US2447186A - Producing lower alkyl esters - Google Patents
Producing lower alkyl esters Download PDFInfo
- Publication number
- US2447186A US2447186A US571016A US57101645A US2447186A US 2447186 A US2447186 A US 2447186A US 571016 A US571016 A US 571016A US 57101645 A US57101645 A US 57101645A US 2447186 A US2447186 A US 2447186A
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- United States
- Prior art keywords
- acid
- alcohol
- lower alkyl
- alkyl esters
- esters
- 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.)
- Expired - Lifetime
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- 125000005907 alkyl ester group Chemical group 0.000 title description 15
- 239000002253 acid Substances 0.000 description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 20
- 239000000194 fatty acid Substances 0.000 description 20
- 229930195729 fatty acid Natural products 0.000 description 20
- 235000019441 ethanol Nutrition 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 150000004665 fatty acids Chemical class 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 235000021588 free fatty acids Nutrition 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- 241000158728 Meliaceae Species 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003925 fat Substances 0.000 description 7
- 235000019197 fats Nutrition 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 238000006136 alcoholysis reaction Methods 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- -1 acid sodium sulfate Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000005456 glyceride group Chemical group 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003333 secondary alcohols Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- 241001323275 Andex Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 241001125046 Sardina pilchardus Species 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 229940110456 cocoa butter Drugs 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 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 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
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
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
-
- 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
- This invention relates to improvements in the preparation of the lower alkyl esters of the fatty acids which occur naturally in the form of glycerides.
- a number of methods, of preparing the ,lower alkyl esters of the higher fatty acids from the naturally occurringfiglycerides. have been do scribed, including processes involving alcoholysis or re-esterification, carried out by heating, the glyceride with the lower alco hol, such as methyl or ethyl alcohol in the presence of a catalyst, usually an alkali catalyst although acid catalysts have been suggested and used under substantially anhydrous conditions. It has been generally considered that the reaction will not proceed in the presence of any substantial amount of water or in the presence of any substantial amount of free fatty acid in the fat or oil.
- the glycerine can be substantially recovered in fairly concentrated form.
- the-process is industrially difiicult, as it'is difficult to maintain substantially anhydrous conditions, and it is expensive to so refine the oil as to reduceni free fatty acid content sufiiciently or, if compensation is made for the presence of the free fatty acid by the addition of a saponifying agent, difficulties are encountered in soperating the giycerine from the alkyl esters which are formed, possibly because of the emulsifying action of the soap.
- the esters of secondary alcohols, .e. g, isopropyl are produced with even greaterdifiicul-ty and with very poor yields. Yields. withacid catalysts, by method heretofore proposed, are not good with both primary and secondaryalcohols.
- the lower alkyl esters have a number of industrial applications as such, and are. con-veniently used for the production of soap, by saponiiication.
- esters The process proceeds efiiciently even thou h the oil or a con a n a ub n a p portion of free fatty acid, and makes unnecessary removing the free fatty acids or converting them to soap with consequent difficulties in separatin the l be a s yc ri h @1 holysis or re-esteriflcation proceeds to substantial completion and the separation of the sl cerine io med f om the a k ste s rmed is rapid and substantially complete.
- Or oils as they naturally occur are prepared by the alcoholysis' or e-es rifica ie O he lyceride. with a lower alcohol, advantageously in the presence of a substantial quantity of water, with the use of an acid us all ul ur c a id. and an .acidwomDfi tible: emulsifying agent, advanta-
- the present invention provides an improved 7 geouslymaho any acids. The reaction proceeds readily at relatively low temperatures, and ordinarily is carried out at reflux temperatures and with thorough agitation.
- reaction mixture is subj pt l 1 t t i tion.
- a lowerlayer which contains the glycerine, acid, water andex ess alcohol dil s par t and may be treated for the recovery of the glycerine and the excess alcohol.
- the upper oily layer consists of the lower alkyl esters of the y a id Conversions ran -ins a hi h a 93 per cent or' higher, are obtained.
