EP3266857A1 - Procédé de fabrication d'acides gras par hydrolyse utilisant dans l'eau à haute température - Google Patents

Procédé de fabrication d'acides gras par hydrolyse utilisant dans l'eau à haute température Download PDF

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Publication number
EP3266857A1
EP3266857A1 EP16400026.7A EP16400026A EP3266857A1 EP 3266857 A1 EP3266857 A1 EP 3266857A1 EP 16400026 A EP16400026 A EP 16400026A EP 3266857 A1 EP3266857 A1 EP 3266857A1
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EP
European Patent Office
Prior art keywords
fatty acid
product
separation
phase
methanol
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP16400026.7A
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German (de)
English (en)
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EP3266857B1 (fr
Inventor
Ingo Bauer
Peter PÖTSCHACHER
Armin Brandner
Günter Bräuner
Matthias Kasper
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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 LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority to EP16400026.7A priority Critical patent/EP3266857B1/fr
Priority to PCT/EP2017/025181 priority patent/WO2018007022A1/fr
Priority to BR112019000037-2A priority patent/BR112019000037A2/pt
Priority to US16/316,248 priority patent/US10696922B2/en
Priority to MYPI2018002995A priority patent/MY197420A/en
Priority to SG11201811694XA priority patent/SG11201811694XA/en
Priority to CN201710550533.0A priority patent/CN107586622B/zh
Priority to CN201720825169.XU priority patent/CN207468571U/zh
Publication of EP3266857A1 publication Critical patent/EP3266857A1/fr
Priority to PH12019500013A priority patent/PH12019500013A1/en
Priority to CONC2019/0001040A priority patent/CO2019001040A2/es
Application granted granted Critical
Publication of EP3266857B1 publication Critical patent/EP3266857B1/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
    • 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
    • C11C1/04—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis
    • 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
    • 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

