CA2032676A1 - Process for refining organic-solvent containing crude polyol fatty-acid polyester products - Google Patents
Process for refining organic-solvent containing crude polyol fatty-acid polyester productsInfo
- Publication number
- CA2032676A1 CA2032676A1 CA002032676A CA2032676A CA2032676A1 CA 2032676 A1 CA2032676 A1 CA 2032676A1 CA 002032676 A CA002032676 A CA 002032676A CA 2032676 A CA2032676 A CA 2032676A CA 2032676 A1 CA2032676 A1 CA 2032676A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- reaction product
- crude
- fatty
- soap
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
- C07H13/06—Fatty acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S203/00—Distillation: processes, separatory
- Y10S203/06—Reactor-distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S203/00—Distillation: processes, separatory
- Y10S203/22—Accessories
Abstract
ABSTRACT
The present invention pertains to a process for refining organic-solvent containing crude polyol fatty-acid polyester reaction product, comprising the steps of distilling the crude reaction product to substantially remove the organic solvent, and subsequently subjecting the distilled reaction product to a bleaching treatment. The process allows an economic use of bleaching accents while achieving good colour and colour stability of the refined product.
The present invention pertains to a process for refining organic-solvent containing crude polyol fatty-acid polyester reaction product, comprising the steps of distilling the crude reaction product to substantially remove the organic solvent, and subsequently subjecting the distilled reaction product to a bleaching treatment. The process allows an economic use of bleaching accents while achieving good colour and colour stability of the refined product.
Description
~32~
PROCESS FOR REFINING
ORG~NIC-SOLVENT CONTAINING CRUDE POI,YOL F~TTY--ACID POLYESrER PR0D~CTS
Ihe present invention relates to a pro oe ss for refining organic-solvent containing crude polyol fatty-acid polyester reaction products, and in particular, although not exclusively, to such a prooess for refining crude sugar fatty-acid polyester reaction products.
Polyol fatty-acid polyesters and in particular, the sugar fatty-acid polyesters such as e.g. the sucrose fa~ty-acid polyester~s, are knKwn as suitable lcw-calorie fat-repla oers in edible products.
Substantially indigestible for human b~ings they have physical and crganoleptic properties very similar to triglyceride oils and fats conventionally used in edible products. In a~;tion, polyol fatty-acid polyesters are reported to have use as pharmaoeutical agents e.g. in view of their ability to take up fat-soluble sub6t~no~s, such as in parti~lar cholesterol, in the gastro-intestmal tract, and subsequently remove these substanils from the human body.
In this specification the term "polyol" is intended to include any aliphatic or aramatic ccmpound which comprises at least four free hydroxyl groups. Such polyols in particular include the group of sugar polyols, ~hich cQmprises the sugars, i.e. the mono-, di- and polysaccharides, the corresponding sugar alcohols and the derivatives thereof having at least four free hydroxyl groups. EXamples of sugar polyols include glucose, mannose, galactose, xylose, fructose, sorbose, tagatose, ribulose, xylulose, maltose, lactose, cellobiose, raffinose, sucrose, erythritol, mannitol, lactitol, sorbitol, xylitol and ~-methylglucoside. A generally used sugar polyol is sucrose.
The term "polyol fatty-acid polyester" is intended to include any .
.
~V3~
PROCESS FOR REFINING
ORG~NIC-SOLVENT CONTAINING CRUDE POI,YOL F~TTY--ACID POLYESrER PR0D~CTS
Ihe present invention relates to a pro oe ss for refining organic-solvent containing crude polyol fatty-acid polyester reaction products, and in particular, although not exclusively, to such a prooess for refining crude sugar fatty-acid polyester reaction products.
Polyol fatty-acid polyesters and in particular, the sugar fatty-acid polyesters such as e.g. the sucrose fa~ty-acid polyester~s, are knKwn as suitable lcw-calorie fat-repla oers in edible products.
Substantially indigestible for human b~ings they have physical and crganoleptic properties very similar to triglyceride oils and fats conventionally used in edible products. In a~;tion, polyol fatty-acid polyesters are reported to have use as pharmaoeutical agents e.g. in view of their ability to take up fat-soluble sub6t~no~s, such as in parti~lar cholesterol, in the gastro-intestmal tract, and subsequently remove these substanils from the human body.
In this specification the term "polyol" is intended to include any aliphatic or aramatic ccmpound which comprises at least four free hydroxyl groups. Such polyols in particular include the group of sugar polyols, ~hich cQmprises the sugars, i.e. the mono-, di- and polysaccharides, the corresponding sugar alcohols and the derivatives thereof having at least four free hydroxyl groups. EXamples of sugar polyols include glucose, mannose, galactose, xylose, fructose, sorbose, tagatose, ribulose, xylulose, maltose, lactose, cellobiose, raffinose, sucrose, erythritol, mannitol, lactitol, sorbitol, xylitol and ~-methylglucoside. A generally used sugar polyol is sucrose.
The term "polyol fatty-acid polyester" is intended to include any .
.
~V3~
2 L 7216 (R) such polyesters or mixtures thereof of which, on an average, 70 % or more of the polyol hydroxyl groups have been esterified with fatty-acids, i.e. which have degrccs of esterification of 70 % or more.
m e term "fatty acid" refers to C8-C24 fatty acids which may be saturated or unsaturated, and may ha~e straight or branched aIkyl chains.
In general polyol fatty-acid po]yesters are synthesized by a prccess in which a polyol, such as a mono- or disaccharide, is reacted with a fatty-acid lower alkylester, in general the fatty-acid methylester, in the presence of a traisesterification catalyst, such as e.g. an aIkali metal hydroxide or carbonate, and an emulsifier, such as an alkali metal soap. In a first stage a polyol fatty-acid mono- or oligoester is formed, which in a second stage is further reacted with the fatty-acid lower aIkylester to form polyesters of the desired degree of esterification. It is also possible to combine the two stages of the reaction into a single step.
Proc.sses of this type have been described in e.g. the US pate~t specifications Nos. 3,963,699, 4,517,360, and 4,518,772, and EP patent spscifications Nos. 0 256 585, 0 301 634 and 0 320 043.
qhe crude polyol fatty-acid polyester reaction products resulting from conventional syntheses contain in addition to the desired polyesters, components such as fatty-acid soaps, excess fatty-acid lower aIkylesters and polyol fatty-acid oligoesters. Also, due to the relatively high temperatures at which conventional processes are carried out, often by-products are formed which may ke undesirable in view of their chemical characteristics, such as in particular discolouring proFerties. In general it is therefore nec~ss~ry to further purify or refine the crude polyol fatty-acid polyester reaction products resulting from such conventional synth~cPc.
me term "crude polyol fatty-acid polyester reaction product" is intended to refer to unrefinsd or partially refined reaction products of processes for the synthesis of polyol fatty-acid polyesters. m e two volumeJwise major ccmponents in such crude ccmpositions in general are 2~326~
m e term "fatty acid" refers to C8-C24 fatty acids which may be saturated or unsaturated, and may ha~e straight or branched aIkyl chains.
In general polyol fatty-acid po]yesters are synthesized by a prccess in which a polyol, such as a mono- or disaccharide, is reacted with a fatty-acid lower alkylester, in general the fatty-acid methylester, in the presence of a traisesterification catalyst, such as e.g. an aIkali metal hydroxide or carbonate, and an emulsifier, such as an alkali metal soap. In a first stage a polyol fatty-acid mono- or oligoester is formed, which in a second stage is further reacted with the fatty-acid lower aIkylester to form polyesters of the desired degree of esterification. It is also possible to combine the two stages of the reaction into a single step.
