CA2090750A1 - Enzymic diglyceride removal - Google Patents
Enzymic diglyceride removalInfo
- Publication number
- CA2090750A1 CA2090750A1 CA002090750A CA2090750A CA2090750A1 CA 2090750 A1 CA2090750 A1 CA 2090750A1 CA 002090750 A CA002090750 A CA 002090750A CA 2090750 A CA2090750 A CA 2090750A CA 2090750 A1 CA2090750 A1 CA 2090750A1
- Authority
- CA
- Canada
- Prior art keywords
- process according
- conversion zone
- glyceride
- enzyme
- aqueous
- 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
- 238000000034 method Methods 0.000 claims abstract description 59
- 102000004190 Enzymes Human genes 0.000 claims abstract description 57
- 108090000790 Enzymes Proteins 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008346 aqueous phase Substances 0.000 claims description 12
- 150000003626 triacylglycerols Chemical class 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 235000021588 free fatty acids Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 241000228143 Penicillium Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009884 interesterification Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6409—Fatty acids
- C12P7/6418—Fatty acids by hydrolysis of fatty acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fats And Perfumes (AREA)
Abstract
F 7071 (R) ABSTRACT
The invention concerns a process for the enzymic removal of diglycerides from glyceride mixtures. Herefore, the glyceride mixture is contacted with an enzyme specific for the conversion of diglycerides. This contact is performed in an aqueous emulsion of the diglycerides, wherein the droplet size of the dispersed phase is less than 100 µm.
The invention concerns a process for the enzymic removal of diglycerides from glyceride mixtures. Herefore, the glyceride mixture is contacted with an enzyme specific for the conversion of diglycerides. This contact is performed in an aqueous emulsion of the diglycerides, wherein the droplet size of the dispersed phase is less than 100 µm.
Description
2 0 9 ~ 7 ~ 0 F 707l (R) .
~NZ.YMIC D GLYCE:~D E~EMOVA~
At present, many methods for the preparation of triglycerides are known in the prior art. Among these, the directed enzymic interesterification methods are the most elegant ones for the preparation of triglycerides with a required specific distribution of the fatty acid residues over the triglyceride. Although in this directed, enzymic esterification process a minimum amount of water is used, i.e. just enough water to activate the enzyme, it is inevitable that some amount (2-10 wt.~) of diglyceride is formed. The presence of these diglycerides in the main product (= triglycerides) is very unfavourable as the diglycerides have an adverse effect on the product properties of the triglycerides.
A number of processes coping with this problem are disclosed in literature. These are focussed on the removal of diglycerides from mixtures with ~rlglycerides, wherein an enzymic conversion of diglycerides is carried out by using an enzyme specific for the hydrolysis of diglycerides into glycerol and free fatty acids.
In JP 62/51997, e.g., a method for the improvement of fats is disclosed, wherein a mixture containing at least 70 wt.%
of triglycerides and not less than 2 wt.% of diglycerides ; 25 is contacted with an enzyme specific for partial glycerides in the presence of a small amount of water.
A similar process is disclosed in JP 62/61590. The hydrolysis of the partial glycerides is now followed by an esterification process using a 1,3-specific enzyme.
In JP 62/287 a similar process is disclosed by which the hydrolysis of monoglycerides and/or diglycerides is carried 2 2 ~ 9 ~ 7 ~ 0 F 7071 (R) out by usin~ the lipase pr~duced ~y PenicilliUm ayclopium ATCC 34613.
Although these prior art processes perform rather well with respect to the level of diglycerides present in the end product, they have one main disadvantage : the reaction time is long because of a rather slow reaction rate.
Although this could be overcome, at least partly, by using big reactors, the cost of investment involved will be high.
We have now found a new process by which the high cost of investment can be avoided and wherein the reaction rate is increased.
Therefore, our invention concerns a process for the enzymic removal of diglycerides from glyceride mixtures containing at least diglycerides and triglycerides by contacting the glyceride mi~tures in an enzymic conversion zone with an aqueous solution of an enzyme specific for the conversion of diglycerides, wherein the contact of the aqueous enzyme solution and glyceride mixture is established in an emulsion of the glyceride mixtuxe in the aqueous enzyme solution, the water content of the emulsion being 15-50 wt.% and the droplet size of the glycerides in the emulsion being less than 100 ~m.