Definitions

  • the invention relates to a process for the preparation of fatty acids by hydrolytic cleavage of fatty acid alkyl esters, in particular fatty acid methyl esters (FAME), or alternatively of fatty acids in plant and animal origin contained in oils and fats, at high temperature and high pressure in the liquid phase without the addition of external, foreign substances as homogeneous or heterogeneous catalysts, as well as the workup of the obtained cleavage product to free fatty acids.
  • FAME fatty acid methyl esters
  • the invention further relates to a system for carrying out the method.
  • the reverse reaction of the esterification is the so-called ester cleavage or ester hydrolysis.
  • ester cleavage one mole of water is consumed per mole of ester bond, with one mole of free acid and alcohol being formed in each case.
  • hydrolysis is also an equilibrium reaction.
  • triglycerides are hydrolytically split with the addition and consumption of water at temperatures of 200 ° C and higher and corresponding water vapor pressure in the liquid phase in glycerol and free fatty acids (FFA).
  • FFA free fatty acids
  • the patent publication describes DE 69321607 T2 operated at ambient pressure cleavage of a FAME mixture of methyl caprylate and methyl capronate in the range of 70 to 110 ° C, wherein an acidic, homogeneously dissolved catalyst comprising alkylbenzenesulfonic acids, is used.
  • an acidic, homogeneously dissolved catalyst comprising alkylbenzenesulfonic acids
  • Also described here is a work-up by distillation of the reaction mixture under reduced pressure, methanol, water and unreacted being used in a first stage Fatty acid methyl ester is removed. In a second stage, the FFA product is then separated from the catalyst and this recycled back into the reaction system.
  • the catalyst separation is indeed simplified, but the conversions described in comparison to the achieved conversions in homogeneous catalysis (sulfuric acid, toluene-p-sulfonic acid) significantly lower or it will be high concentrations of, for example, 12 up to 27 g of ion exchanger per 100 g of FAME needed to achieve high sales in a reasonable time.
  • the added propionic acid must be finally removed from the reaction mixture.
  • the present invention is therefore based on the object of providing a very simple process for the preparation of fatty acids by hydrolytic cleavage of fatty acid alkyl esters at high temperature and high pressure in the liquid phase without the addition of external substances foreign to the process as homogeneous or heterogeneous catalysts, in which the above-mentioned disadvantages not or only to a minor extent occur.
  • Hydrolysis conditions are understood as meaning those reaction conditions which bring about at least partial conversion, preferably a technically or economically relevant conversion, of the fatty acid alkyl esters or of the fatty acid triglycerides to free fatty acids.
  • the person skilled in the art will know hydrolysis conditions known from the prior art and, if appropriate, modify it on the basis of routine experiments in order to adapt it to other boundary conditions of process execution.
  • phase separation conditions are understood as meaning all physico-chemical parameters which enable, favor or accelerate the formation of the two liquid phases obtained from the cleavage product.
  • Important parameters in this context are the temperature and the strength of the gravitational field (eg earth gravity or higher gravitational effect, for example during centrifugation).
  • Thermal separation processes are understood as meaning all separation processes which are based on the setting of a thermodynamic phase equilibrium. In particular, this is in the context of the present invention, the distillation or rectification, which make use of the setting of the evaporation equilibrium of the substances involved.
  • the person skilled in the art will be able to design the underlying thermal separation process so that this objective is achieved.
  • the person skilled in the art will be able to design the underlying thermal separation process so that this objective is achieved.
  • he will choose the temperature profiles in the distillation apparatus, the reflux ratio and the flow rates of the top product and the bottom product accordingly.
  • all parts of the system are in fluid communication with each other.
  • Under fluid connection between two parts of the system is understood as any type of connection, which allows a fluid, such as the reaction mixture, the cleavage product or the individual separation products, can flow from one to the other of the two parts of the plant, irrespective of any intermediate areas or components ,
  • a suitable reactor In particular, these are reactors with high mixing or backmixing. Therefore, batch reactors, in particular stirred reactors, in continuous stirred reactors, for example continuous stirred tank reactors, stirred tank cascades or tower reactors with segmented mixing (splitting tower), are suitable. These are to be designed so that they are suitable for setting the required pressure, which is done inter alia by the selection of appropriate wall thicknesses and the provision of suitable pressure-retaining members.
  • the invention is based on the finding that the hydrolytic cleavage of fatty acid alkyl esters and fatty acid triglycerides can be accelerated autocatalytically. As soon as the first, minor conversion to the reaction products takes place (initiation phase), the resulting free fatty acid, due to its acidity, acts as a catalyst for the hydrolysis reaction, whereby the ester cleavage is subsequently accelerated. In terms of time, this results in a typical S-shaped course of the sales curve.
  • the invention in the case of a batch reaction reaction, can be used in such a way that a portion of the free fatty acids obtained is retained from a preceding reaction batch and then added to a subsequent reaction mixture as catalyst.
  • a preferred embodiment of the process according to the invention provides that the separation of the light phase (step e)) and / or the recycling of at least a portion of the second separation product to the reaction step b) (step g)) take place during the reaction step b)
