WO2009075762A1 - Procédé de fabrication de biodiesel et d'esters d'acides gras - Google Patents

Procédé de fabrication de biodiesel et d'esters d'acides gras Download PDF

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Publication number
WO2009075762A1
WO2009075762A1 PCT/US2008/013354 US2008013354W WO2009075762A1 WO 2009075762 A1 WO2009075762 A1 WO 2009075762A1 US 2008013354 W US2008013354 W US 2008013354W WO 2009075762 A1 WO2009075762 A1 WO 2009075762A1
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Prior art keywords
catalyst
reaction
reactor
reagent
fatty acid
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PCT/US2008/013354
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English (en)
Inventor
Xiangsheng S. Meng
Paraskevas Tsobanakis
Ian C. Purtle
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Cargill, Incorporated
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Publication of WO2009075762A1 publication Critical patent/WO2009075762A1/fr

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    • 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
    • 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

Definitions

  • the invention discloses a method for the manufacturing of a fatty acid ester.
  • the ester is manufactured in a reaction between a fatty acid source and at least one reagent, which are of limited mutual solubility. More specifically, the reaction is conducted in a reactor involving at least two tubes, wherein at least one of said tubes spins relatively to the other.
  • FAME fatty acids methyl esters
  • biodiesel is manufactured by trans-esterification of vegetable oil with methanol and is catalyzed by a basic catalyst. Since the oil and methanol are of limited mutual miscibility, the reaction takes place in a two-phases system and is therefore slow.
  • reaching high oil conversion yield requires multiple steps, long residence time in the range of hours, elevated temperatures, large excess of methanol and a strong basic catalyst, such as sodium methoxide.
  • reaction mixture contains biodiesel, unreacted methanol and glycerol byproduct.
  • Glycerol has limited solubility in biodiesel so that settling forms two phases, a more lipophilic (and lighter) one containing essentially the biodiesel and a hydrophilic (heavier) one with the glycerol.
  • Phase separation is slow, typically of several hours, requiring large settler volume, which adds to the investment cost.
  • the unreacted methanol is separated, typically by distillation, and recycled to the reaction.
  • the base catalyst in the hydrophilic phase has to be neutralized and removed.
  • the lighter biodiesel phase is washed by acidic water solution (adding hydrochloric acid)) after separation from the heavier glycerol phase to remove the excess methanol and a small amount of dissolved base catalyst and glycerol.
  • the water washing solution is combined with the glycerol phase and reacted with hydrochloric acid to neutralize the base catalyst there.
  • the methanol in the glycerol phase is recovered by evaporation and recycled back to the biodiesel production.
  • water in the glycerol phase is evaporated, followed by the glycerol distillation to reject the salts formed on catalyst neutralization (e.g. NaCl or KCl) and other impurities.
  • catalyst neutralization e.g. NaCl or KCl
  • the whole glycerol purification process is a highly-energy intensive, highly corrosive and therefore a costly process.
  • the usage of HCl to neutralize the base catalyst requires all mixing tanks, pipes and distillation columns to be made from high-cost and corrosion-resistant materials such as titanium.
  • An objective of the present invention is an improved process for the manufacturing of fatty acid esters for applications such as in biodiesel. More specifically, the objective is manufacturing such esters at reduced cost, e.g. as a result of shorter reaction time, operating at lower temperatures, consumption of less and/or cheaper catalyst, possibly via catalyst recovery and producing high quality coproducts.
  • fatty acid esters are manufactured in a reaction between a fatty acid source and at least one reagent, the method being characterized in that the source and the reagent are of limited mutual solubility and in that said reacting is conducted in a reactor involving at least two tubes, wherein at least one of said tubes spins relatively to the other.
  • the method involves the steps of (a) forming in the reactor a reaction medium comprising the fatty acid source and a reagent; (b) spinning at least one of the tubes for a reaction time to generate a product medium; (c) removing product medium from the reactor, and (d) separating the removed product medium into at least one lipophilic phase and at least one hydrophilic phase.
  • the fatty acid source is selected from a group consisting of triglycerides, diglycerides, monoglycerides, free fatty acids, fatty acid salts and phospholipids, preferably triglyceride.
  • the reagent is selected from a group consisting of alcohols with single or multiple hydroxyl functions and their esters, hydroxycarboxylic acids and their esters, hydroxyamines and their esters and mixtures thereof.
