EP2358851B1 - Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras - Google Patents
Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras Download PDFInfo
- Publication number
- EP2358851B1 EP2358851B1 EP09756298.7A EP09756298A EP2358851B1 EP 2358851 B1 EP2358851 B1 EP 2358851B1 EP 09756298 A EP09756298 A EP 09756298A EP 2358851 B1 EP2358851 B1 EP 2358851B1
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- EP
- European Patent Office
- Prior art keywords
- fatty acid
- process according
- oil
- transesterification
- methanesulfonic acid
- Prior art date
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 57
- 239000000194 fatty acid Substances 0.000 title claims description 57
- 229930195729 fatty acid Natural products 0.000 title claims description 57
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 title claims description 40
- -1 fatty acid esters Chemical class 0.000 title claims description 36
- 229940098779 methanesulfonic acid Drugs 0.000 title claims description 20
- 238000000034 method Methods 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 32
- 238000005809 transesterification reaction Methods 0.000 claims description 31
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000003925 fat Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 9
- 235000019198 oils Nutrition 0.000 claims description 9
- 235000019197 fats Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 235000019486 Sunflower oil Nutrition 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 3
- 239000002600 sunflower oil Substances 0.000 claims description 3
- 235000013912 Ceratonia siliqua Nutrition 0.000 claims description 2
- 240000008886 Ceratonia siliqua Species 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 235000008524 evening primrose extract Nutrition 0.000 claims description 2
- 239000010475 evening primrose oil Substances 0.000 claims description 2
- 229940089020 evening primrose oil Drugs 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims 1
- 238000010924 continuous production Methods 0.000 claims 1
- 239000003346 palm kernel oil Substances 0.000 claims 1
- 235000019865 palm kernel oil Nutrition 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 239000003225 biodiesel Substances 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- PVNIQBQSYATKKL-UHFFFAOYSA-N tripalmitin Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000021324 borage oil Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009884 interesterification Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- 229960001947 tripalmitin Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- 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 acid esters and / or fatty acid ester mixtures of monohydric alcohols having 1 to 5 carbon atoms by transesterification of fatty acid glycerides with short-chain monohydric alcohols having 1 to 5 carbon atoms in the presence of a basic catalyst, in which methanesulfonic acid is used. Furthermore, the invention relates to the use of methanesulfonic acid for the preparation of these fatty acid esters.
- the fatty acid esters prepared according to the invention are suitable as pharmaceutical, dietary or cosmetic raw materials, as intermediates for further fatty acid derivatives, such as fatty alcohols, fatty amines or surfactants.
- Fatty acid esters are also particularly suitable as lubricants, plasticizers, hydraulic oils, fuels or fuels for the operation of diesel engines.
- fatty acid esters has long been known.
- biodiesel is nowadays obtained on an industrial scale by means of a catalytic transesterification of vegetable oil.
- This is usually dehydrated, deacidified and degummed oil with a molar excess of alcohol (usually methanol) of 6: 1 using 1 wt .-% catalyst based on the amount of the oil used (usually KOH) above the boiling point of the alcohol reacted.
- the fatty acids contained in the fat molecules of the oil are split off catalytically and react with the present alcohol to the fatty acid ester.
- Fats and oils are usually triglycerides, which means that one fat molecule contains three fatty acids bound to one glycerol molecule.
- a complete transesterification reaction as it is carried out in the production of biodiesel, per molecule of fat or oil, three "molecules of biodiesel" and one molecule of glycerol.
- Intermediates of this reaction are mono- and diglycerides.
- Mono- and diglycerides consist of a glycerol backbone, hereinafter also referred to as glycerol backbone, to which one (monoglyceride) or two (diglyceride) fatty acids are bound. Since both polar hydroxide groups and apolar hydrocarbon chains are present in mono- and diglycerides, these have amphiphilic properties and almost always change the polarity of this solvent in organic solvents.
- the transesterification requires a reaction time of about 8 h, with currently a conversion of about 98% is achieved.
- the glycerol which is insoluble in the fatty acid alkyl ester (FASE), is removed from the biodiesel by means of a phase separator and used as a technical or pharmaceutical raw material after chemical and distillative purification.