- Free fatty acid in the fat or oil used is converted to the lower alkyl ester in the course of the reaction, so that the alkyl esters produced will contain but a very small amount of free fatty acid, even though the original fat or oilcpntains asubstantialproportion of free fatty acid, Most of the impurities present in the original fat or oil will separate intothe lower layer.
- esters may be distilled under a relatively high vacuum, advantageously with the use of steam.
- esters particularly the methly and ethyl esters, distill at lower temperatures than the free fatty acids do, and the distillation does not involve the formation of pitch or tar to the extent that the distillation of fatty acids does.
- the mahogany acid or other agent such as toluene sulfonic acid
- Example I One thousand parts of tallow having an acid value of about 5 are melted and added to a solution or mixture containing parts of water, 67 parts of 95% sulfuric acid, 330 parts of cornmercial methyl alcohol and parts of mahogany acid. The mixture is heated to refluxing temperature for 12 hours with agitation. The heat is then shut off and the mixture allowed to remain quiescent until it separates into two clean layers. The lower layer, containing the glycerine, water and methyl alcohol, is separated from the oily layer, consisting of the methyl esters of the tallow fatty acid. Conversion to the methyl esters was in one case 97% of theoretical. glycerine-containing layer may be treated to re cover the glycerin by any suitable procedure, such as by treating the lower layer, after separation from the oily layer, with soda ash until neutral,
- the crude glycerine so obtained may be further purified by vac uum distillation.
- the oily layer consisting of the methyl esters of the tallow fatty acids, is
- Example II One thousand parts of tallow are melted and added to a solution or mixture containing 100 parts sulfuric acid, 650 parts of 91% isopropyl alcohol and 20 parts of mahogany acids. The mixture is refluxed for 12 hours with agitation. The heat is then shut off and the mixture al-. lowed to settle, whereupon it separates into a lower layer and a floating oily layer consisting of about 95% isopropyl esters of the tallow fatty acids, which latter layer may be washed with water or an aqueous salt solution to facilitate the settling and separation.
- the quantity of water present in the reaction mixture in the practice of the present invention is substantial, although anhydrous or substantially anhydrous conditions may be used. It may range as high as 50% of the total mixture of water and alcohol, or even higher, e. g., up to 90% or somewhat more. Ordinarily, to reduce the reaction volume as much as is feasible, such large quantities of water as- 50% will not be used, but smaller quantities,
- sulfuric acid instead of sulfuric acid, other acids, such as hydrochloric acid or phosphoric acid, or acid salts, such as acid sodium sulfate, may be used, but because of its economy, sulfuric acid is the acid of choice.
- the use of the mahogany acids is of marked advantage, as compared with other acidcompatible emulsifying agents, in promoting the efficiency and completeness of the re-esterification reaction, other agents such as toluene sulfonic acid, naphthalene or alkyl naphthalene sulfonic acids, etc., in general, the acid-compatible emulsifying agents, promote the efficiency and completeness of the reaction.
- the invention is applicable to the production of the lower alkyl esters of any of the naturally occurring fatty acids, and in particular, to the re-esterification or alcoholysis of any of the natural fats or oils, including tallow, coconut oil, olive oil, palm oil, sardine oil, castor oil, whale oil, linseed oil, cocoa butter, etc. It may also be applied to the esterification of the free acids with the alcohol or alcohols, similar conditions being used.
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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)
Description
Patented Aug. 17, 1948 PRODUCING LOWER ALKYL ESTERS Robert Gardner King, Norwalk, and Robert JoshuaKing, New Canaan, Conn., assignors to The Photo 1echnical Corporation, Norwalk, Conn, a corporation of Connecticut 7 No Drawing. gll p plication January 1, 1945,
7 Serial No. 571,016
[8 Claims. 01.260-4103) This invention relates to improvements in the preparation of the lower alkyl esters of the fatty acids which occur naturally in the form of glycerides.