The above-mentioned process is new and inventive over a process for the transesterification of a triglyceride with - a fatty acid in the presence of a lipase, wherein the transesterification is carried out in a thermodynamically stable solution, such as a micro emulsion, which requires the use of a hydrophobic part, a surface-active part and water, as described in EP 237,092. According to this prior art process, esterification is aimed at, for which only a small amount of water needs to be present. Moreover, the use of an enzyme for the specific removal of diglycerides 2~10~
F 7071 (P) is not disclo~ed in t~is document. Furthermore, in this known process it is essential to use surfactants, which might be difficult to remove from the end product.
Very acceptable results are achieved, in particular with respect to reaction times, by carrying out our process as a counter-current process wherein fresh glyceride mixture is fed to one end of the conversion zone and the enzyme solution is fed to the opposite end of the conversion zone.
The conversion zone used can be a contactor, whereby the contactor can be of any known type, such as a rotating disc contactor, a multi-stage sieve tray column, a packed column or mixer/settler devices.
It is important to control the droplet size of the glyceride mixture in the emulsion. A droplet size of less than 100 ~m already leads to favourable results. It is, however, preferred to use smaller droplet sizes. The preferred droplet sizes are therefore less than 50 ~m, t~-~mean diameter of the droplets being 5-20 ~m.
In order to achieve such a mean diameter, it is preferred that the oil and water phase be fed into a high-shear mixer of the Silverson type.
A very convenient procedure i5 obtained when the mixing device is part of an enzymic conversion zone.
In the above-mentioned processes, the contact time of the reactants in the conversion zone can be kept at 1 minute to 60 minutes, in particular at 5-30 minutes.
The crude reaction product from the conversion zone is normally separated into a glyceride phase and into an aqueous phase rich in controllable levels of glycerol and 20~07~
F '1rJ11 (~) containiny part of the enzymes. Any type of separator can be used; however, centrifuges are pre~erred.
The level of glycerol in the aqueous phase can be controlled by taking samples and determining the reaction parameters, such as ratio of components, reaction time, droplet size in the emulsion etc., depending on the glycerol level of the aqueous stream.
In a very convenient process, the aqueous phase containing part of the enzymes is recirculated to the enzymic conversion zone. In this way, the enzyme solution is used in a very efficient way. However, in order to maintain a desired activity in the enzyme solution, it will be necessary to add fresh, make-up enzyme solution to the recycle stream of aqueous enzyme. Suitable make-up enzyme is added in such an amount that the concentration of enzyme in the recirculated enzyme solution is at least 0.05 wt.%, calculated on the oil.
In order to avoid the glycerol concentration building up to undesirably high levels, at least part of the aqueous phase, rich in glycerol, is removed as purge from the system.
The glyceride phase obtained in the process can be washed with water, whereupon a triglyceride-rich product, ~rom which most of the diglycerides have been removed, is separated from an aqueous phase containing at least part of the enzymes, which aqueous phase is at least partly recirculated.
Although the recycle enzyme solution can be used in a manner co-current to the process stream, it is also possible to use the recycle stream in a way that is counter-current to the process stream.
2~07~
F 70~/1 (R) This ]ast-mentioned process is preferably applie~ when several mi~er/conversion devices and several separators are used. The aqueous stream(s) containing the enzymes withdrawn from the separator(s) are then used in a manner counter-current to the process stream. The processes that can be carried out are illustrated by the processes according to the different flow sheets.
In the Figures :
lo - Fig. 1 illustrates a counter-current process;
- Fig. 2 illustrates a co-current process with recycle;
- Fig. 3 as Fig. 2, but including a wash step;
- Fig. 4 illustrates a counter-current process with recycle;
- Fig. 5 illustrates an alternative counter-current process with recycle.
According to the process of Fig. 1, an enzymic conversion zone (1) is fed with a glyceride mixture (2) in a way counter-current to an aqueous enzyme solution (3). The enzymic conversion zone (1) can be a rotating disc contactor, a multi-stage sieve-tray column, a packed column or mixer/settler devices, the only requirement being that a droplet size of the glyceride mixture in the water phase of less than 100 ~m can be achieved. From the conversion zone (1), a product consistiny of triglycerides and free fatty acids, but with a reduced level of diglycerides is removed via (4), while an aqueous enzyme solution, also containing glycerol, is removed via ~5).
