US3413324A - Process for alkali refining of glyceride oils and fatty acid esters - Google Patents

Process for alkali refining of glyceride oils and fatty acid esters Download PDF

Info

Publication number
US3413324A
US3413324A US541436A US54143666A US3413324A US 3413324 A US3413324 A US 3413324A US 541436 A US541436 A US 541436A US 54143666 A US54143666 A US 54143666A US 3413324 A US3413324 A US 3413324A
Authority
US
United States
Prior art keywords
oil
fatty acid
free fatty
alkali
refining
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
Application number
US541436A
Other languages
English (en)
Inventor
Seip Paulus Johannes
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.)
Lever Brothers Co
Original Assignee
Lever Brothers Co
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
Priority claimed from LU48221A external-priority patent/LU48221A1/xx
Priority claimed from LU50100A external-priority patent/LU50100A1/xx
Application filed by Lever Brothers Co filed Critical Lever Brothers Co
Application granted granted Critical
Publication of US3413324A publication Critical patent/US3413324A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases

Definitions

  • a process for the alkali refining of glyceride oils and other fatty acid esters containing free fatty acid which gives unexpectedly low refining losses comprises mixing the ester with an ester (of the same or different chemical constitution) containing a lower percentage of free fatty acid in such proportions that the percentage of free fatty acid in the mixture is not greater than 4% and substantially less than in the first-mentioned esters, and the free fatty acid in the mixture is then substantially neutralized by the action of aqueous alkali thereon.
  • Continuous methods for carrying out the invention are described, in one of which part of the neutralized oil issuing from a reaction space in which neutralization has been effected is recirculated to that space.
  • the invention relates to improvements in the treatment of fatty acid derivatives and especially to the alkali re fining of glyceride oils and other functional fatty acid derivatives, containing free fatty acids and other impurities.
  • glyceride oils will be used throughout this specification to include animal and vegetable glyceride oils which .are normally solid, as well as those which are normally liquid.
  • a method for the alkali refining of crude glyceride oils and other functional derivaties of fatty acids, containing free fatty acids and other impurities, especially those having a relatively high initial free fatty acid content, in which to the oils or derivatives before the alkali treatment oils or derivatives are added having a lower free fatty acid content than said crude oils and derivatives.
  • the process of the invention is suitably carried out by mixing oils and other functional derivatives of fatty acids of the same type.
  • an oil or derivative may be added which has already been alkali-refined.
  • oils containing substantial amounts of free fatty acids either saturated or unsaturated, with a chain length of 16 carbon atoms or more, which generally tend to give higher refining losses than those oils containing free fatty acids with a chain length below 16 carbon atoms
  • oils of the lauric acid class such as coconut oil and palmkernel oil
  • oils which contain predominantly saturated free fatty acids with a chain length of 16 carbon atoms or more, such as cocoa butter, beef tallow, lard, mutton tallo, Borneo tallow, as well as hardened fats
  • oils may also be mixed with oils containing predominantly unsaturated free fatty acids with a chain length of 16 carbon atoms or more, such as vegetable liquid oils of the kind of cottonseed oil, soybean oil, olive oil, sunflower oil and groundnut oil, so as to obtain a reduction in refining losses.
  • the free fatty acid content in the oil mixture to be treated may differ appreciably for each particular oil if good results are to be obtained, it can be broadly indicated that this content is in the range of 14%, with preference for 25%.
  • the process may be carried out batchwise or continuously; in the latter case oil with a lower free fatty acid content is mixed with the crude oil prior to the alkali treatment.
  • oil with a lower free fatty acid content is mixed with the crude oil prior to the alkali treatment.
  • the amount of oil to be added to the crude oil orin the continuous processto be recirculated is dependent on the kind of crude oil treated, the amount and type of free fatty acids present in the crude oil, and on other process conditions, like temperature and concentration of the alkali.
  • the amount of oil to be recirculated must not be chosen too high in order not to reduce the throughput more than necessary, nor too low lest the process be ineffective.
  • the amount must be so chosen that the free fatty acid content of the mixture obtained, which has to be refined, is in the range which is advantageous for the particular oil to be treated.
  • the reduction of the free fatty acid content of the oil coming into contact with the aqueous alkaline solution must be so that the soap content of the refined oil is generally not more than about 0.1% by weight.
  • the preferred recirculation ratio is about 0.5.
  • the recirculation ratio is defined as the amount of oil which is recirculated in proportion to the amount of crude oil which is introduced into the refining apparatus.
  • the concentration of the aqueous alkali used usually lies in the range of 0.05 N to 2 N.
  • the method of the present invention may be carried out in a variety of ways.
  • the oil may, for instance, be neutralized in the still frequently used stirred cylindrical kettle having a cone-shaped bottom, the alkali being sprayed onto the oil.