  • Proportion of free fatty acids based on the proportion of fatty acid alkyl esters or fatty acid triglycerides,> 0 to 10 wt .-%, preferably 0.1 to 8 wt .-%, most preferably 0.5 to 5 wt .-% is. It has been shown that in these concentration ranges of the free fatty acid a favorable compromise between the catalytic acceleration of the reaction on the one hand and the negative influence of the equilibrium position on the other hand is obtained.
  • the reaction step b) is carried out at a temperature of at least 220 ° C., preferably at least 240 ° C., most preferably at least 260 ° C. These reaction temperatures are favorable compromises between high reaction rates, onset of side reactions due to thermal decomposition of the substances involved and technical effort for pressure maintenance to keep water in the liquid phase.
  • the heavy phase comprising methanol obtained in step d) is fed to a second separation apparatus operating according to a thermal separation process and into a third separation product enriched in methanol and methanol separated into a water-enriched, fourth separation product, wherein the third separation product discharged as a methanol product from the process and the fourth separation product is at least partially recycled to the reaction step b).
  • a second separation apparatus operating according to a thermal separation process and into a third separation product enriched in methanol and methanol separated into a water-enriched, fourth separation product, wherein the third separation product discharged as a methanol product from the process and the fourth separation product is at least partially recycled to the reaction step b).
  • the use of fresh water as starting material is reduced and it will - possibly after further workup - contain a marketable methanol product as a byproduct.
  • methanol can be discharged as overhead product from the reactor.
  • the reaction equilibrium is shifted in the direction of the cleavage products and thus favors the hydrolysis reaction
  • the cleavage product obtained in reaction step b) is first fed to the second separation apparatus in which a methanol-enriched overhead product is selectively separated from the cleavage product and converted into methanol Product is discharged from the process.
  • a methanol-enriched overhead product is selectively separated from the cleavage product and converted into methanol Product is discharged from the process.
  • the amount or the mass flow of the cleavage product is reduced, so that the downstream phase separation device can be made smaller. If the cleavage product freed from a part of the methanol is to be cooled before it is introduced into the phase separator in order to promote the phase separation, the amount of cooling energy required is additionally reduced by the reduction in quantity.
  • the second separation device is designed as a flash stage (Flash), which is preferably adiabatic designed and operated.
  • Flash flash stage
  • pre-cooling of the cleavage product freed from a part of the methanol already takes place before being introduced into the phase separation device, so that the required amount of cooling energy is reduced.
  • this can be completely eliminated by a cooling device upstream of the phase separation device.
  • there also be a cooling device upstream of the phase separation device since this results in greater degrees of freedom with regard to the adjustment of the temperature in the phase separation device.
  • the cooling is effected by a cooling device upstream of the phase separation device and / or by performing the removal of the methanol-enriched overhead product from the split product adiabatically.
  • the adiabatic cooling already precedes the cleavage product freed from a portion of the methanol prior to introduction into the phase separation device, so that the required amount of cooling energy is reduced.
  • this can be completely eliminated by a cooling device upstream of the phase separation device.
  • the rest of the cooling is done by a cooling device upstream of the phase separation device, but which can be made smaller due to the adiabatic pre-cooling.
  • the ratio of water to fatty acid methyl ester is at least 2 mol / mol, preferably at least 10 mol / mol, most preferably at least 20 mol / mol. It has been found that in this way a favorable compromise between the desired high degrees of conversion and the required reactor volume is obtained.
  • a second separation device suitable for separating the heavy phase into a methanol enriched third separation product and a water enriched fourth separation product
  • means for feeding the heavy phase into the second separation device means for discharging the third separation product from the second separation device, and for discharging from the plant as a methanol product
  • means for discharging the fourth separation product from the second separation device means for recycling at least a portion of the fourth separation product to the at least one hydrolysis reactor.
  • the plant for producing fatty acids by hydrolytic cleavage of fatty acid methyl esters (FAME) further comprises means for supplying the methanol-depleted cleavage product to the phase separation device, means for recycling at least a portion of the heavy phase to the at least one hydrolysis reactor, means for Feeding the light phase to the first separator.
  • the removal of part of the methanol from the cleavage product improves and facilitates the phase separation in the phase separation device, since methanol acts as a solubilizer between the light, organic or non-polar and the heavy, aqueous or polar phase.
  • the system according to the invention preferably also comprises a cooling device arranged upstream of the phase separation device. This can be used advantageously if the cooling effect of the adiabatic expansion stage for the partial separation of methanol alone is insufficient to achieve a good and rapid phase separation in the phase separation device.