Proc.sses of this type have been described in e.g. the US pate~t specifications Nos. 3,963,699, 4,517,360, and 4,518,772, and EP patent spscifications Nos. 0 256 585, 0 301 634 and 0 320 043.
qhe crude polyol fatty-acid polyester reaction products resulting from conventional syntheses contain in addition to the desired polyesters, components such as fatty-acid soaps, excess fatty-acid lower aIkylesters and polyol fatty-acid oligoesters. Also, due to the relatively high temperatures at which conventional processes are carried out, often by-products are formed which may ke undesirable in view of their chemical characteristics, such as in particular discolouring proFerties. In general it is therefore nec~ss~ry to further purify or refine the crude polyol fatty-acid polyester reaction products resulting from such conventional synth~cPc.
me term "crude polyol fatty-acid polyester reaction product" is intended to refer to unrefinsd or partially refined reaction products of processes for the synthesis of polyol fatty-acid polyesters. m e two volumeJwise major ccmponents in such crude ccmpositions in general are 2~326~
3 L 7216 (R) the polyol fatty-acid polyester compone~t and ~the organic solvent.
For the purposes of the present specification ~he term 'organic solvent' is intended to refer to the grcup of relatively volatile fatty-acid sources as may be used in excess amcunt in the synthesis reaction of the polyol fatty-acid po]yester, and any organic solvents used or introduced during synthesis or refining.
A prominent example of such a relatively volatile fatty-acid source is e.g. fat~y-acid lower alky]es~er used in the tr~i :esberification reaction described hereinbefore.
In the crude reaction product the polyol fatty-acid polyester component is generally present in an amount of 10 to 95 ~ by weight of the crude product, and the organic solvent is generally present in an amount of 5 to 90 ~ by weight.
Conventional refining methods comprise a variety of different treatments including washings with water, organic solvents, acid or alkaline solutions, salting-out treatments, bleachLng steps, distillation, stripping and deodorisation treatments.
In general the washing treatments aim at a substantial reduction of the soap component which can be present in the crude polyol fatty-acid polyester reaction product by reason of its use as the emulsifiersystem in the preceding synthesis reaction of the polyester or, to a limited extent, due to partial conversion to scap of ~he fatty-acid source, such as the fatty-acid lower aIkylester.
These washing treatments are often followed by a bleaching treatment with adsorbents such as bleaching earth, activated carbon and silicas, primarily aimed at removing coloured mat~er, discolouring mat~rials, residual soap and metal ions. Descriptions thereof can be found in US 4,334,061, EP O 319 091 and EP O 319 092.
Adsorbents are well-known in conventional oil technology. Although very suitable and to some extent indispensible for the purpose of their use, large volume use thereof is uneconomical in view of the costs 2 0 3 2 ~ J ~
For the purposes of the present specification ~he term 'organic solvent' is intended to refer to the grcup of relatively volatile fatty-acid sources as may be used in excess amcunt in the synthesis reaction of the polyol fatty-acid po]yester, and any organic solvents used or introduced during synthesis or refining.
A prominent example of such a relatively volatile fatty-acid source is e.g. fat~y-acid lower alky]es~er used in the tr~i :esberification reaction described hereinbefore.
In the crude reaction product the polyol fatty-acid polyester component is generally present in an amount of 10 to 95 ~ by weight of the crude product, and the organic solvent is generally present in an amount of 5 to 90 ~ by weight.
Conventional refining methods comprise a variety of different treatments including washings with water, organic solvents, acid or alkaline solutions, salting-out treatments, bleachLng steps, distillation, stripping and deodorisation treatments.
In general the washing treatments aim at a substantial reduction of the soap component which can be present in the crude polyol fatty-acid polyester reaction product by reason of its use as the emulsifiersystem in the preceding synthesis reaction of the polyester or, to a limited extent, due to partial conversion to scap of ~he fatty-acid source, such as the fatty-acid lower aIkylester.
These washing treatments are often followed by a bleaching treatment with adsorbents such as bleaching earth, activated carbon and silicas, primarily aimed at removing coloured mat~er, discolouring mat~rials, residual soap and metal ions. Descriptions thereof can be found in US 4,334,061, EP O 319 091 and EP O 319 092.
Adsorbents are well-known in conventional oil technology. Although very suitable and to some extent indispensible for the purpose of their use, large volume use thereof is uneconomical in view of the costs 2 0 3 2 ~ J ~
4 L 7216 (R) associat~d with the adsorbents themselves, reductions in oil yield, and the disposal of spent adsorbents.
It is therefore a first object of the present invention to provide a bleaching treatment suitable for the refining of crude polyol fatty-acid polyester reaction products which al~ows a reduoad level, or alternatively a re effective use, of the adsorbent u~ed in the bleaching treatment.
It is a further object of the present invention to provide a bleaching treatment by which 1~ oolour characteristics and low levels of discolouring oamponRnts are achieved and the discolouring problems during sub6equent refining steps are avoided.
Accordingly, in its broadest aspects the present invention prcvides a process for refining organic-solvent containing crude polyol fatty-acid polyester reaction product, comprising the steps of:
(a) distilling tha crude reaction product to substantially remove said organic solvent; and 0 (b) subsequently subjecting the distilled reaction product to a bleaching treatment.
The key feature of the present invention is that the distilling step by which the organic solvent and optionally further volatile components present in the crude reaction product are removed to a substantial degree, takes place before the bleaching treatment to remcve coloured mat~ers.
Aocordingly, in the refining process according to the invention a substantial part of the organic solvent is removed by distillation before a further bleaching treatment. Also further volatile o~mponents such as e.g. free fatty acids may be removed in the distilling step.
m e distillation of the crude reaction product may be carried out in oonventional manner using temperatures in the range of from 60 to 300C. In general temperatures of above 150C will be used since these allow reducad pressure regimes economically feasible on a technical scale. Preferred distilling temperatures lie within the range of 160 to ~ ~ 3 ~
L 7216 (R) 240C, temperatures of 200 to 240C being preferred m~st.
As already indicated the distilling step is prefexably carried out under reduced pressure, in particular pressures of below 100 mbar, such as between 30 and 70 mkar. Pressures of between 1 and lO mbar and in particular pressures between 1 and 5 mkar are preferred.
Althou3h appropriate distilling times will strongly depend upon temperature and pressure conditions applied, e.g batch-wise distilling times of between 30 and 100 minutes have been found suitable, whereas continuous distilling times can be ~uch shorter and are determined by the equipment used.
In exoeptional circum:tances where the crude reaction product at the distilling stage still comprises significant levels of relatively temperature-sensitive components it may be n~c~ssary to use relatively low distilling temperatures within the range of 60 to 150C, in particular, 80 to 120C. Removal from or reduction in the crude reaction product of the relevant organic components by distilling at such low temFeratures will reguire more severe reduoed pressure conditions, in particular, of below 1 mbar, or even b~low 0.1 mbar.
Although technically best results are achieved when the organic solvent is substantially removed from the crude reaction product prior to a subsequent bleaching treatment, worthwhile advantages are already obtained at removal levels of 40 % or more by weight of the organic solvent, removal levels of 70 ~ or more being preferred, and levels of 95 ~ or more being preferred most.
