatty acids that is formed through the transesterification of long-chained fatty acids with an alcohol (methanol).
• the fatty acid esters of natural fats consist mainly of triglycerides, whereby a water-soluble glycerol that is unacceptable as biodiesel is released in the transesterification.
• an alcohol (methanol) mixed into the aqueous glycerol solution and salts of fatty acids (later soap) are released in the process.
• This fraction containing glycerol, alcohol and soap still has, particularly with regard to the soap, a high energy content.
• 10% by weight of glycerol is generated from the triglyceride.
• the proportion of the soap can vary greatly and rise up to tens of percent from the original total amount of triglyceride. Since the soap compounds are dispersed and partly dissolved in the aqueous solution of the formed glycerol, their separation from the aqueous solution is difficult. The soap disrupts the phase between the fat-soluble fatty acid esters and the water-soluble glycerol and tends to form different degrees of emulsions, creating a challenging problem in large-scale processes with regard to separation techniques. Removal of the alcohol, such as methanol, would also require expensive vacuum distillation.
• the present invention concerns a process for forming a fatty acid, a fatty acid ester or a mixture thereof from a starting material comprising soap.
• the invention provides a new solution to a problem that relates to a process wherein esters of fatty acids are produced according to an established method using methanol or other short-chained alcohols from glycerolipid-containing fat by treating them with alkali metal alkoxides.
• Glycerol and other alcohols as well as a water-soluble alkali metal salt of fatty acids, soap, are formed in the process.
• the glycerol and the soap of the mixture decrease the utilization degree of the total carbon contained in the original fat used in the process and, thus, the economic efficiency of the process.
• An essential disadvantage of the utilization of the glycerol that is formed in the production of biodiesel, compared with pure glycerol, is the water, the soap and the toxic methanol or other short-chained alcohol it contains as impurity.
• An advantage of the invention is an integrated unit operation entity, by means of which an ester that is formed from a hydrocarbon-chain-containing fatty acid and short-chain alcohols can be reformed from a difficultly energy-economically utilizable impure glycerol minor flow, which is released from the transesterification of organic fats.
• the apparatus used in the process is simple and the technology associated with it is known with regard the production and the use.
• the process according to the invention is not bound to production scale, but it is readily scalable.
• the invention enables, inter alia, the recovery of the energy-rich soap and the recycling into alcohol esters of fatty acids or free fatty acids.
• a process technical and economical advantage of the invention is that, by means of it, the total utilization of the carbon of the fraction consisting of compounds that contain alcoholic groups and containing impurities can be solved for the manufacturing of fatty acid esters and fatty acids by a process that neither demands energy requiring unit operations, such as heating, nor pressurized unit operations and, which for functioning requires only the use of such chemicals, which can be incorporated into the inner circulation of the process according to the invention.
• the invention more efficiently fulfils the principles of sustainable development by intensifying the total utilization of the raw materials and by thus decreasing the need for using other raw materials.
• the process according to the invention consists of a functional entity having the prerequisites for updating the production costs of fatty acids and alcohol esters thereof to a level accepted by consumers.
• Fig. 1 depicts the main execution steps of the process according the invention.
• the present invention concerns a process for forming a fatty acid, a fatty acid ester or a mixture thereof from a starting material comprising soap, preferably an alcohol and soap.
• the alcohol is preferably methanol, ethanol, 1-propanol or a polyhydric alcohol, most preferably glycerol.
• soap means a salt of a fatty acid.
• the present invention concerns a process, which comprises steps, wherein a metal-ion forming agent is added to said starting material to produce a mixture comprising an insoluble phase and a liquid phase.
• the insoluble phase is separated from the liquid phase and acid is added to the former.
• acid is added to the former.
• the precipitating ion-forming agent is added to the liquid phase and to treat the formed precipitate as above. This step can be repeated until the formation of precipitate has essentially decreased.
• Acid is added to the combined insoluble phase to form fatty acid.
• the fatty acids are recovered and used as such or a monohydric alcohol and an acid catalyst are added to form fatty acid ester.
• two phases are formed, an aqueous phase and an organic phase.
• the organic phase thus contains the fatty acid ester.
• a monohydric alcohol and an acid are added to the insoluble phase without separate recovery of the fatty acid, whereby an aqueous phase and an organic phase is also formed, of which the organic phase contains the fatty acid ester.
• the fatty acid can be used as such or a fatty acid ester, suitable for biodiesel, can be formed therefrom using a monohydric short-chained alcohol by treating the fatty acid with said alcohol.
• a monohydric short-chained alcohol by treating the fatty acid with said alcohol.
• the invention comprises a process based on mainly natural steps, by which a long-chained fatty acid or a fatty acid ester is produced from an organic soap or mixtures thereof.
• long-chained means a hydrocarbon chain of at least C 4 , i.e. a hydrocarbon chain, having at least 4 carbon atoms.
• the hydrocarbon chain has a length of C] 0 to C 20 , more preferably C 12 to C 2 o.