  • FIG. 1 schematic flow diagram of a first embodiment of the method according to the invention or the inventive system of fatty acid methyl ester (FAME) and water (H 2 O) via lines 1 and 2 are fed to the hydrolysis reactor 3.
  • Part of the water needed for the ester hydrolysis can also be introduced as steam into the hydrolysis reactor. This is preferably done in a manner which additionally contributes to the mixing of the liquid reaction mixture, that is, for example, by blowing into the liquid mixture.
  • the steam also serves as a heat carrier for heating the reactor contents.
  • the reactor pressure is selected so that the reaction mixture remains in the liquid phase at the reaction temperature set by a heater not shown in the drawing.
  • the pressure is adjusted in a known manner via the vapor pressure of the components involved and, if appropriate, additionally by adding an inert gas.
  • the cleavage product leaves the hydrolysis reactor via line 4, is cooled in the cooling device 5 and then fed via line 6 to the phase separation device 7.
  • the phase separation device is a simple container with overflows and discharges for a heavy and a light liquid phase in which the phase separation takes place gravitationally driven due to the different density of the two liquid phases.
  • the phase separation device From the phase separation device, the light, non-polar phase containing the free fatty acid product (FFA) and unreacted fatty acid methyl ester, discharged via line 8 and introduced into the first separator, which is configured in the example shown as distillation.
  • first separation product a fraction enriched in free fatty acids is obtained (first separation product), which is discharged from the process via line 10 as FFA product.
  • second separation product which is recycled via lines 11 and 1 to the hydrolysis reactor 3, contains not only unreacted fatty acid methyl ester but also traces of methanol and significant amounts of free fatty acid. The latter acts after its return to the hydrolysis reactor as a catalyst for the reaction of further fatty acid methyl ester to free fatty acid.
  • the heavy, polar phase containing unreacted water and methanol as a coproduct of ester hydrolysis is removed via line 12 from the phase separation device 7 and introduced into the second separation device 13, which is also equipped in the example shown as distillation.
  • a methanol product (MeOH) (third separation product) is obtained as the top product of the distillation, which is discharged via line 14 from the process and optionally fed to the further work-up.
  • the bottom product obtained is a water-enriched fraction (fourth separation product), which is recycled via lines 15 and 2 to the hydrolysis reactor 3.
  • a schematic representation of a second embodiment of the method according to the invention or the system according to the invention corresponds to the process flow up to the reference numeral 3 that in Fig. 1 .
  • the cleavage product leaves via line 4 the hydrolysis reactor, but now by means of expansion valve 16 adiabatically depressurized (flash) and introduced via line 17 into the second separation device 13a, here as a simple phase separation device for separating a gaseous, methanol-enriched phase (Third separation product) of a methanol-depleted liquid phase (fourth separation product) is designed.
  • a simple phase separation device for separating a gaseous, methanol-enriched phase (Third separation product) of a methanol-depleted liquid phase (fourth separation product) is designed.
  • a methanol product (MeOH) third separation product
  • the temperature of the fourth separation product is smaller than that of the late product leaving the hydrolysis reactor 3.
  • the cooling device 5, which is the methanol-depleted liquid phase is fed via line 18, be designed smaller in terms of the required cooling capacity, which is needed to set a defined temperature in the phase separator 7.
  • the phase separation device 7 Via line 6, the methanol-depleted liquid phase of the phase separation device 7 is abandoned, the properties and operation of which largely correspond to those in Fig. 1 was explained. However, the phase separation is in comparison to that in Fig. 1 shown embodiment easier or faster, since the liquid phase was previously withdrawn methanol, which acts as a solubilizer between the polar and the non-polar phase, thus complicating the phase separation. Due to the more rapid phase separation, the phase separation device 7 can thus in the in Fig. 2 shown embodiment are designed to be smaller.
  • the light phase is fed via line 8
  • a fraction enriched in free fatty acids is recovered (first separation product), which is discharged via line 10 as FFA product from the process.
  • the remaining fraction (second separation product), which is recycled via lines 11 and 1 to the hydrolysis reactor 3 contains not only unreacted fatty acid methyl ester but also traces of methanol and significant amounts of free fatty acid. The latter acts after its return to the hydrolysis reactor as a catalyst for the reaction of further fatty acid methyl ester to free fatty acid.
  • the effect of the water / FAME ratio is shown by the test series 2 and 3.
  • the level of the achieved conversion in the final state is increasingly with an increased amount of water.
  • a temperature increase causes a shortening of the necessary reaction time to reach this final state.
  • the invention provides a process and a plant with which free fatty acids can be obtained in a simple manner by hydrolytic cleavage of fatty acid alkyl esters, in particular fatty acid methyl esters (FAME), or alternatively of fatty acid triglycerides contained in oils and fats of plant and animal origin. Since the process does not require the use of external substances foreign to the process as homogeneous or heterogeneous catalysts, particular economic and ecological advantages are obtained, since no catalysts have to be recovered from the cleavage product and subsequently regenerated or disposed of in a complicated manner. The autocatalytic action of the free fatty acids added to the reaction mixture allows a reduction in the number of reactors used to achieve a fixed rate of production.
  • FAME fatty acid methyl esters