A number of methods, of preparing the ,lower alkyl esters of the higher fatty acids from the naturally occurringfiglycerides. have been do scribed, including processes involving alcoholysis or re-esterification, carried out by heating, the glyceride with the lower alco hol, such as methyl or ethyl alcohol in the presence of a catalyst, usually an alkali catalyst although acid catalysts have been suggested and used under substantially anhydrous conditions. It has been generally considered that the reaction will not proceed in the presence of any substantial amount of water or in the presence of any substantial amount of free fatty acid in the fat or oil. In the procedures heretofore used, therefore, it has been necessaryto use substantially anhydrous alcohol, and to use refined fats or oils, substantially free fromwaterand with alow free fatty acid content or, in the case of oilsor fats with relatively high fatty acid .content,- to
take special precautionasuch as the conversion thereof to soap, prior to carrying out the-alcoholysis reaction. With alkali catalysts, anhydrous conditions, and the substantial absence of free fatty acid, high yields of the lower alkyl esters of primary alcohols can be obtained, and
the glycerine can be substantially recovered in fairly concentrated form. However, the-process is industrially difiicult, as it'is difficult to maintain substantially anhydrous conditions, and it is expensive to so refine the oil as to reduceni free fatty acid content sufiiciently or, if compensation is made for the presence of the free fatty acid by the addition of a saponifying agent, difficulties are encountered in soperating the giycerine from the alkyl esters which are formed, possibly because of the emulsifying action of the soap. The esters of secondary alcohols, .e. g, isopropyl, are produced with even greaterdifiicul-ty and with very poor yields. Yields. withacid catalysts, by method heretofore proposed, are not good with both primary and secondaryalcohols.
The lower alkyl esters have a number of industrial applications as such, and are. con-veniently used for the production of soap, by saponiiication.
esters. The process proceeds efiiciently even thou h the oil or a con a n a ub n a p portion of free fatty acid, and makes unnecessary removing the free fatty acids or converting them to soap with consequent difficulties in separatin the l be a s yc ri h @1 holysis or re-esteriflcation proceeds to substantial completion and the separation of the sl cerine io med f om the a k ste s rmed is rapid and substantially complete.
In accordance with th e en nve i n. the lowerallsyl este s o the t y ac o th f .Or oils as they naturally occur are prepared by the alcoholysis' or e-es rifica ie O he lyceride. with a lower alcohol, advantageously in the presence of a substantial quantity of water, with the use of an acid us all ul ur c a id. and an .acidwomDfi tible: emulsifying agent, advanta- The present invention provides an improved 7 geouslymaho any acids. The reaction proceeds readily at relatively low temperatures, and ordinarily is carried out at reflux temperatures and with thorough agitation. When the reaction has proceeded to substantial completeness, the reaction mixture is subj pt l 1 t t i tion. A lowerlayer, which contains the glycerine, acid, water andex ess alcohol dil s par t and may be treated for the recovery of the glycerine and the excess alcohol. The upper oily layer consists of the lower alkyl esters of the y a id Conversions ran -ins a hi h a 93 per cent or' higher, are obtained. Free fatty acid in the fat or oil used is converted to the lower alkyl ester in the course of the reaction, so that the alkyl esters produced will contain but a very small amount of free fatty acid, even though the original fat or oilcpntains asubstantialproportion of free fatty acid, Most of the impurities present in the original fat or oil will separate intothe lower layer.
The glycerine, isv readily recovered by neutralizing the lower layer with solid soda ash .or
other alkali, filtering 9f the inorganic salts formed and d stilling. the excess alcohol and -water-froin the filtrate. If necessary, the glycduced impractical, whether the use is of the esters as such or for the production of soap. In such case, the esters may be distilled under a relatively high vacuum, advantageously with the use of steam. These esters, particularly the methly and ethyl esters, distill at lower temperatures than the free fatty acids do, and the distillation does not involve the formation of pitch or tar to the extent that the distillation of fatty acids does. At least a portion of the mahogany acid or other agent, such as toluene sulfonic acid, remains in the ester layer, and the esters may be rapidly and completely split through the action of this agent by the addition of dilute acid and carrying out the hydrolysis under conditions such that the alcohol, as formed, is distilled off.