- the excess alcohol contained in the fatty acid alkyl esters is separated by distillation and returned to the process.
- a dilute organic or inorganic acid is added to neutralize the remaining alkaline catalysts (eg KOH) and, after phase separation, the fatty acid ester phase is stripped off.
- alkaline catalysts eg KOH
- organic or inorganic acids are phosphoric, sulfuric, hydrochloric, nitric, boron.
- Sulfuric acid is currently preferably used in the neutralization of the alkaline catalysts.
- the object of the present invention is to provide a process for the preparation of fatty acid esters with improved yields.
- the process for the preparation of fatty acid esters should be able to be integrated into known production processes without great expenditure on equipment.
- step (b) The treatment of the fatty acid ester and / or fatty acid ester mixture with the methanesulfonic acid in step (b) can be carried out directly after the transesterification in order to at least substantially neutralize the basic catalyst used in the transesterification.
- the residence time of the reaction products before carrying out step (b) can be selected so that a phase separation into a fatty acid ester phase and a glycerol phase takes place.
- the heavy glycerol phase can then be removed, and the catalyst residues remaining in the ester phase can be neutralized by adding the methanesulfonic acid.
- the transesterification in step (a) can generally be carried out in one or two or more stages, i. the fatty acid glyceride is either transesterified with the entire amount of lower alcohol and catalyst or in a first stage, only a portion of the required amount of short-chain monohydric alcohol and catalyst is used for transesterification and after the deposition and separation of a glycerol phase in a second stage or in further stages, the remaining amount (s) of short-chain, monohydric alcohol and catalyst for transesterification used in the same way, the two- and multi-stage operations bring the advantage of further reduction of excess alcohol and also increased yields of fatty acid ester with it.
- the transesterification is carried out according to an embodiment of the invention according to the two-stage procedure, in the first stage preferably 60% to 90% of the total required amount of short-chain alcohol and catalyst and used in the second stage 10% to 40% of the total required amount of short-chain alcohol and catalyst.
- the treatment with the methanesulfonic acid can take place immediately after the second or the last transesterification stage, i. if appropriate, without previously separating off the glycerol fraction formed in the second or last stage.
- the transesterification by the process according to the invention is usually carried out at ambient temperatures of about +5 to + 40 ° C and atmospheric pressure and can in principle in any open or closed container of any size, which is advantageously equipped with a discharge device on the ground, are running.
- the method according to the invention can be carried out using agitators or mechanical intensive mixers.
- the corresponding apparatus and designs are known to those skilled in the field of apparatus engineering, for this reason will not be discussed in more detail here.
- the inventive method can also be carried out continuously.
- Suitable fatty acid glycerides which can be transesterified in the process according to the invention are naturally occurring vegetable and animal fats and oils, such as soybean oil, palm oil and palm fat, coconut oil and coconut fat, sunflower oil, rapeseed oil, cottonseed oil, linseed oil, castor oil, peanut oil, olive oil, safflower oil, Evening primrose oil, borage oil, carob seed oil, etc., as well as mono-, di- and triglycerides, such as triolein, tripalmitin, tristearin, glycerol monooleate and glycerol monostearate, isolated from the aforementioned vegetable oils and fats or obtained by interesterification or synthetically prepared.
- waste oils such as used frying oil can also be used in the context of the process according to the invention.
- Sunflower oil and rapeseed oil are preferably used in the process according to the invention.
- the vegetable oils and fats can be used in a refined or unrefined manner and can contain, in addition to mucilages, turbid substances and other impurities, free fatty acids up to a proportion of 20% by weight and beyond.
- dehydrated, deacidified and degummed fatty acid glycerides are used as starting materials for the process according to the invention used. The use of these leads to a simplified control of the process and also brings increased yields with it.
- monohydric alcohols those having 1 to 5 carbon atoms are used. These are preferably selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 3-methyl-1-butanol and neopentyl alcohol, and mixtures thereof. Especially preferred are methanol and ethanol, most preferred is methanol.