A further essential element of the present invention is the bleaching treatment subsequent to the distilling of the reaction product. m e bleaching treatment and the bleaching agent selected is particularly triggered tcwards effective removal of the coloured matter. Sui~able bleaching agents are carbons and bleaching earths, which may or nay not be activated by appropriate acid treatment, silicas, clays and synthetic adsorbents.
Suitably, the bleaching agents are added to the reaction product 2~3~7~
6 L 7216 (R) in amounts of 0.2 to 5 ~ by weight and preferably in amounts of 0.5 to 3 ~ by weight. Often very good results are obtained with amounts of 1 to 2 % by weight.
In general the bleaching treatment is carried out at an elevated temperature. Suitable bleaching temp~lratures are within the range of 70 to 140C, temperatures of 80 to 120C being preferred.
Dependent upon the ~leaching agent selected bleaching results may be i~proved by the presence in the reaction product of low levels of water. In particular when silicas are used water levels are best between 0.1 and 0.5 %. Where bleaching is best carried out under dry conditions, such as e.g. when bleaching earths are used, suitably oonditions of reduced pressure are applied, pressures of below 100 mbar and in particular between 30 and 70 mbar being preferred.
Normal bleaching times vary between 30 and 120 minutes, times of between 30 and 60 minutes in many mstancas being sufficient.
After the bleaching treatment the bleaching agent togethPr with the absorbed coloured materials are in general removed by filtration which may be assisted by introduction of a filter aid such as cellulose.
In addition to the distilling and subeeauent bleaching treatment the refining process in accordance with the present invention preferably comprises refining treatments preceding the distilling step to substantially remove the soap and metal ion components in the crude reaction product. Removal of these components will av~id problems of discolouring during subsequent high-temperature refining treatments, such as the distilling step. At the stage before the distilling step it is not so much an object to remove the coloured matt~r and this may suitably be primarily effected during the bleaching step subsequent to the distilling.
m ese pre-distilling treatments may comprise any suitable method to substantially remove in particular the soap and aIkali metal ions which may be prlesent in the crude reaction product. Suitable such 2~3~7~
7 L 7216 (R) refining treatments include conventional washing treatments such as water washings with or without added electrolytes, and aIkaline or acid wzshings as described in EP o 319 092 herein incorporated by reference.
Instead of or in addition to such conventional washing treatments preceding the distillation it may be especially useful to contact the crude polyester reaction product with an acid to substantially convert the soap component to its corresponding free fatty acids.
The acid is used to establish conversion of the soap ccmponent to its free fatty acids and the amount 1hereof in principle must be sufficient to substantially convert all of the scap present in the crude polyester product. The amount of acid will depend upon the level of the soap emulsifier system used in the synthesis reaction as well as the amounts of soap formed or intrcduced d~ring the synthesis reaction.
For reasons of cost it is preferred that the amo~nt of acid is as close to the precise amount needed as technically feasible to establish full neutralising of all the soap present in the crude reaction product, amounts of acid in excess over what is theoretically needed to fully neutralize the aIkaline components in the crude polyester reaction product preferably being as lcw as o to 10 %, the range of o to 5 %
being particularly preferred.
To ensure subs~antially full conversion of t`he soap to free fatty acids the strength of the acid mNst be such that the equilibrium of the conversion reaction lies substantially fully at the side of the free fatty acids, the pH-values resulting from the addition of the acid to the crude reaction product, in general in the form of an aqueous solution thereof, preferably keing kelow 6, the range of pH 3 to 5 keing preferred most.
&itably, both inorganic and organic acids can be used which in view of the important application of the polyol fatty-acid polyesters in focd products preferably are food grade. Suitable inorganic acids are phosphoric acid and dihydrogen phosphoric acid alkali metal salts.
&itable organic acids include acetic, lactic, succinic and citric acid, the latter acid keing preferred.
2 ~J 3 .~
8 L 7216 (R) Preferably, a relatively concentrated aqueous acid solution is used. Suitable concentrations lie within the range of 25 % by weight or more. To allcw convenient removal of the salt resulting from the acid step, conoe ntrated acid solutions of 40 % to 85 % are preferred, concenLl~tions of 40 to 60 % being preferred most.
m e acid step has to be followed by substantial removal from the crude polyester reaction product of any salts present therein, in general alkali-metal salts which together with the free fatty acids result from the soap conversion by th~e acid. The substantial removal of the salt may be effected by using conventional separation techniques, such as centrifuge or filtration techniques. Suitable filtration techniques may involve the use of filter-aids, such as e.g. oe llulose.
In particular, when the salt is removed by way of fil~tion, it has been found that the removal of this salt, generally being the alkali metal salt of the acid used in the soap-conversion step, is improved if the water level in the acidulated reaction pro~uct resulting e.g. from the aqueous acid solution, is reduced to very low levels which preferably correspond to a system substantially without free water being present, i.e. all water being either dissolved in the polyester phase or being present as crystal or bound water of further components in the reaction product. Suitable such water levels are below 0.3 % by weight, and preferably lie below 0.1 or even 0.05 % by weight. This can be conveniently effected by subjecting the reaction product to appropriate drying conditions at elevated temperature and reduced pressure. This drying step may be carried out subsequent to or during ~he contact times discusssd herein-before.
A preferred method of reducing the water to very low levels is flash-drying by which the reaction product is passed into a low-pressure chamber and any water present is vaporised adiabatically. The heat needed for such evaporation is drawn from the reaction mixture and accordingly this method can be used for the simultaneous drying and cooling of the reaction mixture from the temperature of the acid step to well below 100C, in particular 70 to 90C. If flash-drying is used for sinultaneous drying and cooling, the water level in the reaction mixture after the addition of the acid solution may be higher than 2 ~
g L 7216 (R) descriked hereabove, in order to ensure sufficient cooling during the flash-drying process. Water levels of 2 to 5 % by weight will ensure a cooling of about 20 to 50C which in general will avoid any further separate coolLng step.
It has further been found that the removal of the salt as also the colour and discolouring properties of the fLnal refined p~lyester product are advantageously affected, if prior to the introduction of the acid in the pre-distilling treatment first a relatively small amount of an aqueous aIkaline solution is addPd to the crude polyester product which is subsequently neutralized by the acid simLltaneous to the conversion of the soap component to its free fatty acid.
Within the constraint of avoiding or minimizing the risk of the formation of undesirable components the particular combination of source, volume and level of alkalinity is not very critical and can be any of the readily available aIkaline materials, such as the aIkali metal hydroxides, carbonates or silicates, generally at a level within the range of 0.1 to 6 N, in particular, 0.2 to 4 N, or even, 0.2 to 1 or 2.5 N. m e a~ueous alkaline solution is suitably added to the crude polyester product in an amount of 0.5 to 5 % by weight of the product. Preferably, some agitation is applied to improve the contact between the crude polyester product and the aqueous alkaline solution.
In a batch-wise operation contact times in the acid step and optional prior alkaline step of between 1 and 10 minutes between the introduction of the aqueous alkaline solution and the introduction of the acid have been found sufficient. In a continuous operation contact times are generally shorter than 3 minutes, such as l~ than about 1 munute, and can be as short as 5 to 30 seconds.
Although in the pre-distilling refining treatment the acid step and optional prior aIkaline step can be combined with further conventional washings as described hereinbefore, it is preferred to apply the acid step and the optional prior addition of an aqueous alkaline solution without further washing steps.
A preferred pre-distilling treatment to substantially remove any ~ t7 ~
L 7216 (R) soap and alkali metal ion components may further consist of a bleaching treatment which contrary to the bleaching treatment sub6eguent to the distilliny step is not so much directed to removal of coloured matter but directed to the removal of residual scap and alkali metal ions.