  • the oil in the form of droplets may be caused to rise through a static body of aqueous alkali.
  • Another advantageous method of carrying out the invention is the one described in my co-pending application No.
  • Another advantageous process is that in which the alkali refining process is effected continuously in a bed of chemically inert packing material by causing the glyceride oil and the alkaline liquid to make random contacts with each other while flowing along tortuous paths through said bed and subsequently separating the oil and aqueous liquids by virtue of their different specific gravities.
  • This process may be carried out at temperatures from 60-100 C., but also temperatures above 100 C. are suitable, in which case the refining process has generally to be carried out at superatmospheric pressures to avoid evaporation of the aqueous phase.
  • Such a process is described in my co-pending application, Ser. No. 441,378, filed Mar. 19, 1965.
  • the process of the present invention may also be carried out continuously with the aid of centrifuges.
  • the improved method is also applicable to functional derivatives of fatty acids other than glyceride oils, which, for instance owing to their way of preparation or by other circumstances, contain appreciable amounts of free carboxylic acids, in particular free fatty acids.
  • functional derivatives can be mentioned esters, amides and the like, which, owing to their way of preparation or as a result of hydrolysis, thermal decomposition or other causes contain free carboxylic acids, in particular free fatty acids.
  • polycarboxylic acids which may be substituted, such as, e.g., the aliphatic dicarboxylic acids (adipic acid, azelaic acid, succinic acid), aromatic dicarboxylic acids (phthalic acid, tercphthalic acid, etc.), polymerized fatty acids and other polycarboxylic acids, such as, e.'g., citric acid.
  • the polycarboxylic acids maybe epoxidized.
  • esters can be prepared from the above acids with as an alcohol component one or more of the alcohols belonging to the following classes:
  • Aliphatic or aromatic polyvalent alcohols like propyleneglycol, triethyleneglycol, butanediol, neopentylglycol, glycerol, trimethylolpropane, trimethyolbutane, pentaerythritol, polypentaerythritol, allylalcohol, etc., which may be substituted.
  • the process is also applicable to mixtures of glyceride oils or mixtures of other fatty acid derivatives.
  • a flow sheet of the modification of the process according to the invention is indicated, in which a glyceride oil is continuously refined with an aqueous alkaline solution and part of the refined oil is recirculated.
  • the oil is stored in the vessel 1 and is after heating introduced into a neutralizing column 2 via pipe 3.
  • the neutralizing vessel may be one as described in our British patent application No. 11,861/ 64, but the figure is applicable to a variety of continuously refining processes.
  • the oil is introduced at the bottom of the column in the figure, but of course it can be introduced at any other place if desired, depending on the P evailing process conditions.
  • the alkali stored in another vessel 4 is after heating introduced into the column by pipe 5, but it can be introduced at any other place, if necessary.
  • the oil separated from the alkali leaves the column through pipe 6 and is collected in a vessel 7.
  • the pent alkali leaves the column through an outlet 8 and is transported to a collecting vessel 9.
  • Part of the refined oil is recirculated by means of pipe 10 and introduced into the stream of crude oil.
  • another oil which may be of a different kind, but which has a sufiiciently low free fatty'acid content to 'bring the free fatty acid content of the crude oil to the desired low level. In the figure this is indicated by conduit 11.
  • the supply of this oil with a low free fatty acid content is stopped, for instance by switching valve 12 and part of the neutralized oil is recirculated in the desired amount.
  • Example I Tallow was neutralized in an apparatus of the kind as described in British patent application No. 19,008/ 63.
  • the apparatus consisted of 36 zig-zag mounted guide plates having a length of 18 cm. and a width of 5 cm., placed in a slope of 5 in a housing having a length of 18 cm., a width of 5 cm. and a height of 100 cm.
  • a pipe was mounted in the middle of the plate at a distance of 1 cm. from the end of the plate.
  • the pipe ha to carry the alkaline solution downward through the oil layer onto the plate below.
  • the alkaline solution had a strength of 0.1 N to which 1% salt was added. This solution was dosed in an excess of 25%.
  • the temperature during neutralization was C. After this treatment the neutralized oil was post-treated with a 10 volume percent solution of 0.1 N caustic soda solution and subsequently washed with 10 volume percent (based on the amount of oil) of water to remove the soap.
  • Example 2 Palm oil was alkali-refined in a column of stainless steel with a height of 125 cm. and a diameter of cm. of the kind as described in British patent application No. 11,861/ 64. In the column a bed of inert fillings was present which had a height of 90 cm. and consisted of stainless Raschig rings of 8 by 8 by 0.5 mm. The column was closed to the atmosphere and the refining effected under a pressure of about 6.5 atm., the atmosphere being composed of introgen saturated with water vapour. The alkaline solution flowed countercurrently to the dispersed oil phase, the oil being introduced in the column just below the bed. The initial free fatty acid content of the crude oil was 6.1% and the water content 0.02%. The alkaline solution has a concentration of 0.3 N and was present in an excess of The temperature during the neutralization was kept at 140 C.