- alkali metal or alkaline earth metal compounds in the form of the oxides, hydroxides, hydrides, carbonates, acetates or alcoholates of the short-chain alcohols having 1 to 5 carbon atoms, preferably sodium hydroxide, potassium hydroxide, sodium and potassium alkoxides of the short-chain monohydric compounds, are used as basic catalysts for transesterification Alcohols having 1 to 5 carbon atoms in question.
- the basic catalysts are particularly preferably selected from KOH, NaOH, sodium and potassium methylate. Particularly preferred are potassium and sodium methylate.
- the basic catalyst in the transesterification of fatty acid glycerides in an amount of 0.1 to 5 wt .-%, preferably in an amount of 0.5 to 1.5 wt .-%, based on the mass of the fatty acid glyceride used.
- the lower, monohydric alcohol is added in an excess of 0.1 mol to 2.0 mol, based on 1 mol of glycerol-bound fatty acid.
- water is used in an amount of from 0.5 to 20% by weight, based on the reaction mixture, of the transesterification of the fatty acid glycerides.
- the basic catalyst in the form of an aqueous or alcoholic solution is added to the fatty acid glyceride.
- the reaction mixture formed thereby can be added with a certain amount of water, which is in the range from 0.5 to 20% by weight, based on the total mass.
- the addition of the water can be isolated or carried out in conjunction with the methanesulfonic acid.
- the methanesulfonic acid is in the form of a 50 to 99%, preferably in the form of a 60 to 80%, particularly preferably in the form of a 70% aqueous solution added.
- FIG. 1 shows a block diagram of the process for the production of rapeseed oil methyl ester (RME).
- rapeseed oil As fatty acid glyceride, rapeseed oil (Vollraffinat) was used from retail.
- the catalysts NaOH, KOH, sodium methylate and potassium methylate, the solvent methanol and the sulfuric acid for the neutralization were purchased from the laboratory retailer.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Fats And Perfumes (AREA)
Claims (15)
- Procédé pour la préparation d'esters d'acides gras et/ou de mélanges d'esters d'acides gras d'alcools monovalents à courte chaîne comprenant 1 à 5 atomes de carbone, comprenant(a) la transestérification de glycérides d'acides gras avec des alcools monovalents à courte chaîne comprenant 1 à 5 atomes de carbone en présence d'au moins un catalyseur basique pour former un mélange réactionnel qui contient les esters d'acides gras et/ou le mélange d'esters d'acides gras, et(b) le traitement d'au moins une partie du mélange réactionnel formé lors de la transestérification dans l'étape (a) avec de l'acide méthanesulfonique.
- Procédé selon la revendication 1, où, dans l'étape (a), après la fin de la transestérification et avant la réalisation de l'étape (b), le temps de séjour du mélange réactionnel est choisi de manière telle qu'il se produit une séparation des phases en une phase d'esters d'acides gras et une phase de glycérol.
- Procédé selon la revendication 1 ou 2, la transestérification dans l'étape (a) étant réalisée en plusieurs étapes.
- Procédé selon la revendication 3, la transestérification dans l'étape (a) étant réalisée en deux étapes.
- Procédé selon la revendication 4, où on utilise, dans la première étape, 60% à 90% de la quantité totale utilisée d'alcool et de catalyseur et, dans la deuxième étape, 10% à 40% de la quantité totale utilisée d'alcool et de catalyseur.
- Procédé selon l'une quelconque des revendications 1 à 5, où on utilise, comme glycérides d'acides gras, des graisses et des huiles végétales et animales naturelles, choisies parmi l'huile de soja, de palme, de palmiste, de coco, de tournesol, de colza, de lin, de ricin, d'arachide, d'olive, d'onagre et de caroube ainsi que leurs mélanges.
- Procédé selon l'une quelconque des revendications 1 à 6, où on utilise, comme alcool monovalent à courte chaîne du méthanol ou de l'éthanol.
- Procédé selon l'une quelconque des revendications 1 à 7, où on utilise comme catalyseurs basiques des composés basiques de métal alcalin ou alcalino-terreux, choisis parmi l'hydroxyde de sodium, l'hydroxyde de potassium, les alcoolates de sodium et de potassium des alcools monovalents à courte chaîne comprenant 1 à 5 atomes de carbone ou leurs mélanges.