Suitably, similar adsorbent agents and bleaching conditions can be us~d as described hereinbefore.
PccYrdingly, in a preferred :mbndlment of the present inYention the refining process comprises subjecting the crude reaction product to a first bleaching treatment, subsequently distilling the once bleached reaction product to substantially remove the organic solvent; and subjecting the distilled reaction product to a second bleaching treatment.
In a particul æ ly preferred emkodlment the present invention provides a refining process in ~hich before the distilling step the crude reaction product is contacted with an acid followed by removal of salt as described hereinbefore, and subjected to a first bleaching treatment, the absorbent of said first bleaching treatment keing introduced before said removal of salt. In such a process the removal of salt and adsorbent is suitably be cGmbined.
Subsequent to the second bleaching treatment the resulting polyester product may be subjected to a high-temperature refining treatment to remove volatile components and any residual free fatty acids. Such high-temperature refining treatment in particular will include a further deodorizing step, such as steam-stripping, at a temperature of above 150C, such as 150 to 300C. Preferred temperatures are 180 to 260C, in particular 190 to 240C, temperatures of 220 to 240C being preferred most.
m e invention is in particul æ directed to the refining of crude polyol fatty-acid polyester reaction products of transesterification reactions involving excess amounts of fatty-acid lower aIkylesters.
This type of transesterification reaction is particularly suitable for the synthesis of polyol fatty-acid polyesters having high degrees of esterification of 70 % or more, and accordingly, the present process is ~'~3~'7'~
ll L 7216 (R) p æticularly applicable to the refining of crude polyol fatty-acid polyester having such high degrees of esterification, in particular crude products ccmprising polyol fatty-aeid polyesters having degr~
of esterification of 80 % or more, or even 90 % or more. Preferably, sueh crude polyester reaction prcducts derived from the suyar polyols selected from the group of disaccharides or the alcohol derivatives thereof, such as sucrose, and esterified to over 95 % fatty-aeid su~stitution, are suitably refined by the process in accordance with the present invention.
Having a reduoed risk of discolouring the polyol fatty-acid polyesters refined in accordance with the prooess of the present invention æe partic~ul æly suitable to replace fully or partially conventional trigly oeride fats in focd ccmpositions intended for high-temperature purposes, such as b~king and frying oils. Generally, insuch food cQmpositions at least 10 % by wei~ht of the conventional triglyceride fat is replaoed by the polyol fatty-acid polyesters in aelordanee with the present invention. ~referably, at least 50 % of the conventional fat is replaoed by the polyesters.
Ihe invention is now further illustrated with reference to the follcwing examples, percentages being by weight unless indicated otherwise.
EX~MPLE 1 A batch of crude sucrose fatty-acid polyester reaction product, synthesized in a solvent-free trarsesterification reaction between sucrose and touch-h ædened soybean oil derived, non-distilled fatty-acid methylester to a degree of esterification of over 95 %, consistedof the following co~ponents:
sucrose fatty-acid polyester 44.6 %
fatty-acid methylester 46.9 %
soap (mainly coconut-derived potassium soap)3.8 %
minor components 4.7 %
m is batch ~as first washed with 7.5 % of water, agitated during 7 ~
12 L 7216 (R) 15 minut~ at 80C and oe ntrifuged (3000 rpm for 10 minutes) to separate the water with the bulk of the soap and dried at 90C and 50 mbar pressure. The water-washed sucrose polyester reaction product was further refined using 3 different procedures:
procedure 1 20 grams bleaching earth (Supre~e FF ex TonsilR) was added per kg water-washed sucrose polyester reaction product and the resulting mixture ~as stirred for 30 min at 90C and atmospheric pressure. The suspension was filtered throu~h a 2 microns filter and distilledtdeodorised (3 hours, 200C) The colour values of the refined reaction product as measured in a 2" cell of an Au~cmatic Colori Meter ex Morgan Smith Electronics LtdR
were 24.0 Yellow and 3.4 Red.
~rooedure 2 10 grams bleaching earth (Supreme FF ex TbnsilR) was added per kg water-washed sucrose polyester reaction product and the r ~lltLng mixture was stirred for 30 min at 90C and atmospheric pressure. The suspension was filtered through a 2 microns filter and distilled (1 hour, 200C) to remove the bulk of the fatty-acid methylester (> 95 ~ removal). After distillation the reaction product was dried (50 m~ar, 90C) and 10 grams bleaching earth (Supreme FF ex TbnsilR) was added per kg distille~ reaction product. The suspension was stirred for 30 min (atmospheric, 90C) and filtered through a 2 microns filter, followed by deodorisation at 200c for 2 hours.
The colour values of the refined reaction product as measured in a 2" oe ll of an Autcmatic Colori Meter ex Morgan Smith Electranics Lt were 19.0 Yellow and 2.5 Red.
procedure 3 10 grams b~eaching earth (Supreme FF ex TbnsilR) per kg water-washed sucrose polyester reaction product was added and the resulting 13 L 7216 (R) mixture was stirred for 30 min at 90C and atmospheric pressure. m e suspension was filtered throu~h a 2 microns filter. me reactant product was subsequently dried (50 mkar, 90C) and the bleaching treatment repeated. Subseguently, ~he twioe bleached product was distilled/deodoris~d at 200C for 3 hours.
Ihe colour values of the refined reaction product as measured in a 2" cell of an Automatic Colori Meter ex M~rgan Smith Electronics LtdR
were 25.0 Yellow and 3.2 Red.
Co~parison of the colour results after the 3 different procedures indicate that pro oedure 2, which embodies the prooess of the present inNention, is the most effective having the best colour results while requiring 1~ bleaching earth than the procedures 1 and 3 (15 grams compared to 20 grams per kg crude reaction product).
EX~MPLE 2 A batch of crude sucrose fatty-acid polyester reaction product, synthesized in a solvent-free transesterification reaction between sucrose and touch-hardened soybean oil derived, distilled fatty-acid methylester to a degree of esterification of over 95 %, consisted of the following components:
sucrose fatty-acid polyester 49.8 %
fatty-acid methylester 43.2 %
soap (mainly coconut-derived potassium soap)3.8 %
minor components 3.2 %
miS batch was first washed with 7.5 % of water, agitated during 15 minutes at aooc and centrifuged at 3000 rpm for 10 minutes to separate the water with the bulk of the soap and dried at 90C and 50 mbar pressure. After drying 0.2 % by weight of water was added.
Subsequently, after 5 minutes stirring 0.5 % of Trisyl ex Gra oeR was added to remove residual soap and the resulting mixture was stirred for 30 min at 90C and atmospheric pressure and filtered through a 2 microns filter.
14 L 7216 (R) Ihe resulting product was further refined using two different procedures.
Procedure 1 15 grams of blea_h mg earth (St~dard FF ex TonsilR) was added per Xg of partially refined sucrose polyester reaction produc~ and the resulting mixture was stirred for 30 min at 90C and atmoepheric pressure. Ihe suspension was filtered through a 2 microns filter and distilled/deodorizt~s (3 hours, 215C).
The colour values of the refined reaction product as me2sured in a 2"
cell of an Automatic Colori Meter ex Morgan Smith Electronics LtdR were 30.0 Yellow and 3.7 Red.
procedure 2 The partially refined sucrose polyester reac~ion product was first distilled (1 hour, 215C) to remove the }ulk of the fatty-acid methylester (> 95 % removal). After distillation the reaction product was dried (50 mbar, 90C) and 15 ~rams of bleaching earth (Star.dard FF
ex IonsilR) was added per kg distilled reaction product. m e suspension was stirred for 30 min (atmospheric, 90C) and filtered throu3h a 2 microns filter, followed by deodorization at 215C for 2 hours.