  • the reagent is water soluble, preferably methanol, ethanol and their mixtures.
  • the reaction medium comprises a catalyst.
  • Suitable catalysts include basic compounds, but not limited to, alkaline metal hydroxides and carbonates such as sodium hydroxide and carbonate, potassium hydroxide and carbonate, alkaline metal alcoholates such as sodium methoxide and ethoxide, potassium methoxide and ethoxide, alkaline earth metal hydroxides and oxides, such as magnesium, calcium, strontium and barium hydroxides, magnesium, calcium, strontium and barium oxides, barium alcoholates such as barium methoxide and ethoxide, ammonia, ammonium hydroxide, alkylammonium hydroxide, amines, zeolites, and their combinations.
  • the reaction time is less than 10 seconds.
  • the preferred reaction temperature is in the range between about 2O 0 C and about 6O 0 C.
  • the concentration of the catalyst in the reaction medium is in a range between about 0.1 and about 10 percent.
  • the molar ratio between the source and the reagent is in the range between about 1 and about 10.
  • separating the product medium into two phases is essentially completed within about 60 minutes.
  • the catalyst used is volatile, and the method also includes the steps of separating unreacted reagent by distillation, separating catalyst by distillation, and recycling both to the reactor.
  • catalyst recycle uses reaction with carbon dioxide to form a carbonate, a bicarbonate or their combination.
  • the catalyst used is solid, separating catalyst by filtration and/or centrifugation, and recycling to the reactor.
  • the catalyst used is basic compound, removing and separating catalyst uses reaction with carbon dioxide to form a carbonate, a bicarbonate or their combination.
  • the catalyst used is basic compound, removing and separating catalyst uses reaction with sulfuric acid to form a sulfate.
  • the reaction product is a methyl or an ethyl ester of fatty acid and meeting ASTM specification for biodiesel.
  • the present invention discloses a method for manufacturing of fatty acid esters, e.g. methyl esters, ethyl esters or their combinations. Also suitable are esters of fatty acids with polyols, such as glycerol, ethylene glycol and propylene glycol. Also suitable are esters of fatty acids with hydroxy-carboxylic acids.
  • the method involves reacting a fatty acid source with at least one suitable reagent. Particularly desired are products that meet the ASTM specifications for biodiesel. One of ASTM the specifications is total glycerol in biodiesel less than 0.25%.
  • a characteristic of the method of the present invention is that the fatty acid source and the reagent are of limited mutual solubility. This means that, on mixing the fatty acid source with the reagent in the weight/weight (or molar) ratios and at the temperature selected for the reaction, at least two phases are observed. Typically, at least two of the observed phases are liquid at the reaction temperature, but a solid phase and/or a vapor phase are also optional.
  • Another characteristic of the method of the present invention is that the reaction is conducted in a reactor involving at least two tubes, wherein at least one of said tubes spins or rotates relatively to the other.
  • a specific example of such reactor is the Spinning Tube in Tube (STTTM) reactor as disclosed in US Patents 5,279,463, 5,538,191, 6,471,392, 6,723,999, 6,742,774, 6,752,529 and 6,994,330 and Patent Applications 20040013587, 20040052158 and 20050033069 incorporated here by reference and as manufactured by Kreido Laboratories.
  • the method involves the following steps: (a) forming in the reactor a reaction medium comprising the fatty acid source, the reagent and optionally also a catalyst; (b) spinning at least one of the tubes for a reaction time to generate a product medium; (c) removing product medium from the reactor, and (d) separating a product from the removed product medium.
  • free fatty acids, their salts, various mixtures of those, their esters and their amides, those include acids with additional functional groups, e.g. dicarboxylic acids and carboxylic acids carrying hydroxyl, carboxyl and/or amino functions are suitable fatty acid sources.
  • suitable sources include triglycerides, diglycerides, monoglycerides, free fatty acids, fatty acid salts and phospholipids.
  • the preferred fatty acid sources are triglyceride, such as oils and fats.
  • Suitable oils include, but not limit to, soybean oil, rapeseed oil, corn oil, sunflower oil, linseed oil, cottonseed oil, peanut oil, palm oil, palm kernel oil, oak oil, almond oil, apricot oil, walnut oil, babassu oil, perilla oil, oiticica oil, castor oil, olive oil, safflower oil, canola oil, groundnut oil, sesame oil, coconut oil, and etc.