The invention will be illustrated by the following specific examples, but it is not limited thereto.
Example I One thousand parts of tallow having an acid value of about 5 are melted and added to a solution or mixture containing parts of water, 67 parts of 95% sulfuric acid, 330 parts of cornmercial methyl alcohol and parts of mahogany acid. The mixture is heated to refluxing temperature for 12 hours with agitation. The heat is then shut off and the mixture allowed to remain quiescent until it separates into two clean layers. The lower layer, containing the glycerine, water and methyl alcohol, is separated from the oily layer, consisting of the methyl esters of the tallow fatty acid. Conversion to the methyl esters was in one case 97% of theoretical. glycerine-containing layer may be treated to re cover the glycerin by any suitable procedure, such as by treating the lower layer, after separation from the oily layer, with soda ash until neutral,
filtering off the sodium sulfate, and distilling off the methyl alcohol and water. The crude glycerine so obtained may be further purified by vac uum distillation. The oily layer, consisting of the methyl esters of the tallow fatty acids, is
The
washed with water or an aqueous solution of salt to facilitate the separation of the glycerine, and to remove such impurities as may be removed by this washing. If, in this procedure, tallow fatty acids are used in place of tallow a high yield of the same methyl esters is obtained, but, of course, no glycerine is obtained as a byproduct.
Example II One thousand parts of tallow are melted and added to a solution or mixture containing 100 parts sulfuric acid, 650 parts of 91% isopropyl alcohol and 20 parts of mahogany acids. The mixture is refluxed for 12 hours with agitation. The heat is then shut off and the mixture al-. lowed to settle, whereupon it separates into a lower layer and a floating oily layer consisting of about 95% isopropyl esters of the tallow fatty acids, which latter layer may be washed with water or an aqueous salt solution to facilitate the settling and separation.
Advantageously, the quantity of water present in the reaction mixture in the practice of the present invention is substantial, although anhydrous or substantially anhydrous conditions may be used. It may range as high as 50% of the total mixture of water and alcohol, or even higher, e. g., up to 90% or somewhat more. Ordinarily, to reduce the reaction volume as much as is feasible, such large quantities of water as- 50% will not be used, but smaller quantities,
such as 10 to 20%, based on the alcohol, will be used. One of the advantages of the presence of water in the reaction mixture is that it permits the use of sulfuric acid as a catalytic agent without incurring risk of side reactions, such as the formation of ethers, charring, or the like, which results from the use of concentrated sulfuric acid.
Instead of sulfuric acid, other acids, such as hydrochloric acid or phosphoric acid, or acid salts, such as acid sodium sulfate, may be used, but because of its economy, sulfuric acid is the acid of choice.
One of the indications of the eficiency of the process of the present invention is that even secondary alcohol, such as the isopropyl alcohol of Example II, may be used in the re-esterification reaction with high efiiciency. Most of the processes heretofore proposed have not been workable with secondary alcohols, such as isopropyl alcohol, at least in the sense that substantial conversion of the glyceride to the alkyl ester has not been obtainable. Any of the lower alcohols, including methyl, ethyl, iso and normal propyl, butyl and amyl alcohols may be used in the practice of the invention. Tertiary alcohols, such as tertiary butyl alcohol, may also be used, as may mixtures of alcohols, to produce mixed esters.
While the use of the mahogany acids is of marked advantage, as compared with other acidcompatible emulsifying agents, in promoting the efficiency and completeness of the re-esterification reaction, other agents such as toluene sulfonic acid, naphthalene or alkyl naphthalene sulfonic acids, etc., in general, the acid-compatible emulsifying agents, promote the efficiency and completeness of the reaction.
The invention is applicable to the production of the lower alkyl esters of any of the naturally occurring fatty acids, and in particular, to the re-esterification or alcoholysis of any of the natural fats or oils, including tallow, coconut oil, olive oil, palm oil, sardine oil, castor oil, whale oil, linseed oil, cocoa butter, etc. It may also be applied to the esterification of the free acids with the alcohol or alcohols, similar conditions being used.