The colour values of the refined reaction product as neasured in a 2" cell of an Automatic Colori Meter ex Morgan 5mith Electronics LtdR
were 29.0 Yellow and 3.7 Red.
Ccmparison of the 2 procedures shows that procedure 2 in accordance with the invention gives equal or even scmewhat better colour results but requires less bleaching earth to achieve this (15 grams per kg distilled product ccmpared to 15 grams of non-distilled pro~uct which amounts to about 67 %).
It is therefore a first object of the present invention to provide a bleaching treatment suitable for the refining of crude polyol fatty-acid polyester reaction products which al~ows a reduoad level, or alternatively a re effective use, of the adsorbent u~ed in the bleaching treatment.
It is a further object of the present invention to provide a bleaching treatment by which 1~ oolour characteristics and low levels of discolouring oamponRnts are achieved and the discolouring problems during sub6equent refining steps are avoided.
Accordingly, in its broadest aspects the present invention prcvides a process for refining organic-solvent containing crude polyol fatty-acid polyester reaction product, comprising the steps of:
(a) distilling tha crude reaction product to substantially remove said organic solvent; and 0 (b) subsequently subjecting the distilled reaction product to a bleaching treatment.
The key feature of the present invention is that the distilling step by which the organic solvent and optionally further volatile components present in the crude reaction product are removed to a substantial degree, takes place before the bleaching treatment to remcve coloured mat~ers.
Aocordingly, in the refining process according to the invention a substantial part of the organic solvent is removed by distillation before a further bleaching treatment. Also further volatile o~mponents such as e.g. free fatty acids may be removed in the distilling step.
m e distillation of the crude reaction product may be carried out in oonventional manner using temperatures in the range of from 60 to 300C. In general temperatures of above 150C will be used since these allow reducad pressure regimes economically feasible on a technical scale. Preferred distilling temperatures lie within the range of 160 to ~ ~ 3 ~
L 7216 (R) 240C, temperatures of 200 to 240C being preferred m~st.
As already indicated the distilling step is prefexably carried out under reduced pressure, in particular pressures of below 100 mbar, such as between 30 and 70 mkar. Pressures of between 1 and lO mbar and in particular pressures between 1 and 5 mkar are preferred.
Althou3h appropriate distilling times will strongly depend upon temperature and pressure conditions applied, e.g batch-wise distilling times of between 30 and 100 minutes have been found suitable, whereas continuous distilling times can be ~uch shorter and are determined by the equipment used.
In exoeptional circum:tances where the crude reaction product at the distilling stage still comprises significant levels of relatively temperature-sensitive components it may be n~c~ssary to use relatively low distilling temperatures within the range of 60 to 150C, in particular, 80 to 120C. Removal from or reduction in the crude reaction product of the relevant organic components by distilling at such low temFeratures will reguire more severe reduoed pressure conditions, in particular, of below 1 mbar, or even b~low 0.1 mbar.
Although technically best results are achieved when the organic solvent is substantially removed from the crude reaction product prior to a subsequent bleaching treatment, worthwhile advantages are already obtained at removal levels of 40 % or more by weight of the organic solvent, removal levels of 70 ~ or more being preferred, and levels of 95 ~ or more being preferred most.
A further essential element of the present invention is the bleaching treatment subsequent to the distilling of the reaction product. m e bleaching treatment and the bleaching agent selected is particularly triggered tcwards effective removal of the coloured matter. Sui~able bleaching agents are carbons and bleaching earths, which may or nay not be activated by appropriate acid treatment, silicas, clays and synthetic adsorbents.
Suitably, the bleaching agents are added to the reaction product 2~3~7~
6 L 7216 (R) in amounts of 0.2 to 5 ~ by weight and preferably in amounts of 0.5 to 3 ~ by weight. Often very good results are obtained with amounts of 1 to 2 % by weight.
In general the bleaching treatment is carried out at an elevated temperature. Suitable bleaching temp~lratures are within the range of 70 to 140C, temperatures of 80 to 120C being preferred.
Dependent upon the ~leaching agent selected bleaching results may be i~proved by the presence in the reaction product of low levels of water. In particular when silicas are used water levels are best between 0.1 and 0.5 %. Where bleaching is best carried out under dry conditions, such as e.g. when bleaching earths are used, suitably oonditions of reduced pressure are applied, pressures of below 100 mbar and in particular between 30 and 70 mbar being preferred.
Normal bleaching times vary between 30 and 120 minutes, times of between 30 and 60 minutes in many mstancas being sufficient.
After the bleaching treatment the bleaching agent togethPr with the absorbed coloured materials are in general removed by filtration which may be assisted by introduction of a filter aid such as cellulose.
In addition to the distilling and subeeauent bleaching treatment the refining process in accordance with the present invention preferably comprises refining treatments preceding the distilling step to substantially remove the soap and metal ion components in the crude reaction product. Removal of these components will av~id problems of discolouring during subsequent high-temperature refining treatments, such as the distilling step. At the stage before the distilling step it is not so much an object to remove the coloured matt~r and this may suitably be primarily effected during the bleaching step subsequent to the distilling.
m ese pre-distilling treatments may comprise any suitable method to substantially remove in particular the soap and aIkali metal ions which may be prlesent in the crude reaction product. Suitable such 2~3~7~
7 L 7216 (R) refining treatments include conventional washing treatments such as water washings with or without added electrolytes, and aIkaline or acid wzshings as described in EP o 319 092 herein incorporated by reference.
Instead of or in addition to such conventional washing treatments preceding the distillation it may be especially useful to contact the crude polyester reaction product with an acid to substantially convert the soap component to its corresponding free fatty acids.
The acid is used to establish conversion of the soap ccmponent to its free fatty acids and the amount 1hereof in principle must be sufficient to substantially convert all of the scap present in the crude polyester product. The amount of acid will depend upon the level of the soap emulsifier system used in the synthesis reaction as well as the amounts of soap formed or intrcduced d~ring the synthesis reaction.
For reasons of cost it is preferred that the amo~nt of acid is as close to the precise amount needed as technically feasible to establish full neutralising of all the soap present in the crude reaction product, amounts of acid in excess over what is theoretically needed to fully neutralize the aIkaline components in the crude polyester reaction product preferably being as lcw as o to 10 %, the range of o to 5 %
being particularly preferred.
To ensure subs~antially full conversion of t`he soap to free fatty acids the strength of the acid mNst be such that the equilibrium of the conversion reaction lies substantially fully at the side of the free fatty acids, the pH-values resulting from the addition of the acid to the crude reaction product, in general in the form of an aqueous solution thereof, preferably keing kelow 6, the range of pH 3 to 5 keing preferred most.
&itably, both inorganic and organic acids can be used which in view of the important application of the polyol fatty-acid polyesters in focd products preferably are food grade. Suitable inorganic acids are phosphoric acid and dihydrogen phosphoric acid alkali metal salts.
&itable organic acids include acetic, lactic, succinic and citric acid, the latter acid keing preferred.