  • Suitable fats include animal fat, beef tallow, chicken oil, sheep oil, lard, suet, goose fat, fish oil, milk fat, butterfat, and etc.
  • oil or fat is provided and is hydrolyzed prior to the reaction with the reagent.
  • Hydrolysis forms glycerol and free fatty acids, which are separated by known methods, such as decantation, centrifugation or extraction (free fatty acids and glycerol are of very small mutual solubility).
  • the hydrolysis also referred to as oil/fat splitting, can be catalyzed chemically (e.g. using acid as a catalyst) or biologically (e.g. using a lipase). Alternatively, the hydrolysis is conducted at somewhat higher temperatures with no need for catalyst usage.
  • the formed free acids are used as sources in the reaction of the present invention.
  • the embodiment of using no catalyst and that of using a biological catalyst have an advantages over those of using a chemical catalyst and that of manufacturing the fatty acid esters by direct reaction between oil/fat and a reagent.
  • the main advantage is forming a much more pure glycerol coproduct, saving on its purification cost.
  • hydrolysis of fat/oil to generate free fatty acid and glycerol of high purity is conducted in a spinning-tube reactor, e.g. similar to the one used for the reaction between the fatty acid source and the reagent.
  • Suitable reagents include organic molecules carrying at least one hydroxyl function and products of such molecules, such as esters. Examples of suitable reagents include monohydric alcohols, such as methanol, ethanol, propanol, iso-propanol, butanol, sec-butanol and tert-butanol.
  • suitable alcohols are polyhydric ones, such as ethylene glycol, propylene glycol, glycerol, erythritol, inositols and sugar alcohols. Esters of such monohydric and polyhydric alcohols are also suitable. Also suitable are hydroxycarboxylic acids, such as glycolic, lactic and 3-hydroxy propionic acid and their esters. Other suitable reagents include hydroxyamines, hydroxy amino acids and their derivatives. Mixtures of such reagents are also suitable. In many of the processes the reagent is water soluble, preferably methanol, ethanol and their mixtures. Water-soluble reagents can reach in water at 25C concentrations of at least 15% by weight.
  • the reaction medium comprises a catalyst.
  • Suitable catalysts include basic compounds, but not limited to, alkaline metal hydroxides and carbonates such as sodium hydroxide and carbonate, potassium hydroxide and carbonate, alkaline metal alcoholates such as sodium methoxide and ethoxide, potassium methoxide and ethoxide, alkaline earth metal hydroxides and oxides, such as magnesium, calcium, strontium and barium hydroxides, magnesium, calcium, strontium and barium oxides, barium carbonate, barium alcoholates such as barium methoxide and ethoxide, ammonia, ammonium hydroxide, alkylammonium hydroxide, amines, compounds carrying amine, amide and/or pyrrolidone functions, zeolites, and their combinations.
  • Suitable catalysts are either hydrophilic (water and alcohol soluble, such as alkaline metal hydroxides) or lipophilic (e.g. organic amines).
  • the catalyst could be introduced in any form, e.g. in liquid or solid form.
  • Suitable solid catalysts also include basic metal oxides and resins.
  • An important advantage of the method of the present invention is that the reaction can be conducted at relatively low temperatures, where practically any basic resin is stable. Obviously, resins of high thermal stability, such as Reillex, are also suitable.
  • the inventors have surprisingly found that catalysts which are not working well in conventional method (producing many undesirable byproducts) are suitable in the method of the present invention, e.g. metal hydroxides. Such catalysts are of considerably lower cost than those used in conventional methods, e.g. metal methoxides.
  • the method of the present invention enables further reduction of catalyst-related cost by minimizing or avoiding the need of neutralization and by enabling catalysts recycle, as explained in the following.
  • any concentration of catalyst that facilitates the reaction is suitable.
  • the inventors have surprisingly found that, in the process of the present invention, high reaction rates are obtained at relatively low concentrations of catalyst.
  • the preferred catalyst concentration depends on the fatty acid source, on the reagent, on the selected catalyst and on the reaction medium, e.g. solvent if used, and reaction conditions, e.g. temperature.