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (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)
  • Microbiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
EP16400026.7A 2016-07-08 2016-07-08 Procédé de fabrication d'acides gras par hydrolyse utilisant dans l'eau à haute température Active EP3266857B1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
EP16400026.7A EP3266857B1 (fr) 2016-07-08 2016-07-08 Procédé de fabrication d'acides gras par hydrolyse utilisant dans l'eau à haute température
BR112019000037-2A BR112019000037A2 (pt) 2016-07-08 2017-06-27 processo para preparar ácidos graxos por meio de hidrólise de éster
US16/316,248 US10696922B2 (en) 2016-07-08 2017-06-27 Process for preparing fatty acids by ester hydrolysis
MYPI2018002995A MY197420A (en) 2016-07-08 2017-06-27 Process for preparing fatty acids by ester hydrolysis
SG11201811694XA SG11201811694XA (en) 2016-07-08 2017-06-27 Process for preparing fatty acids by ester hydrolysis
PCT/EP2017/025181 WO2018007022A1 (fr) 2016-07-08 2017-06-27 Procédé de préparation d'acides gras par hydrolyse d'ester
CN201710550533.0A CN107586622B (zh) 2016-07-08 2017-07-07 通过酯水解制备脂肪酸的方法
CN201720825169.XU CN207468571U (zh) 2016-07-08 2017-07-07 通过酯水解制备脂肪酸的设备
PH12019500013A PH12019500013A1 (en) 2016-07-08 2019-01-03 Process for preparing fatty acids by ester hydrolysis
CONC2019/0001040A CO2019001040A2 (es) 2016-07-08 2019-01-31 Proceso para preparar ácidos grasos por hidrólisis de éster