2 ~J 3 .~
8 L 7216 (R) Preferably, a relatively concentrated aqueous acid solution is used. Suitable concentrations lie within the range of 25 % by weight or more. To allcw convenient removal of the salt resulting from the acid step, conoe ntrated acid solutions of 40 % to 85 % are preferred, concenLl~tions of 40 to 60 % being preferred most.
m e acid step has to be followed by substantial removal from the crude polyester reaction product of any salts present therein, in general alkali-metal salts which together with the free fatty acids result from the soap conversion by th~e acid. The substantial removal of the salt may be effected by using conventional separation techniques, such as centrifuge or filtration techniques. Suitable filtration techniques may involve the use of filter-aids, such as e.g. oe llulose.
In particular, when the salt is removed by way of fil~tion, it has been found that the removal of this salt, generally being the alkali metal salt of the acid used in the soap-conversion step, is improved if the water level in the acidulated reaction pro~uct resulting e.g. from the aqueous acid solution, is reduced to very low levels which preferably correspond to a system substantially without free water being present, i.e. all water being either dissolved in the polyester phase or being present as crystal or bound water of further components in the reaction product. Suitable such water levels are below 0.3 % by weight, and preferably lie below 0.1 or even 0.05 % by weight. This can be conveniently effected by subjecting the reaction product to appropriate drying conditions at elevated temperature and reduced pressure. This drying step may be carried out subsequent to or during ~he contact times discusssd herein-before.
A preferred method of reducing the water to very low levels is flash-drying by which the reaction product is passed into a low-pressure chamber and any water present is vaporised adiabatically. The heat needed for such evaporation is drawn from the reaction mixture and accordingly this method can be used for the simultaneous drying and cooling of the reaction mixture from the temperature of the acid step to well below 100C, in particular 70 to 90C. If flash-drying is used for sinultaneous drying and cooling, the water level in the reaction mixture after the addition of the acid solution may be higher than 2 ~
g L 7216 (R) descriked hereabove, in order to ensure sufficient cooling during the flash-drying process. Water levels of 2 to 5 % by weight will ensure a cooling of about 20 to 50C which in general will avoid any further separate coolLng step.
It has further been found that the removal of the salt as also the colour and discolouring properties of the fLnal refined p~lyester product are advantageously affected, if prior to the introduction of the acid in the pre-distilling treatment first a relatively small amount of an aqueous aIkaline solution is addPd to the crude polyester product which is subsequently neutralized by the acid simLltaneous to the conversion of the soap component to its free fatty acid.
Within the constraint of avoiding or minimizing the risk of the formation of undesirable components the particular combination of source, volume and level of alkalinity is not very critical and can be any of the readily available aIkaline materials, such as the aIkali metal hydroxides, carbonates or silicates, generally at a level within the range of 0.1 to 6 N, in particular, 0.2 to 4 N, or even, 0.2 to 1 or 2.5 N. m e a~ueous alkaline solution is suitably added to the crude polyester product in an amount of 0.5 to 5 % by weight of the product. Preferably, some agitation is applied to improve the contact between the crude polyester product and the aqueous alkaline solution.
In a batch-wise operation contact times in the acid step and optional prior alkaline step of between 1 and 10 minutes between the introduction of the aqueous alkaline solution and the introduction of the acid have been found sufficient. In a continuous operation contact times are generally shorter than 3 minutes, such as l~ than about 1 munute, and can be as short as 5 to 30 seconds.
Although in the pre-distilling refining treatment the acid step and optional prior aIkaline step can be combined with further conventional washings as described hereinbefore, it is preferred to apply the acid step and the optional prior addition of an aqueous alkaline solution without further washing steps.
A preferred pre-distilling treatment to substantially remove any ~ t7 ~
L 7216 (R) soap and alkali metal ion components may further consist of a bleaching treatment which contrary to the bleaching treatment sub6eguent to the distilliny step is not so much directed to removal of coloured matter but directed to the removal of residual scap and alkali metal ions.
Suitably, similar adsorbent agents and bleaching conditions can be us~d as described hereinbefore.
PccYrdingly, in a preferred :mbndlment of the present inYention the refining process comprises subjecting the crude reaction product to a first bleaching treatment, subsequently distilling the once bleached reaction product to substantially remove the organic solvent; and subjecting the distilled reaction product to a second bleaching treatment.
In a particul æ ly preferred emkodlment the present invention provides a refining process in ~hich before the distilling step the crude reaction product is contacted with an acid followed by removal of salt as described hereinbefore, and subjected to a first bleaching treatment, the absorbent of said first bleaching treatment keing introduced before said removal of salt. In such a process the removal of salt and adsorbent is suitably be cGmbined.
Subsequent to the second bleaching treatment the resulting polyester product may be subjected to a high-temperature refining treatment to remove volatile components and any residual free fatty acids. Such high-temperature refining treatment in particular will include a further deodorizing step, such as steam-stripping, at a temperature of above 150C, such as 150 to 300C. Preferred temperatures are 180 to 260C, in particular 190 to 240C, temperatures of 220 to 240C being preferred most.
m e invention is in particul æ directed to the refining of crude polyol fatty-acid polyester reaction products of transesterification reactions involving excess amounts of fatty-acid lower aIkylesters.
This type of transesterification reaction is particularly suitable for the synthesis of polyol fatty-acid polyesters having high degrees of esterification of 70 % or more, and accordingly, the present process is ~'~3~'7'~
ll L 7216 (R) p æticularly applicable to the refining of crude polyol fatty-acid polyester having such high degrees of esterification, in particular crude products ccmprising polyol fatty-aeid polyesters having degr~
of esterification of 80 % or more, or even 90 % or more. Preferably, sueh crude polyester reaction prcducts derived from the suyar polyols selected from the group of disaccharides or the alcohol derivatives thereof, such as sucrose, and esterified to over 95 % fatty-aeid su~stitution, are suitably refined by the process in accordance with the present invention.
Having a reduoed risk of discolouring the polyol fatty-acid polyesters refined in accordance with the prooess of the present invention æe partic~ul æly suitable to replace fully or partially conventional trigly oeride fats in focd ccmpositions intended for high-temperature purposes, such as b~king and frying oils. Generally, insuch food cQmpositions at least 10 % by wei~ht of the conventional triglyceride fat is replaoed by the polyol fatty-acid polyesters in aelordanee with the present invention. ~referably, at least 50 % of the conventional fat is replaoed by the polyesters.
Ihe invention is now further illustrated with reference to the follcwing examples, percentages being by weight unless indicated otherwise.
EX~MPLE 1 A batch of crude sucrose fatty-acid polyester reaction product, synthesized in a solvent-free trarsesterification reaction between sucrose and touch-h ædened soybean oil derived, non-distilled fatty-acid methylester to a degree of esterification of over 95 %, consistedof the following co~ponents:
sucrose fatty-acid polyester 44.6 %
fatty-acid methylester 46.9 %
soap (mainly coconut-derived potassium soap)3.8 %
minor components 4.7 %
m is batch ~as first washed with 7.5 % of water, agitated during 7 ~
12 L 7216 (R) 15 minut~ at 80C and oe ntrifuged (3000 rpm for 10 minutes) to separate the water with the bulk of the soap and dried at 90C and 50 mbar pressure. The water-washed sucrose polyester reaction product was further refined using 3 different procedures:
procedure 1 20 grams bleaching earth (Supre~e FF ex TonsilR) was added per kg water-washed sucrose polyester reaction product and the resulting mixture ~as stirred for 30 min at 90C and atmospheric pressure. The suspension was filtered throu~h a 2 microns filter and distilledtdeodorised (3 hours, 200C) The colour values of the refined reaction product as measured in a 2" cell of an Au~cmatic Colori Meter ex Morgan Smith Electronics LtdR
were 24.0 Yellow and 3.4 Red.