  • Typical suitable catalyst concentrations in the reaction medium for reacting oils and methanol are in a range between about 0.1 and about 1 percent for alkaline metal hydroxides.
  • a particularly advantage is process embodiments wherein fatty acid esters such as biodiesel can be formed in so short reaction time such as 1 second or less from the fatty acid source such as soybean oil, the reagent such as methanol or ethanol and a metal hydroxide catalyst in the spinning tube reactor.
  • catalyst does not exist in the product medium exiting the reactor or is easily separated from that product medium.
  • One objective is saving on catalyst cost by recycling catalyst to the reaction medium, optionally after some purification or bleeding to avoid impurities build up.
  • Another objective is minimizing contamination with the catalyst. Such contamination could be of the product ester, the coproduct, e.g. glycerol, or both.
  • the catalyst is hydrophilic in nature and accumulates in the hydrophilic phase formed on separation of the product medium.
  • the hydrophilic phase is a glycerol-containing medium and the catalyst concentrates in that medium.
  • the basic catalyst is neutralized at the end of the reaction, e.g. with an acid to form a salt. Since the glycerol molecular weight is small compared with that of the oil, the weight ratio between the catalyst (or its neutralization product) and the glycerol is relatively high so that the glycerol is contaminated with relatively large concentration of catalyst. That is particularly problematic when the coproduct is intended for use, e.g.
  • glycerol as such or as a starting material for other compounds, such as glycols, acrylic acid, glyceric acid, etc.
  • Several embodiments of the method of the present invention minimize or avoid these difficulties, saving on catalyst cost, catalyst neutralization cost and product/coproduct purification.
  • the catalyst is bound to at least one surface of the reactor that comes in contact with the fatty acid source, the reagent or both and is kept thereby in the reactor. Binding could use, e.g. glue or a layer of polymeric binder.
  • the catalyst is insoluble in the product medium and is separated from the product medium at the end of the reaction, e.g. by means of filtration or centrifugation.
  • an insoluble catalyst is kept in the reactor, e.g. by means of a filter during the removal of the product medium at the end of the reaction.
  • An insoluble catalyst according to the present invention is a catalyst with less than 5% weight in glycerol at 25C.
  • the catalyst is of high molecular weight, e.g. a polyamine and is separated by means of membrane separation, e.g. ultrafiltration, from the product medium, from the lipophilic phase, and/or from the hydrophilic phase.
  • said high molecular weight catalyst has a molecular weight of at least about 3,000 Dal tons.
  • the catalyst is volatile, e.g. having, at a given temperature, partial vapor pressures lower than those of the manufactured esters and/or lower than those of coproduct glycerol.
  • volatile catalysts are ammonia and low molecular-weighty amines.
  • a volatile catalyst is used and the method comprises a step of distilling catalyst from the product medium at the end of the reaction.
  • the reagent used in the reaction is volatile and is used in excess.
  • the unreacted reagent is separated from the product medium, e.g. by distillation.
  • both the catalyst and the reagent are volatile and both are separated from the product medium by distillation, either simultaneously or sequentially.
  • both the volatile catalyst and the volatile excess reagent are recycled to the reaction medium, preferably together.
  • the catalyst is absorbed on an absorbent and is recovered from the absorbent and recycled to the reaction of the present invention.
  • the absorbed catalyst is recycled with the absorbent to the reaction of the present invention.
  • the catalyst is neutralized at the end of the reaction with CO2, rather than with a strong mineral acid, such as hydrochloric acid.
  • a carbonate salt, a bicarbonate salt or a mixture of those is formed.
  • at least part of the formed salt precipitates out of the product medium or out of the hydrophilic phase formed on separating the product medium and is separated as such.
  • separation of catalyst in that way improves with increasing the concentration of the C02-treated medium. Separation of the salt forms a purer product, coproduct or both. This embodiment also saves on the cost of the neutralizing mineral acid.
  • the separated carbonates and/or bicarbonate have commercial value for various applications.
  • a bicarbonate salt is heated and converted to a carbonate of higher basicity (and CO2 that could be reused for catalyst neutralization).
  • the carbonate formed on CO2 treatment is of an alkaline metal and is reacted after separation with an oxide or hydroxide of an alkaline earth metal.
  • a carbonate of an alkaline earth metal and a hydroxide of the alkaline metal are formed.