We claim:
1. The process of producing lower alkyl esters of higher fatty acids which comprises reacting a material of the class consisting of higher fatty acid glycerides and higher fatty acids with a lower alcohol in the presence of a mineral acid, an acid-compatible emulsifying agent and water.
2. The process of producing lower alkyl esters of higher fatty acids which comprises reacting a material of the class consisting of higher fatty acid glycerides and higher fatty acids with an aqueous lower alcohol in the presence of a mineral acid and a sulfonic acid emulsifying agent.
3. The process as in claim 1 in which the acid is sulfuric acid.
4. The process as in claim 1 in which the agent is mahogany acid.
5. The process as in claim 2 in which the acid is sulfuric acid.
6. The process as in claim 2 in which the agent is mahogany acid.
7. The process of producing lower alkyl esters if higher fatty acids by re-esterification or alcoholysis of higher fatty acid glycerides which comprises reacting a higher fatty acid glyceride with an aqueous lower alcohol in the presence of sulfuric acid and mahogany acids, the quantity of water in the reaction mixture being at least REFERENCES CITED based on the lower 1 The following references are of record in the 8. The process of producing lower alkyl esters file of this patent:
of higher fatty acids which comprises reacting a material of the class consisting of higher fatty 5 UNITED STATES PATENTS acid glycerides and higher fatty acids with a Number Name 7 Date lower alcohol in the presence of a mineral acid, 290 609 G088 July 21 1942 n acid-compatible emulsifying agent and water, 2371284 Cook Man 1945 separating the ester layer from the aqueous layer e Percy Aug 1945 and ysi g it while distilling ofi liber 10 alcohol.
ROBERT GARDNER KING. ROBERT JOSHUA. KING.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US571016A US2447186A (en) | 1945-01-01 | 1945-01-01 | Producing lower alkyl esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US571016A US2447186A (en) | 1945-01-01 | 1945-01-01 | Producing lower alkyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2447186A true US2447186A (en) | 1948-08-17 |
Family
ID=24281989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US571016A Expired - Lifetime US2447186A (en) | 1945-01-01 | 1945-01-01 | Producing lower alkyl esters |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2447186A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4058541A (en) * | 1976-10-18 | 1977-11-15 | Texaco Inc. | Preparation of 2-alkanoyloxy-alkanoic |
| US4668439A (en) * | 1984-06-07 | 1987-05-26 | Hoechst Aktiengesellschaft | Process for the preparation of fatty acid esters of short-chain alcohols |
| US9328054B1 (en) | 2013-09-27 | 2016-05-03 | Travis Danner | Method of alcoholisis of fatty acids and fatty acid gyicerides |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2290609A (en) * | 1940-09-10 | 1942-07-21 | Henry A Wallace | Process for producing fatty acid polyhydric esters from glycerides |
| US2371284A (en) * | 1945-03-13 | Preparation of sulphated fatty | ||
| US2383614A (en) * | 1942-10-17 | 1945-08-28 | Colgate Palmolive Peet Co | Treatment of fatty glycerides |
-
1945
- 1945-01-01 US US571016A patent/US2447186A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2371284A (en) * | 1945-03-13 | Preparation of sulphated fatty | ||
| US2290609A (en) * | 1940-09-10 | 1942-07-21 | Henry A Wallace | Process for producing fatty acid polyhydric esters from glycerides |
| US2383614A (en) * | 1942-10-17 | 1945-08-28 | Colgate Palmolive Peet Co | Treatment of fatty glycerides |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4058541A (en) * | 1976-10-18 | 1977-11-15 | Texaco Inc. | Preparation of 2-alkanoyloxy-alkanoic |
| US4668439A (en) * | 1984-06-07 | 1987-05-26 | Hoechst Aktiengesellschaft | Process for the preparation of fatty acid esters of short-chain alcohols |
| US9328054B1 (en) | 2013-09-27 | 2016-05-03 | Travis Danner | Method of alcoholisis of fatty acids and fatty acid gyicerides |
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