- Procédé selon l'une quelconque des revendications 1 à 8, où le catalyseur basique est utilisé en une quantité de 0,5 à 5% en poids, par rapport à la masse du glycéride d'acides gras utilisé.
- Procédé selon l'une quelconque des revendications 1 à 9, où la quantité d'acide méthanesulfonique dans l'étape (b) est calculée de manière telle qu'elle est au moins équivalente aux quantités de catalyseur basique utilisées dans l'étape (a).
- Procédé selon l'une quelconque des revendications 2 à 10, où, après la fin de la transestérification dans l'étape (a), la phase d'esters d'acides gras est formée, séparée et traitée dans l'étape (b) avec de l'acide méthanesulfonique.
- Procédé selon l'une quelconque des revendications 1 à 11, où l'acide méthanesulfonique est utilisé sous forme d'un acide aqueux à 50 jusqu'à 99% pour le traitement dans l'étape (b).
- Procédé selon l'une quelconque des revendications 1 à 12, où avant la réalisation de l'étape de procédé (b) l'alcool en excès est séparé de l'étape (a).
- Procédé selon l'une quelconque des revendications 1 à 13, qui est réalisé sous forme de procédé continu.
- Utilisation d'acide méthanesulfonique lors de la préparation d'esters alkyliques d'acides gras ou de leurs mélanges en utilisant des catalyseurs basiques lors de la transestérification de glycérides d'acides gras.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL09756298T PL2358851T5 (pl) | 2008-11-17 | 2009-11-16 | Zastosowanie kwasu metanosulfonowego do wytwarzania estrów kwasów tłuszczowych |
EP09756298.7A EP2358851B2 (fr) | 2008-11-17 | 2009-11-16 | Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08169225 | 2008-11-17 | ||
PCT/EP2009/065230 WO2010055158A1 (fr) | 2008-11-17 | 2009-11-16 | Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras |
EP09756298.7A EP2358851B2 (fr) | 2008-11-17 | 2009-11-16 | Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2358851A1 EP2358851A1 (fr) | 2011-08-24 |
EP2358851B1 true EP2358851B1 (fr) | 2014-03-12 |
EP2358851B2 EP2358851B2 (fr) | 2018-01-10 |
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ID=41716465
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Application Number | Title | Priority Date | Filing Date |
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EP09756298.7A Active EP2358851B2 (fr) | 2008-11-17 | 2009-11-16 | Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras |
Country Status (9)
Country | Link |
---|---|
US (1) | US8692008B2 (fr) |
EP (1) | EP2358851B2 (fr) |
CN (1) | CN102257108B (fr) |
BR (1) | BRPI0921034B1 (fr) |
ES (1) | ES2457097T5 (fr) |
MY (1) | MY161118A (fr) |
PL (1) | PL2358851T5 (fr) |
PT (1) | PT2358851E (fr) |
WO (1) | WO2010055158A1 (fr) |
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DE102010055969A1 (de) * | 2010-12-23 | 2012-06-28 | Süd-Chemie AG | Verfahren zur Aufreinigung von organischen Flüssigkeiten |
FR3002936B1 (fr) | 2013-03-06 | 2015-03-06 | Arkema France | Utilisation d'acide sulfonique pour la recuperation de glycerol issu de la reaction de trans-esterification de triglycerides |
US20170066995A1 (en) | 2014-03-04 | 2017-03-09 | Basf Se | Method for Degumming And Esterification Of An Oil |
WO2016028845A1 (fr) * | 2014-08-19 | 2016-02-25 | Archer Daniels Midland Company | Synthèse de tensioactifs non-ioniques à partir de 5-hydroxyméthyl-2-furfurale, de 2,5-diméthanol-furane et de bis-2,5-dihydroxymethyltétrahydrofuranes |