~rooedure 2 10 grams bleaching earth (Supreme FF ex TbnsilR) was added per kg water-washed sucrose polyester reaction product and the r ~lltLng mixture was stirred for 30 min at 90C and atmospheric pressure. The suspension was filtered through a 2 microns filter and distilled (1 hour, 200C) to remove the bulk of the fatty-acid methylester (> 95 ~ removal). After distillation the reaction product was dried (50 m~ar, 90C) and 10 grams bleaching earth (Supreme FF ex TbnsilR) was added per kg distille~ reaction product. The suspension was stirred for 30 min (atmospheric, 90C) and filtered through a 2 microns filter, followed by deodorisation at 200c for 2 hours.
The colour values of the refined reaction product as measured in a 2" oe ll of an Autcmatic Colori Meter ex Morgan Smith Electranics Lt were 19.0 Yellow and 2.5 Red.
procedure 3 10 grams b~eaching earth (Supreme FF ex TbnsilR) per kg water-washed sucrose polyester reaction product was added and the resulting 13 L 7216 (R) mixture was stirred for 30 min at 90C and atmospheric pressure. m e suspension was filtered throu~h a 2 microns filter. me reactant product was subsequently dried (50 mkar, 90C) and the bleaching treatment repeated. Subseguently, ~he twioe bleached product was distilled/deodoris~d at 200C for 3 hours.
Ihe colour values of the refined reaction product as measured in a 2" cell of an Automatic Colori Meter ex M~rgan Smith Electronics LtdR
were 25.0 Yellow and 3.2 Red.
Co~parison of the colour results after the 3 different procedures indicate that pro oedure 2, which embodies the prooess of the present inNention, is the most effective having the best colour results while requiring 1~ bleaching earth than the procedures 1 and 3 (15 grams compared to 20 grams per kg crude reaction product).
EX~MPLE 2 A batch of crude sucrose fatty-acid polyester reaction product, synthesized in a solvent-free transesterification reaction between sucrose and touch-hardened soybean oil derived, distilled fatty-acid methylester to a degree of esterification of over 95 %, consisted of the following components:
sucrose fatty-acid polyester 49.8 %
fatty-acid methylester 43.2 %
soap (mainly coconut-derived potassium soap)3.8 %
minor components 3.2 %
miS batch was first washed with 7.5 % of water, agitated during 15 minutes at aooc and centrifuged at 3000 rpm for 10 minutes to separate the water with the bulk of the soap and dried at 90C and 50 mbar pressure. After drying 0.2 % by weight of water was added.
Subsequently, after 5 minutes stirring 0.5 % of Trisyl ex Gra oeR was added to remove residual soap and the resulting mixture was stirred for 30 min at 90C and atmospheric pressure and filtered through a 2 microns filter.
14 L 7216 (R) Ihe resulting product was further refined using two different procedures.
Procedure 1 15 grams of blea_h mg earth (St~dard FF ex TonsilR) was added per Xg of partially refined sucrose polyester reaction produc~ and the resulting mixture was stirred for 30 min at 90C and atmoepheric pressure. Ihe suspension was filtered through a 2 microns filter and distilled/deodorizt~s (3 hours, 215C).
The colour values of the refined reaction product as me2sured in a 2"
cell of an Automatic Colori Meter ex Morgan Smith Electronics LtdR were 30.0 Yellow and 3.7 Red.
procedure 2 The partially refined sucrose polyester reac~ion product was first distilled (1 hour, 215C) to remove the }ulk of the fatty-acid methylester (> 95 % removal). After distillation the reaction product was dried (50 mbar, 90C) and 15 ~rams of bleaching earth (Star.dard FF
ex IonsilR) was added per kg distilled reaction product. m e suspension was stirred for 30 min (atmospheric, 90C) and filtered throu3h a 2 microns filter, followed by deodorization at 215C for 2 hours.
The colour values of the refined reaction product as neasured in a 2" cell of an Automatic Colori Meter ex Morgan 5mith Electronics LtdR
were 29.0 Yellow and 3.7 Red.
Ccmparison of the 2 procedures shows that procedure 2 in accordance with the invention gives equal or even scmewhat better colour results but requires less bleaching earth to achieve this (15 grams per kg distilled product ccmpared to 15 grams of non-distilled pro~uct which amounts to about 67 %).
Claims (7)
1. A process for refining organic-solvent containing crude polyol fatty-acid polyester reaction product, comprising the steps of:
(a) distilling the crude reaction product to substantially remove said organic solvent; and (b) subsequently subjecting the distilled reaction product to a bleaching treatment.
(a) distilling the crude reaction product to substantially remove said organic solvent; and (b) subsequently subjecting the distilled reaction product to a bleaching treatment.
2. The process of claim 1 in which step (a) is carried out at a temperature within the range of 200 to 240°C.
3. The process of claim 1 in which in step (a) 70 % or more of said organic solvent is removed.
4. The process of claim 1 in which prior to step (a) the soap and metal ion components in the crude reaction product are substantially removed.
5. The process of claim 4 in which the removal of said soap and metal ion components comprises a bleaching treatment.
6. The process of claim 5 in which the removal of said soap and metal ion components further comprises contacting the crude reaction products with an acid to convert the soap into the corresponding free fatty acids.