According to the processes of Fig. 2 and 3, a triglyceride oil containing 1-15 wt.% of diglycerides is mixed with an aqueous enzyme solution (0.02-1 wt.~ of enzymes specific for the hydrolysis or diglycerides) in a mixer (1). An emulsion of fat in water with a mean droplet size of about 2 ~ 5 ~
F 7071 (R) 15 ~m is obtained. This emulsion is led to an enzymic conversion zone which is part of the mixing device. The throughput through the conversion zone is chosen in order to obtain a residence time of about 15 minutes.
The crude reaction product (6) from (1) is led to a separator (7), wherein the product is split into an aqueous stream (8) high in glycerol and a triglyceride stream (4) or (9), which latter can be led to a wash/separator (12), where it is washed with water (ll).
From wash/separator (12) a product stream (4) consisting of the desired triglycerides is obtained. An aqueous stream (5) containing the enzyme is led to a mixer where it is mixed with make-up enzyme (3), whereupon the mixture is recirculated to mixer/conversion zone (1).
The aqueous stream high in glycerol (8) can be removed as purge stream; however, it is, of course, also possible to feed part of this purge stream (8) into the make-up zone in order to re-use the enzymes present in this aqueous stream.
However, it will always be necessary to remove part of stream (8) as a purge; otherwise the level of glycerol will become too high to obtain acceptable results.
In the above-mentioned process, 2~8 parts of glyceride mixture are in general applied for 1 part of enzyme solution. This ratio means therefore that considerable amounts of water are present in the reaction mixture.
In Fig. 4 and 5, multi-stage processes are represented wherein the recycle aqueous enzyme solution is used in a manner counter-current to the process stream.
2 ~
F 7071 (R) /
According to ~ic3. ~, three mixer/conversion zones (1, la and ~b) are used. Each conversion zone is followed by a separator (7, 7a and 7b).
The starting triglyceride mixture (2) is mixed with recycle enzyme solution (5b) from separator (7a) and is converted in zone (1). The crude reaction product is led via (~) to separator ~7). From separator (7), a triglyceride stream (9) and an enzyme solution (8) as purge stream are obtained. The glyceride stream (9) is mixed with recycle enzyme solution (5a) from separator (7b) in mixer/
conversion zone (la). The crude reaction product is led via (6a) to separator (7a) and separated into a glyceride stream (9a) and the recycle enzyme solution (5b). The glyceride stream (9a) is mixed with fresh, make-up enzyme (3) in mixer/conversion zone (lb). The crude material (6b) is separated in separator (7b) into a product stream (4) - and the recycle enzyme stream (5a). In this process also part of the purge (8) can be mixed with make-up enzyme solution (3), whereupon this mixture lS led to zone (lb).
According to Fig. 5, a similar process is carried out.
However, the enzymic solutions (5a, 5b and 5c) obtained in the different separators (7, 7a and 7b) are all led to a main recycle line (5), which is also ~ed with the make-up enzyme solution (3). Part of the recycle enzyme stream (5) is discarded as purge (8). This is done after the recycle stream (5a) has been combined with the main recycle stream (5).
~07~
F 7071 (R) EXAMPLE
The process ls carried out, using the flow sheet of Fig. 2.
In this process, a mixture of 18~0 kg of triglycerides and 160 kg of diglycerides is mixed per hour in a Silverson mixing device with a water phase comprising 836 kg of water, 160 kg of glycerol and 4 kg of enzyme (Amono-G), resulting in an emulsion with a droplet size of about 25 ~m.
This emulsion is converted during a residence time of 15 minutes in the conversion zone.
The crude reaction mixture containing 2 wt.% of diglycerides is separated in centrifuge (7). 1990 Kg/h of a glyceride product (4) containing 2 wt.% of diglycerides and 5 wt.% of free fatty acids are obtained via line ~4).
A water phase comprising 829 kg of water, 178 kg of glycerol and 4.0 kg of enzyme is removed from the centrifuge.
From this water phase, 101 kg/h is discarded as a purge via line (8).
The remainder is mixed with 90 kg of make-up enzyme solution (containing 0.4 kg of enzyme) and the enzyme solution is recirculated to mixer ~1).
~NZ.YMIC D GLYCE:~D E~EMOVA~
At present, many methods for the preparation of triglycerides are known in the prior art. Among these, the directed enzymic interesterification methods are the most elegant ones for the preparation of triglycerides with a required specific distribution of the fatty acid residues over the triglyceride. Although in this directed, enzymic esterification process a minimum amount of water is used, i.e. just enough water to activate the enzyme, it is inevitable that some amount (2-10 wt.~) of diglyceride is formed. The presence of these diglycerides in the main product (= triglycerides) is very unfavourable as the diglycerides have an adverse effect on the product properties of the triglycerides.