US20190301027A1 (en) | 2016-07-18 | 2019-10-03 | Basf Se | Low corrosion alkane sulfonic acids for condensation reactions |
GB201619827D0 (en) * | 2016-11-23 | 2017-01-04 | Lucite Int Uk Ltd | Process for the production of methyl methacrylate |
BR112021006249A2 (pt) | 2018-10-10 | 2021-07-06 | Basf Se | método para produzir éster alquílico de ácido graxo |
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US2360844A (en) † | 1941-11-26 | 1944-10-24 | Du Pont | Preparation of detergents |
DE3319590A1 (de) † | 1983-05-30 | 1984-12-06 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur herstellung von fettsaeureestern kurzkettiger aliphatischer alkohole aus freie fettsaeuren enthaltenden fetten und/oder oelen |
DE3444893A1 (de) † | 1984-12-08 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur herstellung von fettsaeuremethylestern |
US5276204A (en) * | 1988-11-09 | 1994-01-04 | Henkel Kommanditgesellschaft Auf Aktien | Fatty alcohol mixtures and ethoxylates thereof showing improved low-temperature behavior |
AT397510B (de) | 1991-11-06 | 1994-04-25 | Wimmer Theodor | Verfahren zur herstellung von fettsäureestern kurzkettiger alkohole |
FI95367C (fi) * | 1994-09-07 | 1996-01-25 | Raision Tehtaat Oy Ab | Menetelmä synteettisen esterin valmistamiseksi kasviöljystä |
AT410443B (de) † | 2000-11-08 | 2003-04-25 | Wimmer Theodor | Verfahren zur herstellung von fettsäureestern niederer alkohole |
ITMI20032129A1 (it) * | 2003-11-05 | 2005-05-06 | Acs Dobfar Spa | Procedimento per la frammentazione del dna di cellule fungine, batteriche o di lieviti per la inattivazione di antibiotici residui in biomasse da fermentazione |
ITMI20040579A1 (it) * | 2004-03-25 | 2004-06-25 | Zambon Spa | Processo di preparazione di gabapentina |
WO2005123890A1 (fr) * | 2004-06-22 | 2005-12-29 | Akzo Nobel N.V. | Biodiesels ramifies |
BRPI0500333A (pt) | 2005-02-02 | 2006-09-12 | Univ Rio De Janeiro | processo catalìtico para esterificação de ácidos graxos |
BRPI0503631B1 (pt) | 2005-08-19 | 2015-07-21 | Petróleo Brasileiro S A Petrobras | Processo para a produção de biodiesel |
US7872149B2 (en) † | 2006-09-19 | 2011-01-18 | Best Energies, Inc. | Biodiesel processes in the presence of free fatty acids and biodiesel producer compositions |
-
2009
- 2009-11-16 CN CN200980150637.6A patent/CN102257108B/zh active Active
- 2009-11-16 PT PT97562987T patent/PT2358851E/pt unknown
- 2009-11-16 ES ES09756298.7T patent/ES2457097T5/es active Active
- 2009-11-16 BR BRPI0921034-2A patent/BRPI0921034B1/pt not_active IP Right Cessation
- 2009-11-16 WO PCT/EP2009/065230 patent/WO2010055158A1/fr active Application Filing
- 2009-11-16 US US13/129,202 patent/US8692008B2/en active Active
- 2009-11-16 PL PL09756298T patent/PL2358851T5/pl unknown
- 2009-11-16 MY MYPI2011002136A patent/MY161118A/en unknown
- 2009-11-16 EP EP09756298.7A patent/EP2358851B2/fr active Active
Also Published As
Publication number | Publication date |
---|---|
PL2358851T3 (pl) | 2014-08-29 |
BRPI0921034B1 (pt) | 2019-11-19 |
CN102257108B (zh) | 2014-04-09 |
EP2358851B2 (fr) | 2018-01-10 |
ES2457097T3 (es) | 2014-04-24 |
US20110245521A1 (en) | 2011-10-06 |
WO2010055158A1 (fr) | 2010-05-20 |
BRPI0921034A2 (pt) | 2015-12-29 |
PT2358851E (pt) | 2014-04-02 |
EP2358851A1 (fr) | 2011-08-24 |
PL2358851T5 (pl) | 2018-09-28 |
MY161118A (en) | 2017-04-14 |
US8692008B2 (en) | 2014-04-08 |
ES2457097T5 (es) | 2018-04-16 |
CN102257108A (zh) | 2011-11-23 |
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