  • the refining factor was determined as follows:
  • Example 3 Crude palm oil with a free fatty acid content of 12.8% was alkali refined using the same apparatus as described in Example 2. The alkali had a concentration of 0.4 N and was present in an excess of 25%. The temperature was 140 C. In a first trial the palm oil was refined with a throughput of 1.8 tons/m. /hr. without recirculation. A neutral oil was obtained with a rather high soap content (about 1% of soap and 10% of water). In a second trial part of the refined palm oil was recirculated with a ratio of 2. The neutral oil had a final fatty acid content of 0.10, a water content of 1.4 and a soap content of 0.08%.
  • the refining factor was estimated at 1.3.
  • the throughput of the crude oil was increased to 2.5 tons/m. /hr., the recirculation ratio being 1.5, the final free fatty acid content was 0.09, the water content 1.8 and the soap content 0.12.
  • Example 4 Illipe butter was treated in the apparatus as described in Example 2, the initial free fatty acid content being 24.4%.
  • the alkali had a concentration of 0.4 N and was present in an excess of 25%, the temperature was adjusted at 140 C.
  • the crude oil throughput amounted to 1.2 tons/mF/hr.
  • the neutral oil contained a high amount of soap (about 20% of water and 2.0% of soap).
  • a portion of the refined oil was recirculated (the recirculation ratio being 3) and good results were obtained.
  • the final free fatty acid content was 0.12%, the water content 1.3 and the soap content 0.07%.
  • the refining factor was estimated at 1.3.
  • Example 5 Fish oil was treated in the apparatus as described in Example 2.
  • the free fatty acid content of the fish oil was about 3%. It has to be observed that fish oildepending on the source where it comes fromis often difficult to refine, even if the free fatty acid content is in the range which gives no difficulties for other oils.
  • 3.9 tons/m. /hr. of fish oil was refined at a temperature of C. with an alkaline concentration of 0.4 N present in an excess of 50%.
  • the final free fatty acid content was 0.11, the water content 2.5 and the soap content 0.17.
  • 2.2 tons/m. /hr. oil was recirculated, maintaining the throughput of crude oil on 3.9.
  • Example 6 Stearyl stearate was treated in the apparatus as described in Example 2, the initial free fatty acid content being 10%.
  • the alkali had a concentration of 0.4 N and was present in an exces of 25
  • the temperature was kept at C. and the throughput amounted to 1.4 tons/m. /hr.
  • the ester contained a relatively high amount of water (about 12%) and soap (about 1.5%
  • a portion of ester treated was recirculated, the recirculation ratio being 2, and good results were obtained.
  • the final free fatty acid content was 0.1% and the soap content 0.02%.
  • Process according to claim 1 characterized in that the process is carried out continuously and during refining part of the treated material is sefoldted from the aqueous phase, recirculated and added to the crude material to be treated in such proportions that the percentage of free fatty acid in the mixture is not greater than 4% by weight and substantially lower than in the initial ester.
  • Process according to claim 2 which comprises feeding continuously into a reaction space at a temperature above 60 C. aqueous alkali of concentration 0.05 N to 2 N, the said oil and an oil of lower free fatty acid content, in such proportions that the percentage of free fatty acid in the mixture is not greater than 4% and substantially lower than in the first-mentioned oil, allowing the mixture to travel through said reaction space at a temperature above 60 C. until the free fatty acid is substantially neutralized, stopping the flow of said oil of lower free fatty acid content and instead continuously feeding back into the reaction space a proportion of the neutralized oil said proportion being such as to maintain the initial free fatty acid content of the mixture substantially unchanged.
  • Process according to claim 1 which comprises feeding continuously into a reaction space at a temperature above 60 C. aqueous alkali of concentration 0.05 N to 2 N, the said ester and an ester of lower free fatty acid content, in such proportions that the percentage of free fatty acid in the mixture is not greater than 4% and substantially lower than in the first-mentioned ester, allowing the mixture to travel through said reaction space at a temperature above 60 C. until the free fatty acid is substantially neutralized, stopping the flow of said ester of lower free fatty acid content and insttead continuously feeding back into the reaction space a proportion of the neutralized ester said proportion being such as to maintain the initial free fatty acid content of the mixture substantially unchanged.
  • Process according to claim 2 characterized in that the process is carried out continuously and during refining, part of the treated material is separated from the aqueous phase, recirculated and added to the crude material to be treated in such proportions that the percentage of free fatty acid in the mixture is not greater than 4% by weight and substantially lower than in the initial oil.
  • NICHOLAS S. RIZZO Primary Examiner.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
US541436A 1965-03-19 1966-03-14 Process for alkali refining of glyceride oils and fatty acid esters Expired - Lifetime US3413324A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
LU48221A LU48221A1 (enrdf_load_html_response) 1965-03-19 1965-03-19
LU50100A LU50100A1 (enrdf_load_html_response) 1965-12-20 1965-12-20