  • the hydroxide is used as a catalyst as such or after modification, e.g. conversion to methoxide.
  • the carbonate according to another preferred embodiment, is heat treated and converted into CO2 and hydroxide of the alkaline earth metal for reuse.
  • the catalyst is neutralized at the end of the reaction with sulfuric acid, rather than with hydrochloric acid.
  • An insoluble sulfate salt is formed and is separated from the product medium e.g. by means of filtration or centrifugation.
  • any of the above-listed alternative embodiments costs related to catalyst neutralization and purchase are minimized or substantially avoided.
  • Some of those embodiments are characterized in that the hydrophilic phase formed after phase separating the reaction phase is essentially free of catalyst or have a less catalyst.
  • Other embodiments are characterized in that such essentially catalyst free hydrophilic phase is formed by a method other than glycerol distillation. The use of high cost material of construction, typical to the conventional process, is avoided since hydrochloric acid is not used for neutralization and since distillation from chloride solution is not required.
  • the hydrophilic phase can be purified by distillation in the presence of the formed carbonate, bicarbonate or a mixture of carbonate and bicarbonate.
  • the use of high cost material of construction, typical to the conventional process, is avoided since hydrochloric acid is not used for neutralization and since distillation from chloride solution is not required.
  • the inventors have surprisingly found that the rate of reaction conducted according to the embodiments of the present invention is much higher than the reaction conducted in presently known methods. Thus, while a typical time of reaction conducted by conventional methods is about hours, it typically approaches completion in the method of the present invention in less than 10 seconds, more preferably less than 5 seconds, most preferably less than 1 second.
  • the inventors have also found that, according to the present invention, high conversion yields are reached at relatively low temperatures.
  • the preferred reaction temperature is in the range between about 2O 0 C and about 6O 0 C.
  • a typical temperature of reaction conducted by conventional methods is 6O 0 C and above, it typically approaches completion in the method of the present invention at temperatures lower than 6O 0 C, more preferably lower than 4O 0 C, most preferably at room temperature or below than 25 0 C.
  • Conducting the reaction at reduced temperature has an important advantage in saving on energy cost. In particular cases, an even more important advantage is minimizing the amount of degradation products formed during the reaction. This leads to higher yields and lower purification costs.
  • a known method in case of reactions reaching equilibrium, is to use one of the reactants in excess to achieve high yields of converting the other reactant.
  • the formed product medium is then processed to remove the excess reactant for recycling to reaction and for product purification.
  • excess methanol is used on production of biodiesel in a reaction between triglycerides and methanol.
  • methanol excess methanol is used on production of biodiesel in a reaction between triglycerides and methanol.
  • excess methanol is used on production of biodiesel in a reaction between triglycerides and methanol.
  • about 6 to 24 moles of methanol are used per mole of triglyceride (excess of about 100 to 700 percents).
  • the inventors have surprisingly found that, in the method of the present invention much lower excess is required, which saves on the cost of further treatment, e.g. by methanol distillation from the product medium.
  • typically 6 moles or less of reagent are used
  • the method of the present invention has the following advantages, among others. It saves on catalyst consumption, uses catalysts of lower cost and saves on costs related to catalyst neutralization and separation. It is conducted at temperatures lower than in alternative methods, saving on energy cost and minimizing reagents degradation, which also saves on purification costs. It doesn't require high excess of the reagents, saving thereby on costs related to product purification and reagent recycle. Reaction duration is much shorter than in conventional processes. Yet, all those improvements are achieved without compromising on conversion yields.
  • a typical conversion yield in the process of the present invention is at least about 95%, more preferably at least about 97%, most preferably at least 99%.
  • a characteristic of the invention is that the fatty acid source and the reagent are of limited mutual solubility.
  • the reaction product, the fatty acid ester, and coproduct are also of limited miscibility.
  • the product is a fatty acid methyl ester and the coproduct is glycerol.
  • the former is of low hydrophilicity, while the latter is highly hydrophilic.
  • the reagent is used in excess so that part of it is left in the product medium at the end of the reaction.
  • the reagent is also hydrophilic and of low miscibility with the reaction product.
  • the product medium is typically separated into two phases, both of them are liquid in most cases.
  • phase separation is relatively slow, requiring long residence time and therefore large and expensive settling vessels.