A number of processes coping with this problem are disclosed in literature. These are focussed on the removal of diglycerides from mixtures with ~rlglycerides, wherein an enzymic conversion of diglycerides is carried out by using an enzyme specific for the hydrolysis of diglycerides into glycerol and free fatty acids.
In JP 62/51997, e.g., a method for the improvement of fats is disclosed, wherein a mixture containing at least 70 wt.%
of triglycerides and not less than 2 wt.% of diglycerides ; 25 is contacted with an enzyme specific for partial glycerides in the presence of a small amount of water.
A similar process is disclosed in JP 62/61590. The hydrolysis of the partial glycerides is now followed by an esterification process using a 1,3-specific enzyme.
In JP 62/287 a similar process is disclosed by which the hydrolysis of monoglycerides and/or diglycerides is carried 2 2 ~ 9 ~ 7 ~ 0 F 7071 (R) out by usin~ the lipase pr~duced ~y PenicilliUm ayclopium ATCC 34613.
Although these prior art processes perform rather well with respect to the level of diglycerides present in the end product, they have one main disadvantage : the reaction time is long because of a rather slow reaction rate.
Although this could be overcome, at least partly, by using big reactors, the cost of investment involved will be high.
We have now found a new process by which the high cost of investment can be avoided and wherein the reaction rate is increased.
Therefore, our invention concerns a process for the enzymic removal of diglycerides from glyceride mixtures containing at least diglycerides and triglycerides by contacting the glyceride mi~tures in an enzymic conversion zone with an aqueous solution of an enzyme specific for the conversion of diglycerides, wherein the contact of the aqueous enzyme solution and glyceride mixture is established in an emulsion of the glyceride mixtuxe in the aqueous enzyme solution, the water content of the emulsion being 15-50 wt.% and the droplet size of the glycerides in the emulsion being less than 100 ~m.
The above-mentioned process is new and inventive over a process for the transesterification of a triglyceride with - a fatty acid in the presence of a lipase, wherein the transesterification is carried out in a thermodynamically stable solution, such as a micro emulsion, which requires the use of a hydrophobic part, a surface-active part and water, as described in EP 237,092. According to this prior art process, esterification is aimed at, for which only a small amount of water needs to be present. Moreover, the use of an enzyme for the specific removal of diglycerides 2~10~
F 7071 (P) is not disclo~ed in t~is document. Furthermore, in this known process it is essential to use surfactants, which might be difficult to remove from the end product.
Very acceptable results are achieved, in particular with respect to reaction times, by carrying out our process as a counter-current process wherein fresh glyceride mixture is fed to one end of the conversion zone and the enzyme solution is fed to the opposite end of the conversion zone.
The conversion zone used can be a contactor, whereby the contactor can be of any known type, such as a rotating disc contactor, a multi-stage sieve tray column, a packed column or mixer/settler devices.
It is important to control the droplet size of the glyceride mixture in the emulsion. A droplet size of less than 100 ~m already leads to favourable results. It is, however, preferred to use smaller droplet sizes. The preferred droplet sizes are therefore less than 50 ~m, t~-~mean diameter of the droplets being 5-20 ~m.
In order to achieve such a mean diameter, it is preferred that the oil and water phase be fed into a high-shear mixer of the Silverson type.
A very convenient procedure i5 obtained when the mixing device is part of an enzymic conversion zone.
In the above-mentioned processes, the contact time of the reactants in the conversion zone can be kept at 1 minute to 60 minutes, in particular at 5-30 minutes.
The crude reaction product from the conversion zone is normally separated into a glyceride phase and into an aqueous phase rich in controllable levels of glycerol and 20~07~
F '1rJ11 (~) containiny part of the enzymes. Any type of separator can be used; however, centrifuges are pre~erred.
The level of glycerol in the aqueous phase can be controlled by taking samples and determining the reaction parameters, such as ratio of components, reaction time, droplet size in the emulsion etc., depending on the glycerol level of the aqueous stream.