Publications (1)

Publication Number Publication Date
US3413324A true US3413324A (en) 1968-11-26

Family

ID=26639950

Family Applications (1)

Application Number Title Priority Date Filing Date
US541436A Expired - Lifetime US3413324A (en) 1965-03-19 1966-03-14 Process for alkali refining of glyceride oils and fatty acid esters

Country Status (6)

Country Link
US (1) US3413324A (enrdf_load_html_response)
AT (1) AT287880B (enrdf_load_html_response)
DE (1) DE1617020A1 (enrdf_load_html_response)
GB (1) GB1143367A (enrdf_load_html_response)
NL (1) NL6603636A (enrdf_load_html_response)
SE (1) SE341860B (enrdf_load_html_response)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3653842A (en) * 1969-12-16 1972-04-04 Westinghouse Electric Corp Computer control system for refining and hydrogenation of unsaturated hydrocarbons
WO2015076818A1 (en) * 2013-11-22 2015-05-28 Hill's Pet Nutrition, Inc. Method of preparing palatability enhancer
US20170291121A1 (en) * 2016-04-07 2017-10-12 Nikolai Kocherginksy Membrane-based washing and deacidification of oils
EP2611767B1 (en) 2010-09-03 2017-10-25 Stepan Specialty Products, LLC Elimination of organohalo and oxirane species in carboxylic acid ester streams

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3653842A (en) * 1969-12-16 1972-04-04 Westinghouse Electric Corp Computer control system for refining and hydrogenation of unsaturated hydrocarbons
EP2611767B1 (en) 2010-09-03 2017-10-25 Stepan Specialty Products, LLC Elimination of organohalo and oxirane species in carboxylic acid ester streams
USRE48861E1 (en) 2010-09-03 2021-12-28 Stepan Specialty Products, Llc Elimination of organohalo and oxirane species in carboxylic acid ester streams
WO2015076818A1 (en) * 2013-11-22 2015-05-28 Hill's Pet Nutrition, Inc. Method of preparing palatability enhancer
US10561162B2 (en) 2013-11-22 2020-02-18 Colgate-Palmolive Company Method of preparing palatability enhancer
US20170291121A1 (en) * 2016-04-07 2017-10-12 Nikolai Kocherginksy Membrane-based washing and deacidification of oils
US10065132B2 (en) * 2016-04-07 2018-09-04 Nikolai Kocherginksy Membrane-based washing and deacidification of oils

Also Published As

Publication number Publication date
DE1617020A1 (de) 1971-03-04
AT287880B (de) 1971-02-10
SE341860B (enrdf_load_html_response) 1972-01-17
NL6603636A (enrdf_load_html_response) 1966-09-20
GB1143367A (en) 1969-02-19

Similar Documents

Publication Publication Date Title
US2383632A (en) Process of treating fatty glycerides
US2360844A (en) Preparation of detergents
US2383633A (en) Process for treating fatty glycerides
JPS611640A (ja) 短鎖アルコールの脂肪酸エステルの製法
GB2089793A (en) A process for the simplified production of light-coloured washing-active a-sulfofatty acid esters
US2383580A (en) Treating fatty materials
US2383614A (en) Treatment of fatty glycerides
US3413324A (en) Process for alkali refining of glyceride oils and fatty acid esters
US2383602A (en) Process for treatment of fatty glycerides
US2391236A (en) Oxidation of paraffinic hydrocarbons
US2383599A (en) Treating fatty glycerides
US2544725A (en) Method of refining glyceride oils
US2474740A (en) Process of preparing partial esters of glycerine and fatty acids
US2452724A (en) Soap-making process
EP0076682B1 (en) Interesterification process and apparatus
US2359404A (en) Chemical processes and products thereof
IT9020317A1 (it) Procedimento di deodorazione di olii e grassi
US2378006A (en) Process for treating fats and fatty oils
US3160646A (en) Production of monoglycerides
NO175486B (no) Fremgangsmåte for fjerning av uönsket lukt fra fettsyreblandinger
USRE22751E (en) Process of treating fatty
US3095431A (en) Interesterification process
US3141013A (en) Purification of transesterification mixtures
GB1446831A (en) Process for deodorization and steam refining of'fats and oils
US3079412A (en) Continuous manufacture of monoglycerides