  • centrifugation could be used at added cost, particularly since explosion proof equipment is typically required.
  • the inventors have surprisingly found that, in conducting the reaction according to the method of the present invention, phase separation is rapid.
  • the phases in the method of the present invention are typically separated in less than about 30 minutes, more preferably in less than about 20 minutes, most preferably less than about 10 minutes.
  • the present invention provides a methyl or an ethyl ester of fatty acid meeting ASTM specification for biodiesel.
  • TMS trimethylsilane
  • GC cool on-column
  • DB-5HT non-polar column stationary phase
  • FID flame ionization detector
  • the temperature program was 110 0 C (0.2 min) to 14O 0 C at 30°C/min to 340 0 C at 10°C/min (10 min).
  • Hydrogen was the carrier gas, and inlet pressure was 6.7 psi at 1 10 0 C in the constant flow mode.
  • the detector temperature was 370 0 C. Samples were analyzed a single time.
  • the base catalyst NaOH, KOH, NaOMe or amines
  • the soybean oil was preheated to the same temperature as one set for the STTTM reactor before pumping into the STTTM reactor.
  • the soybean oil and the catalyst containing methanol (or ethanol) streams were pumped into the reactor using syringe pumps. About 100-500 ml samples were collected for each experiment. The most samples collected from the reactor were settled for about 2 hours to have a clear phase separation.
  • the top biodiesel phase was taken for water washing (about a 2:1 phase ratio of biodiesel to water) to remove the contained methanol, catalyst and glycerol, and also to stop further transesterification reaction.
  • the washed biodiesel was then centrifuged for 10 minute at 4000 rpm. The clean biodiesel after centrifuge was taken for further analysis by GC.
  • the reaction temperature varied from 25 0 C to 6O 0 C.
  • the reaction time varied from 2 seconds to 10 seconds.
  • Two feed streams of soybean oil and methanol with dissolved catalyst were pump into the reactor at one end of the STTTM reactor by two syringe pumps.
  • the reaction product was collected in another end of the reactor.
  • Two phases (biodiesel and glycerol) in the product stream were separated in about 10 minutes after exiting the reactor. Both phases have the light yellow colors (same as the color).
  • the top phase was taken for analysis of biodiesel composition.
  • the glycerol phase was not analyzed.
  • the biodiesel samples collected in this set of experiments were not treated by water wash. The samples were analyzed by GC several days later.
  • a conversion to biodiesel from triglyceride may be little higher than the real conversion when the samples were treated by water wash to stop the further reaction.
  • the Table 1 shows the reaction conditions and results of the biodiesel production from soybean oil and methanol with the base catalysts using the STTTM reactor.
  • biodiesel produced in the STTTM reactor meets ASTM specification if 1% NaOH is used as a catalyst at either 6O 0 C for 0.5 sec residence time or 25 0 C for 1.0 sec residence time (Examples 23, 24, and 27). It was also confirmed that the rotation varying form 9000 rpm to 12000 rpm of the STTTM reactor has no effect or a little effect on the biodiesel production. The gap varies from 0.0125 inch to 0.0240 inch between the rotor and the stator of the STTTM reactor has no effect on biodiesel production (Examples 23, 38, 40 and 42).
  • the biodiesel production using the STT M reactor having a gap of 0.024 inch can produce more than 2 times biodiesel than the reactor having 0.0125 inch if the rest of the reaction conditions remain the same.
  • FEE fatty acid ethyl ester
  • the ethyl ester biodiesel produced by the STTTM reactor also meets the ASTM specification if 1 % NaOH is used as a catalyst at either 6O 0 C for 0.5 sec residence time or 25 0 C for 1.0 sec residence time (Examples 26 and 41).
  • sample was washed Ih 50 ⁇ iin later than sample 26

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Abstract

Selon l'invention, les esters d'acides gras sont fabriqués au cours de la réaction entre une source d'acides gras et au moins un réactif. La source et le réactif sont de solubilité mutuelle limitée. La réaction est conduite dans un réacteur faisant intervenir au moins deux tubes. Au moins l'un des tubes tourne par rapport à l'autre. La réaction peut comprendre la rotation d'au moins l'un des tubes pendant un temps de réaction pour générer un milieu de produit, l'élimination du milieu de produit du réacteur et la séparation du milieu de produit éliminé en au moins une phase lipophile et au moins une phase hydrophile.