In a very convenient process, the aqueous phase containing part of the enzymes is recirculated to the enzymic conversion zone. In this way, the enzyme solution is used in a very efficient way. However, in order to maintain a desired activity in the enzyme solution, it will be necessary to add fresh, make-up enzyme solution to the recycle stream of aqueous enzyme. Suitable make-up enzyme is added in such an amount that the concentration of enzyme in the recirculated enzyme solution is at least 0.05 wt.%, calculated on the oil.
In order to avoid the glycerol concentration building up to undesirably high levels, at least part of the aqueous phase, rich in glycerol, is removed as purge from the system.
The glyceride phase obtained in the process can be washed with water, whereupon a triglyceride-rich product, ~rom which most of the diglycerides have been removed, is separated from an aqueous phase containing at least part of the enzymes, which aqueous phase is at least partly recirculated.
Although the recycle enzyme solution can be used in a manner co-current to the process stream, it is also possible to use the recycle stream in a way that is counter-current to the process stream.
2~07~
F 70~/1 (R) This ]ast-mentioned process is preferably applie~ when several mi~er/conversion devices and several separators are used. The aqueous stream(s) containing the enzymes withdrawn from the separator(s) are then used in a manner counter-current to the process stream. The processes that can be carried out are illustrated by the processes according to the different flow sheets.
In the Figures :
lo - Fig. 1 illustrates a counter-current process;
- Fig. 2 illustrates a co-current process with recycle;
- Fig. 3 as Fig. 2, but including a wash step;
- Fig. 4 illustrates a counter-current process with recycle;
- Fig. 5 illustrates an alternative counter-current process with recycle.
According to the process of Fig. 1, an enzymic conversion zone (1) is fed with a glyceride mixture (2) in a way counter-current to an aqueous enzyme solution (3). The enzymic conversion zone (1) can be a rotating disc contactor, a multi-stage sieve-tray column, a packed column or mixer/settler devices, the only requirement being that a droplet size of the glyceride mixture in the water phase of less than 100 ~m can be achieved. From the conversion zone (1), a product consistiny of triglycerides and free fatty acids, but with a reduced level of diglycerides is removed via (4), while an aqueous enzyme solution, also containing glycerol, is removed via ~5).
According to the processes of Fig. 2 and 3, a triglyceride oil containing 1-15 wt.% of diglycerides is mixed with an aqueous enzyme solution (0.02-1 wt.~ of enzymes specific for the hydrolysis or diglycerides) in a mixer (1). An emulsion of fat in water with a mean droplet size of about 2 ~ 5 ~
F 7071 (R) 15 ~m is obtained. This emulsion is led to an enzymic conversion zone which is part of the mixing device. The throughput through the conversion zone is chosen in order to obtain a residence time of about 15 minutes.
The crude reaction product (6) from (1) is led to a separator (7), wherein the product is split into an aqueous stream (8) high in glycerol and a triglyceride stream (4) or (9), which latter can be led to a wash/separator (12), where it is washed with water (ll).
From wash/separator (12) a product stream (4) consisting of the desired triglycerides is obtained. An aqueous stream (5) containing the enzyme is led to a mixer where it is mixed with make-up enzyme (3), whereupon the mixture is recirculated to mixer/conversion zone (1).
The aqueous stream high in glycerol (8) can be removed as purge stream; however, it is, of course, also possible to feed part of this purge stream (8) into the make-up zone in order to re-use the enzymes present in this aqueous stream.
However, it will always be necessary to remove part of stream (8) as a purge; otherwise the level of glycerol will become too high to obtain acceptable results.
In the above-mentioned process, 2~8 parts of glyceride mixture are in general applied for 1 part of enzyme solution. This ratio means therefore that considerable amounts of water are present in the reaction mixture.
In Fig. 4 and 5, multi-stage processes are represented wherein the recycle aqueous enzyme solution is used in a manner counter-current to the process stream.
2 ~
F 7071 (R) /
According to ~ic3. ~, three mixer/conversion zones (1, la and ~b) are used. Each conversion zone is followed by a separator (7, 7a and 7b).
The starting triglyceride mixture (2) is mixed with recycle enzyme solution (5b) from separator (7a) and is converted in zone (1). The crude reaction product is led via (~) to separator ~7). From separator (7), a triglyceride stream (9) and an enzyme solution (8) as purge stream are obtained. The glyceride stream (9) is mixed with recycle enzyme solution (5a) from separator (7b) in mixer/
conversion zone (la). The crude reaction product is led via (6a) to separator (7a) and separated into a glyceride stream (9a) and the recycle enzyme solution (5b). The glyceride stream (9a) is mixed with fresh, make-up enzyme (3) in mixer/conversion zone (lb). The crude material (6b) is separated in separator (7b) into a product stream (4) - and the recycle enzyme stream (5a). In this process also part of the purge (8) can be mixed with make-up enzyme solution (3), whereupon this mixture lS led to zone (lb).