• the process of the invention comprises the steps of:
• the method comprises the steps of optionally adding acid, preferably an organic acid, more preferably acetic acid, formic acid or lactic acid, to the starting material to adjust the pH to a value of 3 to
• a metal-ion forming agent such as mineral salt of an alkali earth metal, preferably an agent that forms Ca 2+ or Mg 2+ , more preferably calcium chloride or magnesium chloride, most suitably calcium chloride, to the mixture as a solid or as an aqueous solution, in an amount that precipitates at least 40% of the soap, preferably in an amount, using which a stoichiometric amount of metal-ion is formed with regard to the amount of soap, most preferably a 5 to 10% by weight stoichiometric excess, whereby an insoluble phase and a liquid phase are formed, wherein the insoluble phase comprises the soap and the liquid phase comprises the polyhydric alcohol, preferably glycerol, and the monohydric alcohol, preferably methanol, ethanol or 1 -propanol, most suitably methanol, or a mixture thereof, separating the insoluble phase, where the soap has been transformed into an insoluble soap, from the first liquid phase, preferably
• a metal-ion forming agent such
• a mixture which is a fraction formed as a result of the transesterification of a lipid, is used as a starting material in the process.
• the molar amount of the monohydric alcohol to be added to the fatty acid fraction with regard to the molar amount of the organic matter is at least 40%, preferably an equivalent amount.
• the invention contains the steps, wherein the optional solid matter components are removed from the starting material by filtering. After this, the acidity of the starting material is adjusted using a necessary amount of an acid, preferably acetic acid, formic acid or lactic acid, most suitably acetic acid.
• an acid preferably acetic acid, formic acid or lactic acid, most suitably acetic acid.
• the soluble soap present in the filtered starting material is transformed into an insoluble soap by adding a metal-ion forming agent to the mixture, preferably a mineral salt of a bivalent alkali earth metal, more preferably a mineral salt of Ca 2+ , most preferably CaCl 2 .
• a metal-ion forming agent preferably a mineral salt of a bivalent alkali earth metal, more preferably a mineral salt of Ca 2+ , most preferably CaCl 2 .
• the salt is added as a solid, whereby significant amounts of water can be avoided.
• the mixing time is controlled, until the formation of the precipitate has essentially stopped.
• a moist "soap cake” remains, which according to a particularly preferred embodiment is dried, after which mostly 5% by weight, preferably 0.1 to 4% by weight, most suitably 0.1 to 2.5% by weight of water remains in the precipitate.
• the insoluble fraction (precipitate) formed is separated from the liquid fraction by filtering or by decanting or by other methods generally used for recovering a precipitate.
• An acid treatment is carried out for the insoluble fraction, preferably by using hydrochloric acid as an aqueous solution, most suitably in a concentration of 0.5 to 10%. Acid is added in an amount that is sufficient to release the fatty acids.
• the acid treatment and the esterification are carried out as an acid catalyzed esterification or by gradually esterifying.
• an HCl-methanol treatment is performed on the soap precipitate at a temperature exceeding the boiling point of methanol, more preferably at over 65°C, most suitably at 80°C.
• the second phase i.e. the organic phase
• the phase containing the salt formed in the esterification into the starting material.
• the aqueous solution containing mineral salts released in the esterification can be recycled to the step of mineral salt treatment of the soap.
• the compounds that are added in the different steps of the process do not leave the process totally, but they are preferably recycled internally in the process or they form separate economically utilizable fractions and thus improve the total economics of the process.
• the produced fatty acid is used for manufacturing alcohol esters of fatty acids. More preferably, these fatty acid esters and the fatty acid esters produced by means of the invention are used further in manufacturing biofuels, such as biodiesel.
• the product of the present invention is suitable as a feed in the esterification of fatty acids or in processes, where plant or animal based lipids are hydrotreated, particularly as a feed in processes, where so called HVO ("hydrogenated vegetable oil”) is manufactured.
• the esters of the invention are used in manufacturing biodiesel or renewable diesel.
• the fatty acids can be used for other fuels, analogous to diesel.
• the starting material used in the process of the present invention is preferably obtained, e.g. from the methanol-containing glycerol fraction generated in the manufacturing of biodiesel, which generally contains at least about 2 to 10% of soap. Since water causes the formation of soap in the transesterification, its presence in the present invention is not detrimental, but in the aforementioned transesterification the amounts of water and a monohydric alcohol are minimized. Less than 20%, preferably 2 to 10%, of water is released into said methanol-containing glycerol fraction. This water content is preferred in the starting material used in the process of the present invention.
• Biodiesel means, according to the EU-directive 2003/30/E Y "a methyl-ester produced from vegetable or animal oil, of diesel quality to be used as biofuel". Thus, biodiesel consists of fatty acid esters.
• microbe fat means a fat that is derived from bacteria, yeast, mould, alga or other microorganism.
• Both the fatty acids and the fatty acid esters formed in the invention can be utilized for the manufacturing of biofuels. They can be used as such or they can be blended with other components, or the acid or ester structures can be degraded using methods known in the art and the double bonds can be saturated, whereby an n-paraffin product is obtained, which on the other hand can be mixed into the other components.
• Example 1 The manufacturing of fatty acid esters
• Example 2 The manufacturing of fatty acids and their esterification
• the mixture was heated to 62°C and the surface layer containing fatty acids was separated therefrom.
• the salts were removed from the layer through washing with water, after which the water remaining in the layer after the wash as well as the water formed with the fatty acids was removed by drying using a dehydrating agent, whereby the fatty acids remained.
• Both the obtained fatty acid mixture and the corresponding fatty acid ester mixture are well suited, for example, for the manufacturing of diesel fuels.

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

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• 2007
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  • 2008-09-05 EP EP08805418A patent/EP2188356A1/en not_active Withdrawn
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