PCT/US2008/013354 2007-12-11 2008-12-04 Procédé de fabrication de biodiesel et d'esters d'acides gras WO2009075762A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
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CN103476277A (zh) * 2011-04-18 2013-12-25 R.J.雷诺兹烟草公司 从烟草生产甘油的方法
WO2015050656A3 (fr) * 2013-08-30 2015-06-04 Inventure Renewables, Inc. Méthodes et procédés industriels permettant de générer des acides gras libres et des dérivés de ceux-ci à partir de gommes à base d'huiles
US20150201669A1 (en) * 2014-01-17 2015-07-23 R.J. Reynolds Tobacco Company Process for producing flavorants and related materials
WO2015196243A1 (fr) * 2014-06-26 2015-12-30 Flinders University Of South Australia Fabrication de biodiesel
US9289011B2 (en) 2013-03-07 2016-03-22 R.J. Reynolds Tobacco Company Method for producing lutein from tobacco
EP2454225A4 (fr) * 2009-07-14 2017-06-14 Ceramatec, Inc. Systèmes et procédés permettant l élimination d un catalyseur et la récupération d acides carboxyliques libres à partir d une réaction de transestérification
CN107586622A (zh) * 2016-07-08 2018-01-16 乔治·克劳德方法的研究开发空气股份有限公司 通过酯水解制备脂肪酸的方法
US10499684B2 (en) 2016-01-28 2019-12-10 R.J. Reynolds Tobacco Company Tobacco-derived flavorants
US10881133B2 (en) 2015-04-16 2021-01-05 R.J. Reynolds Tobacco Company Tobacco-derived cellulosic sugar
US11091446B2 (en) 2017-03-24 2021-08-17 R.J. Reynolds Tobacco Company Methods of selectively forming substituted pyrazines

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Cited By (15)

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Publication number Priority date Publication date Assignee Title
EP2454225A4 (fr) * 2009-07-14 2017-06-14 Ceramatec, Inc. Systèmes et procédés permettant l élimination d un catalyseur et la récupération d acides carboxyliques libres à partir d une réaction de transestérification
CN103476277A (zh) * 2011-04-18 2013-12-25 R.J.雷诺兹烟草公司 从烟草生产甘油的方法
US9458476B2 (en) 2011-04-18 2016-10-04 R.J. Reynolds Tobacco Company Method for producing glycerin from tobacco
US9289011B2 (en) 2013-03-07 2016-03-22 R.J. Reynolds Tobacco Company Method for producing lutein from tobacco
WO2015050656A3 (fr) * 2013-08-30 2015-06-04 Inventure Renewables, Inc. Méthodes et procédés industriels permettant de générer des acides gras libres et des dérivés de ceux-ci à partir de gommes à base d'huiles
US10188137B2 (en) 2014-01-17 2019-01-29 R.J. Reynolds Tobacco Company Process for producing flavorants and related materials
US9265284B2 (en) * 2014-01-17 2016-02-23 R.J. Reynolds Tobacco Company Process for producing flavorants and related materials
US20150201669A1 (en) * 2014-01-17 2015-07-23 R.J. Reynolds Tobacco Company Process for producing flavorants and related materials
WO2015196243A1 (fr) * 2014-06-26 2015-12-30 Flinders University Of South Australia Fabrication de biodiesel
US10881133B2 (en) 2015-04-16 2021-01-05 R.J. Reynolds Tobacco Company Tobacco-derived cellulosic sugar
US10499684B2 (en) 2016-01-28 2019-12-10 R.J. Reynolds Tobacco Company Tobacco-derived flavorants
CN107586622A (zh) * 2016-07-08 2018-01-16 乔治·克劳德方法的研究开发空气股份有限公司 通过酯水解制备脂肪酸的方法
EP3266857B1 (fr) * 2016-07-08 2020-01-01 L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude Procédé de fabrication d'acides gras par hydrolyse utilisant dans l'eau à haute température
US11091446B2 (en) 2017-03-24 2021-08-17 R.J. Reynolds Tobacco Company Methods of selectively forming substituted pyrazines
US11891364B2 (en) 2017-03-24 2024-02-06 R.J. Reynolds Tobacco Company Methods of selectively forming substituted pyrazines

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