According to Fig. 5, a similar process is carried out.
However, the enzymic solutions (5a, 5b and 5c) obtained in the different separators (7, 7a and 7b) are all led to a main recycle line (5), which is also ~ed with the make-up enzyme solution (3). Part of the recycle enzyme stream (5) is discarded as purge (8). This is done after the recycle stream (5a) has been combined with the main recycle stream (5).
~07~
F 7071 (R) EXAMPLE
The process ls carried out, using the flow sheet of Fig. 2.
In this process, a mixture of 18~0 kg of triglycerides and 160 kg of diglycerides is mixed per hour in a Silverson mixing device with a water phase comprising 836 kg of water, 160 kg of glycerol and 4 kg of enzyme (Amono-G), resulting in an emulsion with a droplet size of about 25 ~m.
This emulsion is converted during a residence time of 15 minutes in the conversion zone.
The crude reaction mixture containing 2 wt.% of diglycerides is separated in centrifuge (7). 1990 Kg/h of a glyceride product (4) containing 2 wt.% of diglycerides and 5 wt.% of free fatty acids are obtained via line ~4).
A water phase comprising 829 kg of water, 178 kg of glycerol and 4.0 kg of enzyme is removed from the centrifuge.
From this water phase, 101 kg/h is discarded as a purge via line (8).
The remainder is mixed with 90 kg of make-up enzyme solution (containing 0.4 kg of enzyme) and the enzyme solution is recirculated to mixer ~1).
Claims (15)
1. Process for the enzymic removal of diglycerides from glyceride mixtures containing at least diglycerides and triglycerides by contacting the glyceride mixtures in an enzymic conversion zone with an aqueous solution of an enzyme specific for the conversion of diglycerides, characterized by the fact that the contact of the aqueous enzyme solution and glyceride mixture is established in an emulsion of the glyceride mixture in the aqueous enzyme solution, the water content of the emulsion being 15-50 wt.%, and the droplet size of the glycerides in the emulsion being less than 100 µm.
2. Process according to Claim 1, wherein the contact is established as a counter-current process, wherein fresh glyceride mixture is fed to one end of the conversion zone and the enzyme solution is fed to the opposide end of the conversion zone.
3. Process according to Claim 2, wherein the conversion zone is a contactor such as a rotating disc contactor, a multi-stage sieve tray column, a packed column, or mixer/settler devices.
4. Process according to Claim 1, wherein the droplet size of the glyceride mixture in the emulsion is less than 50 µm.
5. Process according to Claim 4, wherein the mean droplet size of the glyceride mixture is 5-20 µm.
6. Process according to Claim 1, wherein the emulsion is obtained by mixing of the glyceride and water phases in a high-shear mixer of the Silverson type.
F 7071 (R) US/CA/JP
F 7071 (R) US/CA/JP
7. Process according to Claim 6, wherein the mixing device is part of an enzymic conversion zone.
8. Process according to Claim 1, wherein the contact time of the reaction components in the conversion zone is kept between 1 and 60 minutes.
9. Process according to Claim 6, wherein the crude reaction product from the conversion zone is separated into a glyceride phase and into an aqueous phase rich in controllable levels of glycerol and containing part of the enzymes.
10. Process according to Claim 9, wherein the aqueous phase containing part of the enzymes is recirculated to the enzymic conversion zone.
11. Process according to Claim 10, wherein make-up enzyme is added to the aqueous phase containing the enzymes in order to increase the concentration of enzyme to the desired concentration of at least 0.05 wt.%, calculated on the oil, which enzyme solution is recirculated to the conversion zone.
12. Process according to Claim 1, wherein at least part of the aqueous phase rich in glycerol is removed as purge from the system.
13. Process according to Claim 9, wherein the glcyeride phase is washed with water, whereupon a product rich in triglycerides, is separated from an aqueous phase containing part of the enzymes, which aqueous phase is at least partly recirculated.