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP16400026.7A EP3266857B1 (fr) 2016-07-08 2016-07-08 Procédé de fabrication d'acides gras par hydrolyse utilisant dans l'eau à haute température

Publications (2)

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EP3266857A1 true EP3266857A1 (fr) 2018-01-10
EP3266857B1 EP3266857B1 (fr) 2020-01-01

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EP16400026.7A Active EP3266857B1 (fr) 2016-07-08 2016-07-08 Procédé de fabrication d'acides gras par hydrolyse utilisant dans l'eau à haute température

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US (1) US10696922B2 (fr)
EP (1) EP3266857B1 (fr)
CN (2) CN207468571U (fr)
BR (1) BR112019000037A2 (fr)
CO (1) CO2019001040A2 (fr)
MY (1) MY197420A (fr)
PH (1) PH12019500013A1 (fr)
SG (1) SG11201811694XA (fr)
WO (1) WO2018007022A1 (fr)

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
EP3844140B1 (fr) * 2018-08-30 2023-06-07 NextChem S.p.A. Procédé et appareil pour produire des acides gras à partir d'esters méthyliques durant un processus non catalytique
CN113337346A (zh) * 2021-07-07 2021-09-03 刘德武 一种酯水解制备脂肪酸的方法
CN117531464A (zh) * 2023-11-09 2024-02-09 广东锦坤实业有限公司 一种大豆油硬脂酸的制备方法及装置

Citations (4)

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Publication number Priority date Publication date Assignee Title
GB594141A (en) * 1943-12-20 1947-11-04 Emery Industries Inc Improvements in or relating to methods of splitting fatty materials
US4185027A (en) 1978-06-15 1980-01-22 The Procter & Gamble Company Hydrolysis of methyl esters
WO1997007187A1 (fr) * 1995-08-21 1997-02-27 Poul Møller Ledelses- Og Ingeniørrådgivning Aps Procede pour scinder des matieres grasses et autres esters par hydrolyse
DE69321607T2 (de) 1992-12-22 1999-03-18 Procter & Gamble Hydrolyse von methylestern zur herstellung der fettsäuren

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PT1270734E (pt) * 2001-06-21 2008-03-24 T & T Oleochemie Gmbh Processo para a clivagem enzimática de óleos e gorduras
US8088183B2 (en) * 2003-01-27 2012-01-03 Seneca Landlord, Llc Production of biodiesel and glycerin from high free fatty acid feedstocks
WO2009075762A1 (fr) * 2007-12-11 2009-06-18 Cargill, Incorporated Procédé de fabrication de biodiesel et d'esters d'acides gras
ITMI20081203A1 (it) * 2008-06-30 2010-01-01 Eni Spa Procedimento per l'estrazione di acidi grassi da biomassa algale
US10087397B2 (en) * 2014-10-03 2018-10-02 Flint Hills Resources, Lp System and methods for making bioproducts

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB594141A (en) * 1943-12-20 1947-11-04 Emery Industries Inc Improvements in or relating to methods of splitting fatty materials
US4185027A (en) 1978-06-15 1980-01-22 The Procter & Gamble Company Hydrolysis of methyl esters
DE69321607T2 (de) 1992-12-22 1999-03-18 Procter & Gamble Hydrolyse von methylestern zur herstellung der fettsäuren
WO1997007187A1 (fr) * 1995-08-21 1997-02-27 Poul Møller Ledelses- Og Ingeniørrådgivning Aps Procede pour scinder des matieres grasses et autres esters par hydrolyse

Non-Patent Citations (3)

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Title
"Ullmann's Encyclopedia of Industrial Chemistry", 1998, article "Fatty Acids"
C. DA SILVA ET AL: "Biodiesel production through non-catalytic supercritical transesterification: current state and perspectives", BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, vol. 31, no. 2, 1 June 2014 (2014-06-01), BR, pages 271 - 285, XP055333536, ISSN: 0104-6632, DOI: 10.1590/0104-6632.20140312s00002616 *
RUSSELL L. HOLLIDAY ET AL: "Hydrolysis of Vegetable Oils in Sub- and Supercritical Water", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH., vol. 36, no. 3, 1 March 1997 (1997-03-01), US, pages 932 - 935, XP055333525, ISSN: 0888-5885, DOI: 10.1021/ie960668f *

Also Published As

Publication number Publication date
PH12019500013A1 (en) 2019-10-28
EP3266857B1 (fr) 2020-01-01
SG11201811694XA (en) 2019-01-30
CO2019001040A2 (es) 2019-02-08
WO2018007022A1 (fr) 2018-01-11
BR112019000037A2 (pt) 2019-04-16
CN207468571U (zh) 2018-06-08
US20190211282A1 (en) 2019-07-11
US10696922B2 (en) 2020-06-30
CN107586622B (zh) 2023-05-30
MY197420A (en) 2023-06-16
CN107586622A (zh) 2018-01-16

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