7. The process of claim 1 which subsequent to step (b) comprises further refining treatments at a temperature of 180 to 260°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP89203313.5 | 1989-12-21 | ||
EP89203313 | 1989-12-21 |
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CA2032676A1 true CA2032676A1 (en) | 1991-06-22 |
Family
ID=8202538
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002032676A Abandoned CA2032676A1 (en) | 1989-12-21 | 1990-12-19 | Process for refining organic-solvent containing crude polyol fatty-acid polyester products |
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US (1) | US5225049A (en) |
EP (1) | EP0435364B1 (en) |
JP (1) | JPH0421656A (en) |
AT (1) | ATE120755T1 (en) |
AU (1) | AU6809890A (en) |
CA (1) | CA2032676A1 (en) |
DE (1) | DE69018413T2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113039001A (en) * | 2021-02-19 | 2021-06-25 | 安徽金禾实业股份有限公司 | Production equipment and production method of sucrose-6-ester |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4140373A1 (en) * | 1991-12-07 | 1993-06-09 | Henkel Kgaa, 4000 Duesseldorf, De | IMPROVED DRY NEUTRALIZATION OF OLEFINIC REACTIVE ORGANIC LIQUID PHASES |
US5490995A (en) * | 1992-10-30 | 1996-02-13 | The Procter & Gamble Company | Solid nondigestible polyol polyesters containing esterified hydroxy fatty acids such as esterified ricinoleic acid |
WO1994009640A1 (en) * | 1992-10-30 | 1994-05-11 | The Procter & Gamble Company | Nondigestible fat compositions containing cocrystallized blend of polyol polyester hardstock and crystal modifier as a passive oil loss control agent |
US5422131A (en) * | 1992-10-30 | 1995-06-06 | The Procter & Gamble Company | Nondigestible fat compositions containing relatively small nondigestible solid particles for passive oil loss control |
CA2146002C (en) * | 1992-10-30 | 1999-02-23 | Patrick Joseph Corrigan | Nondigestible fat compositions containing diversely esterified polyol polyesters for passive oil loss control |
DK0666710T3 (en) * | 1992-10-30 | 1997-10-06 | Procter & Gamble | Indigestible fat compositions containing solid polyol polyester polymer for controlling passive oil loss |
CA2145992C (en) | 1992-10-30 | 1999-01-19 | John Keeney Howie | Nondigestible fat compositions containing solid polyglycereol ester particles for passive oil loss control |
EP0615972A1 (en) * | 1993-03-19 | 1994-09-21 | Unilever N.V. | Process for refining crude sucrose fatty acid polyester products |
GB9323603D0 (en) * | 1993-11-16 | 1994-01-05 | Baxenden Chem | Low fogging polyester polyurethane foams |
US5681948A (en) * | 1995-03-06 | 1997-10-28 | Kraft Foods, Inc. | Two-stage method for preparing polyol fatty acid polyesters |
US5596085A (en) * | 1995-04-11 | 1997-01-21 | Kraft Foods, Inc. | Method for preparing polyol fatty acid polyesters by transesterification |
AU738499B2 (en) * | 1997-01-31 | 2001-09-20 | Procter & Gamble Company, The | Reduced calorie cooking and frying oils having improved hydrolytic stability, and process for preparing |
US6180686B1 (en) * | 1998-09-17 | 2001-01-30 | Thomas M. Kurth | Cellular plastic material |
US7063877B2 (en) | 1998-09-17 | 2006-06-20 | Urethane Soy Systems Company, Inc. | Bio-based carpet material |
US20030191274A1 (en) * | 2001-10-10 | 2003-10-09 | Kurth Thomas M. | Oxylated vegetable-based polyol having increased functionality and urethane material formed using the polyol |
US6979477B2 (en) | 2000-09-06 | 2005-12-27 | Urethane Soy Systems Company | Vegetable oil-based coating and method for application |
US20020058774A1 (en) | 2000-09-06 | 2002-05-16 | Kurth Thomas M. | Transesterified polyol having selectable and increased functionality and urethane material products formed using the polyol |
US6962636B2 (en) * | 1998-09-17 | 2005-11-08 | Urethane Soy Systems Company, Inc. | Method of producing a bio-based carpet material |
US7595094B2 (en) * | 1998-09-17 | 2009-09-29 | Urethane Soy Systems, Co. | Vegetable oil-based coating and method for application |
JP2003512343A (en) | 1999-10-15 | 2003-04-02 | ダニスコ カルター アメリカ,インコーポレイテッド | Method for direct esterification of sorbitol with fatty acids |
AU2002241324A1 (en) * | 2002-03-28 | 2003-10-13 | Fuji Oil Company, Limited | Fat producing method |
US7169946B1 (en) * | 2004-03-05 | 2007-01-30 | Twin Rivers Technologies, L.P. | Alternatives to distilled oleo chemicals in derivatives and production thereof |
AU2006218395A1 (en) | 2005-03-03 | 2006-09-08 | South Dakota Soybean Processors, Llc | Novel polyols derived from a vegetable oil using an oxidation process |
CN112915565B (en) * | 2021-03-04 | 2022-04-08 | 安徽金禾实业股份有限公司 | Rotary continuous production equipment and production method for sucrose-6-ester |
CN112933635B (en) * | 2021-03-04 | 2022-04-12 | 安徽金禾实业股份有限公司 | Surrounding centrifugal type sucrose-6-ester continuous production equipment and production method |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3920523A (en) * | 1971-03-17 | 1975-11-18 | Akzona Inc | Thin film evaporation of a crude amide feed in mixture with an alkali metal hydroxide |
US3963699A (en) * | 1974-01-10 | 1976-06-15 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters |
US4334061A (en) * | 1979-10-29 | 1982-06-08 | Ethyl Corporation | Process for recovery of polyol fatty acid polyesters |
US4480691A (en) * | 1982-09-29 | 1984-11-06 | Herter George L | Recycled fatty acid crude petroleum recovery process |
US4517360A (en) * | 1983-06-23 | 1985-05-14 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters using carbonate catalysts |
US4518772A (en) * | 1983-06-23 | 1985-05-21 | The Proctor & Gamble Company | Synthesis of higher polyol fatty acid polyesters using high soap:polyol ratios |
JPS6115893A (en) * | 1984-06-29 | 1986-01-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Purification of sucrose fatty acid ester |
US4942228A (en) * | 1986-05-06 | 1990-07-17 | The Procter & Gamble Company | Production of polyol polyesters having reduced color content |
NL8601904A (en) * | 1986-07-23 | 1988-02-16 | Unilever Nv | PROCESS FOR THE PREPARATION OF POLYOL FATTY ACID POLYESTERS. |
US4797300A (en) * | 1987-04-10 | 1989-01-10 | The Procter & Gamble Company | Compositions containing novel solid, nondigestible, fat-like compounds |
US4968791A (en) * | 1987-07-23 | 1990-11-06 | Lever Brothers Company | Process for the preparation of polyol fatty acid esters |
US4950140A (en) * | 1987-09-14 | 1990-08-21 | The Procter & Gamble Company | Cookies containing psyllium |
GB8728385D0 (en) * | 1987-12-04 | 1988-01-13 | Unilever Plc | Method of purifying crude polyol fatty acid polyester products |
EP0319091A3 (en) * | 1987-12-04 | 1992-07-01 | Unilever N.V. | Method of purifying crude polyol fatty acid polyesters |
EP0320043B1 (en) * | 1987-12-11 | 1994-04-13 | Unilever N.V. | Process for the synthesis of polyol fatty acid esters |
GB8800087D0 (en) * | 1988-01-05 | 1988-02-10 | Unilever Plc | Process for synthesis of polyol fatty acid polyesters |
US4954621A (en) * | 1988-06-14 | 1990-09-04 | Mitsubushi Kasei Corporation | Process for producing sucrose fatty acid polyester |
US4931552A (en) * | 1988-06-30 | 1990-06-05 | The Procter & Gamble Company | Production of polyol polyesters having reduced color content |
-
1990
- 1990-12-07 EP EP90203229A patent/EP0435364B1/en not_active Expired - Lifetime
- 1990-12-07 AT AT90203229T patent/ATE120755T1/en not_active IP Right Cessation
- 1990-12-07 DE DE69018413T patent/DE69018413T2/en not_active Expired - Fee Related
- 1990-12-13 US US07/626,917 patent/US5225049A/en not_active Expired - Lifetime
- 1990-12-17 AU AU68098/90A patent/AU6809890A/en not_active Abandoned
- 1990-12-19 CA CA002032676A patent/CA2032676A1/en not_active Abandoned
- 1990-12-20 JP JP2411782A patent/JPH0421656A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113039001A (en) * | 2021-02-19 | 2021-06-25 | 安徽金禾实业股份有限公司 | Production equipment and production method of sucrose-6-ester |
CN113039001B (en) * | 2021-02-19 | 2022-10-18 | 安徽金禾实业股份有限公司 | Production equipment and production method of sucrose-6-ester |
Also Published As
Publication number | Publication date |
---|---|
EP0435364B1 (en) | 1995-04-05 |
DE69018413T2 (en) | 1995-08-24 |
US5225049A (en) | 1993-07-06 |
EP0435364A3 (en) | 1991-10-23 |
DE69018413D1 (en) | 1995-05-11 |
ATE120755T1 (en) | 1995-04-15 |
EP0435364A2 (en) | 1991-07-03 |
AU6809890A (en) | 1991-06-27 |
JPH0421656A (en) | 1992-01-24 |
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Legal Events
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EEER | Examination request | ||
FZDE | Discontinued |