F 7071 (R) US/CA/JP
F 7071 (R) US/CA/JP
14. Process according to Claim 1, wherein the recycle stream is added in a manner co-current with the process stream.
15. Process according to Claim 1, wherein several subsequent mixer/conversion devices and several separators are used, the aqueous stream(s), containing the enzymes, withdrawn from the separator(s), being used in a manner counter-current to the process stream.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92301542 | 1992-02-25 | ||
| GB92301542.4 | 1992-02-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2090750A1 true CA2090750A1 (en) | 1993-08-26 |
Family
ID=8211280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002090750A Abandoned CA2090750A1 (en) | 1992-02-25 | 1993-02-24 | Enzymic diglyceride removal |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0558112A1 (en) |
| JP (1) | JPH0680984A (en) |
| CA (1) | CA2090750A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6936289B2 (en) | 1995-06-07 | 2005-08-30 | Danisco A/S | Method of improving the properties of a flour dough, a flour dough improving composition and improved food products |
| EP2251410A3 (en) * | 1996-03-28 | 2011-09-28 | DSM IP Assets B.V. | Preparation of microbial polyunsaturated fatty acid containing oil from pasteurised biomass |
| EP0904339B2 (en) * | 1996-05-15 | 2006-09-20 | DSM IP Assets B.V. | Sterol extraction with a polar solvent to give low sterol microbial oil |
| DE69904941T3 (en) | 1998-07-21 | 2008-01-31 | Danisco A/S | FOOD |
| DE19923785A1 (en) * | 1999-05-25 | 2000-11-30 | Cognis Deutschland Gmbh | Use of PIT emulsions in fermentation processes |
| JP4309137B2 (en) | 2001-05-18 | 2009-08-05 | ダニスコ エイ／エス | Preparation method of dough using enzyme |
| DE602004030000D1 (en) | 2003-01-17 | 2010-12-23 | Danisco | PROCESS FOR IN-SITU-PRODUCTION OF AN EMULSIFIER IN A FOODSTUFF |
| US20050196766A1 (en) | 2003-12-24 | 2005-09-08 | Soe Jorn B. | Proteins |
| US7955814B2 (en) | 2003-01-17 | 2011-06-07 | Danisco A/S | Method |
| GB0716126D0 (en) | 2007-08-17 | 2007-09-26 | Danisco | Process |
| US7906307B2 (en) | 2003-12-24 | 2011-03-15 | Danisco A/S | Variant lipid acyltransferases and methods of making |
| US7718408B2 (en) | 2003-12-24 | 2010-05-18 | Danisco A/S | Method |
| GB0405637D0 (en) | 2004-03-12 | 2004-04-21 | Danisco | Protein |
| DK1776455T3 (en) | 2004-07-16 | 2015-06-22 | Dupont Nutrition Biosci Aps | LIPOLYTIC ENZYM, APPLICATIONS THEREOF IN THE FOOD INDUSTRY |
| EP2405007B1 (en) | 2007-01-25 | 2013-12-04 | DuPont Nutrition Biosciences ApS | Production of a lipid acyltransferase from transformed Bacillus licheniformis cells |
| JPWO2010126136A1 (en) * | 2009-04-30 | 2012-11-01 | 不二製油株式会社 | Method for inhibiting the formation of chloropropanols and their forming substances in glyceride oils |
| JP2018157820A (en) * | 2018-04-24 | 2018-10-11 | 不二製油株式会社 | Edible shea olein and method for producing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4158609A (en) * | 1975-09-23 | 1979-06-19 | Mueller Hans | Process for the continuous conversion of products by enzyme action |
| NZ199218A (en) * | 1981-01-19 | 1985-03-20 | Cpc International Inc | Production of fats and oils by cultivating yeast cells |
| JPH0730352B2 (en) * | 1985-06-25 | 1995-04-05 | 天野製薬株式会社 | Enzymatic purification of fats and oils |
| SE452166B (en) * | 1986-03-10 | 1987-11-16 | Berol Kemi Ab | PROCEDURE FOR TRANSESTERIFICATION OF TRIGLYCERIDES |
| JPH03262492A (en) * | 1990-03-06 | 1991-11-22 | P Macneil Gerald | Preparation of monoglyceride |
-
1993
- 1993-02-05 EP EP93200311A patent/EP0558112A1/en not_active Withdrawn
- 1993-02-18 JP JP5051229A patent/JPH0680984A/en active Pending
- 1993-02-24 CA CA002090750A patent/CA2090750A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0680984A (en) | 1994-03-22 |
| EP0558112A1 (en) | 1993-09-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |