WO2011075802A1 - Production of diacylglycerols by lipase - catalyzed hydrolysis of palm oil - Google Patents

Production of diacylglycerols by lipase - catalyzed hydrolysis of palm oil Download PDF

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WO2011075802A1
WO2011075802A1 PCT/BR2010/000384 BR2010000384W WO2011075802A1 WO 2011075802 A1 WO2011075802 A1 WO 2011075802A1 BR 2010000384 W BR2010000384 W BR 2010000384W WO 2011075802 A1 WO2011075802 A1 WO 2011075802A1
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amano
lipase
palm oil
hydrolysis
reaction
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PCT/BR2010/000384
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French (fr)
Inventor
Rodrigo Octavio Mendonça Alves de SOUZA
Karen Medeiros GONÇALVES
Ivana Correa Ramos Leal
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Companhia Refinadora Da Amazônia
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    • 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

Definitions

  • the present invention relates to the production of diacylglycerols by heterogeneous catalysis using commercial enzymes to catalyze the production of diacylglycerols by hydrolysis reactions of palm oil.
  • the use of diacylglycerols instead of triacylglycerols which are found in oils and fats began at the 80' s. Its use was based on two important health benefits.
  • the first benefit relates to the suppression of triglycerides postprandial increase in serum and the second benefit is the suppression of body fat accumulation.
  • Fats and oils consist of a mixture of triacylglycerols, also called triglycerides, and differ only by the physical state, fats being solid or pasty and oils being liquid at room temperature. Such difference is mainly due to the fact that oils are richer in unsaturated fatty acid residues than fats.
  • Triacylglycerols consist of a highly efficient manner of storing metabolic energy, once they are less oxidized than carbohydrates and proteins and do not absorb much water, due to their apolar condition. Thus, triacylglycerols occupy a smaller volume in the organism, contrary to glycogen, which is another energy source that binds to water in an amount almost twice its weight.
  • Vegetable oils are mainly composed by glycerides of plant fatty acids and may contain phospholipids, free fatty acids and unsaponifiable constituents. Their physical characteristics vary according to the structure and distribution of fatty acids in the present triacylglycerols .
  • the triacylglycerol can be represented by the structure (I) below:
  • Rl, R2 and R3 are fatty acid residues.
  • Oils have a key role in food since they are important sources of essential fatty acids, carry fat-soluble vitamins and participate in the synthesis of many endogenous substances, among others. However, its excessive consumption is directly related to cardiovascular diseases, obesity and insulin resistance.
  • Diacylglycerols or diglycerides are glycerol esters which have two hydroxyl groups esterified by fatty acids, and they can exist in two stereochemical forms, known as sn-l,2-DAG (or 2,3) and sn-l,3-DAG, the natural isomeric relationship being 3:7 as a function of the acyl group migration during the process of oil refining.
  • the 1,2-DAG isoform is considered as a metabolic intermediate, which is formed after the ingestion of triacylglycerol.
  • the 1,3-DAG isoform is responsible for the beneficial effect, since it is metabolized by a route which is different from that of TAG and 1,2-DAG.
  • 1,3-DAG, 2,3-DAG and 1,2-DAG are respectively represented by structures (II), (III) and (IV) below: CH j OCOR
  • Diacylglycerol is a natural component in several and fats, comprising about 10% by weight, as demonstrated in Table 1 below.
  • the diacylglycerol is broadly used as an emulsifier and stabilizer in food, cosmetic and pharmaceutical industries. It has also been used in Japan and in the United States as cooking oil due to its recently discovered properties of reducing lipid levels, thus reducing weight and fat accumulation.
  • the commercial oil was introduced in Japan in 1999 under the trade name Econa. In the United States, said oil was registered as Enova ® oil after 15 years of research, clinical studies and experiments performed by Kao Corporation .
  • Enova contains approximately 20% by weight of triacylglycerol and 80% by weight of diacylglycerol, 56% thereof as the sn-l,3-DAG isoform. Its applications include the use as cooking oil, the use for the preparation of sauces and seasonings and products based on oils and fats.
  • Japan, weight and fat mass can be reduced by replacing 10 to 20 grams of conventional oils of the diet by diacylglycerol .
  • the DAG is produced by glycerolysis, hydrolysis or chemical esterification of oils and fats. These processes often use high temperatures and/or toxic catalysts. Such conditions cause changes in the flavor and in the color of the oil, reduce selectivity and increase energy expenditure, thereby increasing process costs.
  • Enzymatic techniques have several advantages over the chemical process, including increased selectivity, increased product purity, the use of milder temperatures and the suppression of toxic catalysts. To this end, the use of lipases has been widely studied.
  • diacylglycerol The most used processes to obtain diacylglycerol are the glycerolysis and hydrolysis of fatty acid esters as is shown below.
  • Triglyceride Glycerol 1 3-Diacylglycerol 1, 2-Diacylglycerol
  • H 2 C I C0 2 R .
  • Triglyceride 1 3-Diacylglycerol 1, 2-Diacylglycerol
  • a transesterification reaction between a triacylglycerxde and glycerol catalyzed by a lipase occurs in the glycerolysis process.
  • the reactions occur without solvent and mechanical stirring is used, since the triacylglycerides have high viscosity.
  • water is the agent which, together with the lipase, will hydrolyze the ester linkages of the triacylglyceride .
  • the reactions occur in the absence of solvent and mechanical stirring is used.
  • the stoichiometry of the reactants is as important as the adjustment of mechanical (stirring) and thermal (heat) factors. Thus, a huge variety of reaction conditions can be used in order to obtain the desired result.
  • the products are formed by two types of diacylglycerols that differ only in the position of the fatty acid chains (1,3 and 1,2).
  • the enzymatic catalysis provides only one of them due to its high specificity.
  • the state of the art includes some patent documents related to the production of diacylglycerols from fats and oils, catalyzed by lipases.
  • the Japanese document JP 1071495 describes a method for the preparation of diglycerides with high purity and yield, which comprises an esterification reaction between glycerol and saturated or unsaturated fatty acids with 4 to 22 carbon atoms in the presence of an 1 , 3-selective lipase immobilized with an ion exchange resin, and in which water or lower alcohol produced by the reaction are removed to maximum from the reaction system to increase the ester synthesis yield and reduce the amount of monoglycerides .
  • 3-selective lipases are selected among the ones originating from microorganisms of Rhizopus, Mucor and Aspergillus species, more specifically from Rhizopus delemar, Rhizopus japonicus, Rhizopus niveus, Aspergillus niger, Mucor javanicus and Mucor miehei.
  • the process for producing diacylglycerols described in the US document 2007/0148745 involves the use of an immobilized 1 , 3-selective lipase in the presence of water to promote the hydrolysis of triacylglycerols found in oils and fats.
  • Said document teaches a controlled hydrolysis with dehydration at the end of the process, using various vegetable oils, including palm oil.
  • lipases are used as catalysts, preferably lipases immobilized with ion exchange resins. Temperatures between 20 and 90 °C are applied and the amount of water ranges from 20 to 180 parts of water per 100 parts of oil.
  • the amount of enzyme used in the reactions is not specified; however, the examples suggest 10% by weight of enzyme to oil.
  • the diacylglycerol is purified and 0.5% to 25% by weight of phytosterols and ferulic acid esters are added in relation to the weight of diacylglycerol.
  • the reactions are catalyzed by Amano PS and Amano IM enzymes. Nevertheless, the amount of water used in the process of the present invention is four times less than the amount of water added in the process disclosed by document US 2007/0148745, since the minimum percentage used in such document was 20% by weight, while in the present invention only 5% by weight was used.
  • Document WO03/094634 Al relates to the beneficial effects of using diacylglycerols in food and beverages. Said document discloses the physical-chemical changes obtained by adding different amounts of diacylglycerols in food, thus leading to new organoleptic properties.
  • the object of the present invention relates to the production of diacylglycerols by heterogeneous catalysis.
  • Amano PS and Amano IM commercial enzymes are used to catalyze the production of diacylglycerols by the hydrolysis reaction of refined palm oil.
  • the object of the present invention comprises a process for the production of diacylglycerols by the hydrolysis of refined palm oil catalyzed by Amano PS and
  • Amano PS and Amano IM commercial lipases are used as lipase sources to catalyze the hydrolysis of refined palm oil.
  • the reactions should be conducted under optimal conditions for lipase activity, or as near as possible of such conditions.
  • the optimal conditions involve temperature, reactant concentration and stirring.
  • the enzymatic hydrolysis under reference is carried out in aqueous medium during a period of time within the range of 1 to 24 hours, thus resulting in a mixture of diacylglycerols, fatty acids and glycerol.
  • the reaction catalyzed by lipases should be operated in batch.
  • an apolar organic solvent is added to the reaction medium (for example, t- butanol, hexane, heptane or isooctane alone or associated with 10 to 90% by weight of water) and then the reaction mixture is filtered and washed with sodium chloride saturated solution. The organic phases are separated, dried with anhydrous sodium sulfate and the solvent is evaporated at reduced pressure.
  • Example 1 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 60°C for 24h under stirring (1300 rpm) .
  • Example 2 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 60°C for 24h under stirring (1300 rpm) .
  • Example 3 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano PS lipase at 60°C for 24h under stirring (1300 rpm) .
  • Example 4 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano IM lipase at 60°C for 24h under stirring (1300 rpm) .
  • Example 5 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano PS lipase at 60°C for 24h under stirring (1300 rpm) .
  • Example 6 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano IM lipase at 60°C for 24h under stirring (1300 rpm) .
  • Example 7 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 40°C for 24h under stirring (1300 rpm) .
  • Example 8 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 40°C for 24h under stirring (1300 rpm) .
  • Example 9 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 50°C for 24h under stirring (1300 rpm) .
  • Example 10 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 50°C for 24h under stirring (1300 rpm) .
  • Example 11 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 55°C for 24h under stirring (1300 rpm) .
  • Example 12 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 55°C for 24h under stirring (1300 rpm) .
  • Example 13 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (700 rpm) .
  • Example 14 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (700 rpm) .
  • Example 15 Hydrolysis of palm oil by Amano PS lipase. The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (700 rpm) .
  • Example 16 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (700 rpm) .
  • Example 17 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (700 rpm) .
  • Example 18 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (700 rpm) .
  • Example 19 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 40°C for 24 hours under stirring (700 rpm) .
  • Example 20 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 40°C for 24 hours under stirring (700 rpm) .
  • Example 21 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 50°C for 24 hours under stirring (700 rpm) .
  • Example 22 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 55°C for 24 hours under stirring (700 rpm) .
  • Example 24 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 55°C for 24 hours under stirring (700 rpm) .
  • Example 25 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 60 °C for 24 hours under stirring (100 rpm).
  • Example 26 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (100 rpm) .
  • Example 27 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (100 rpm) .
  • Example 28 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (100 rpm) .
  • Example 29 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (100 rpm) .
  • Example 30 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (100 rpm) .
  • Example 31 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 40°C for 24 hours under stirring (100 rpm) .
  • Example 32 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 40°C for 24 hours under stirring (100 rpm) .
  • Example 33 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 50 °C for 24 hours under stirring (100 rpm) .
  • Example 34 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 50°C for 24 hours under stirring (100 rpm) .
  • Example 35 Hydrolysis of palm oil by Amano PS lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 55°C for 24 hours under stirring (100 rpm) .
  • Example 36 Hydrolysis of palm oil by Amano IM lipase.
  • the reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 55°C for 24 hours under stirring (100 rpm) .
  • Amano PS and Amano IM enzymes are an alternative to the use of other commercial enzymes, showing that their results depend on the reaction temperature, concentration of the enzyme and stirring speed.

Abstract

The present invention relates to a process for the production of 1,2 and 1,3-diacylglycerols catalyzed by enzymes from the hydrolysis of lipidic material. In the process under reference, Amano PS and Amano IM commercial lipases are used to catalyze the production of diacylglycerols by hydrolysis of lipidic material from palm oil. Different reaction conditions were employed, wherein variations in temperature, amount of enzyme and stirring speed were studied.

Description

PRODUCTION OF DIACYLGLYCEROLS BY LIPASE - CATALYZED
HYDROLYSIS OF PALM OIL
TECHNICAL FIELD
The present invention relates to the production of diacylglycerols by heterogeneous catalysis using commercial enzymes to catalyze the production of diacylglycerols by hydrolysis reactions of palm oil.
BACKGROUND ART
The use of diacylglycerols instead of triacylglycerols which are found in oils and fats began at the 80' s. Its use was based on two important health benefits. The first benefit relates to the suppression of triglycerides postprandial increase in serum and the second benefit is the suppression of body fat accumulation.
Fats and oils consist of a mixture of triacylglycerols, also called triglycerides, and differ only by the physical state, fats being solid or pasty and oils being liquid at room temperature. Such difference is mainly due to the fact that oils are richer in unsaturated fatty acid residues than fats.
Triacylglycerols consist of a highly efficient manner of storing metabolic energy, once they are less oxidized than carbohydrates and proteins and do not absorb much water, due to their apolar condition. Thus, triacylglycerols occupy a smaller volume in the organism, contrary to glycogen, which is another energy source that binds to water in an amount almost twice its weight.
Vegetable oils are mainly composed by glycerides of plant fatty acids and may contain phospholipids, free fatty acids and unsaponifiable constituents. Their physical characteristics vary according to the structure and distribution of fatty acids in the present triacylglycerols . The triacylglycerol can be represented by the structure (I) below:
CHjOCOR1
R2OCOCH
CHjOCOR3
(I)
wherein Rl, R2 and R3 are fatty acid residues.
Oils have a key role in food since they are important sources of essential fatty acids, carry fat-soluble vitamins and participate in the synthesis of many endogenous substances, among others. However, its excessive consumption is directly related to cardiovascular diseases, obesity and insulin resistance.
Diacylglycerols or diglycerides are glycerol esters which have two hydroxyl groups esterified by fatty acids, and they can exist in two stereochemical forms, known as sn-l,2-DAG (or 2,3) and sn-l,3-DAG, the natural isomeric relationship being 3:7 as a function of the acyl group migration during the process of oil refining.
The 1,2-DAG isoform is considered as a metabolic intermediate, which is formed after the ingestion of triacylglycerol. The 1,3-DAG isoform is responsible for the beneficial effect, since it is metabolized by a route which is different from that of TAG and 1,2-DAG. 1,3-DAG, 2,3-DAG and 1,2-DAG are respectively represented by structures (II), (III) and (IV) below: CHjOCOR
HOCH
CH-OCORJ
Figure imgf000004_0001
Diacylglycerol is a natural component in several and fats, comprising about 10% by weight, as demonstrated in Table 1 below.
TABLE 1
Acylglycerol content in edible oils from different sources
(g/100g)
Total
Oil TAG 1,2-DAG 1,3-DAG MAG Others
DAG
Soybean 97.9 1.0 ND1 ND1 0.0 1.1
Palm 93.1 5.8 ND1 ND1 <LD2 1.1
Cotton 87.0 9.5 ND1 ND1 0.2 3.3
Corn 95.8 2.8 1.5 2.9 <LD2 1.4
Saffron 96.0 2.1 1.2 2.7 <LD2 1.9
Olive 93.3 5.5 ND1 ND1 0.2 2.3
Olive (mol%) 18-41 8-20 - - - -
Rapeseed 96.8 0.8 ND1 ND1 0.1 2.3
Vegetal (canola +
98.3 1.7 0.6 1.1 <LD2 ND1 soybean)
Canola 97.1 2.9 1.0 1.9 <LD2 ND1
Sesame 95.2 4.1 1.2 2.9 0.8 ND1
Pure sesame 95.5 3.9 1.2 2.7 0.6 ND1
Rice 92.4 7.6 2.4 5.2 <LD2 ND1
Rice germ 91.2 8.8 2.7 6.1 <LD2 ND1
Corn germ 95.5 4.5 1.5 2.9 <LD2 ND1
Grape seed 94.2 5.8 2.1 3.7 <LD2 ND1 DAG 17.3 81.4 28.4 53.0 1.2 ND1
Not detected
Below the detection limit
The diacylglycerol is broadly used as an emulsifier and stabilizer in food, cosmetic and pharmaceutical industries. It has also been used in Japan and in the United States as cooking oil due to its recently discovered properties of reducing lipid levels, thus reducing weight and fat accumulation.
The commercial oil was introduced in Japan in 1999 under the trade name Econa. In the United States, said oil was registered as Enova® oil after 15 years of research, clinical studies and experiments performed by Kao Corporation .
Enova contains approximately 20% by weight of triacylglycerol and 80% by weight of diacylglycerol, 56% thereof as the sn-l,3-DAG isoform. Its applications include the use as cooking oil, the use for the preparation of sauces and seasonings and products based on oils and fats.
According to clinical studies in the United States and
Japan, weight and fat mass can be reduced by replacing 10 to 20 grams of conventional oils of the diet by diacylglycerol .
The DAG is produced by glycerolysis, hydrolysis or chemical esterification of oils and fats. These processes often use high temperatures and/or toxic catalysts. Such conditions cause changes in the flavor and in the color of the oil, reduce selectivity and increase energy expenditure, thereby increasing process costs.
Enzymatic techniques have several advantages over the chemical process, including increased selectivity, increased product purity, the use of milder temperatures and the suppression of toxic catalysts. To this end, the use of lipases has been widely studied.
The most used processes to obtain diacylglycerol are the glycerolysis and hydrolysis of fatty acid esters as is shown below.
GLYCEROLYSIS REACTIONS
H2C I C02 H2CI OH H2C C02R H2C C02R
Lipase I J
CH C02R + CH OH →■ CH OH CH C02R
¾C I C02R H2CI OH H2CI C02R H2CI OH
Triglyceride Glycerol 1 , 3-Diacylglycerol 1, 2-Diacylglycerol
HYDROLYSIS REACTIONS
H2C I C02R . H2C C02R h½C C02R
Lipase
CH CO2R + water ^ CH—0H or CH COiR
H2C C02R H2C C02R Hfi OH
Triglyceride 1 , 3-Diacylglycerol 1, 2-Diacylglycerol
These reactions do not necessarily lead to the formation of diacylglycerol, since the reaction conditions must be controlled so that it does not lead to the total breakdown . of the fatty acid ester. In this case, reaction byproducts like fatty acids, monoacylglycerols and glycerol can be obtained.
A transesterification reaction between a triacylglycerxde and glycerol catalyzed by a lipase occurs in the glycerolysis process. Typically, the reactions occur without solvent and mechanical stirring is used, since the triacylglycerides have high viscosity. In hydrolysis reactions, water is the agent which, together with the lipase, will hydrolyze the ester linkages of the triacylglyceride . As in glycerolysis reaction, the reactions occur in the absence of solvent and mechanical stirring is used. The stoichiometry of the reactants is as important as the adjustment of mechanical (stirring) and thermal (heat) factors. Thus, a huge variety of reaction conditions can be used in order to obtain the desired result.
After the hydrolysis and glycerolysis reactions, the products are formed by two types of diacylglycerols that differ only in the position of the fatty acid chains (1,3 and 1,2). However, the enzymatic catalysis provides only one of them due to its high specificity.
The state of the art includes some patent documents related to the production of diacylglycerols from fats and oils, catalyzed by lipases.
The Japanese document JP 1071495 describes a method for the preparation of diglycerides with high purity and yield, which comprises an esterification reaction between glycerol and saturated or unsaturated fatty acids with 4 to 22 carbon atoms in the presence of an 1 , 3-selective lipase immobilized with an ion exchange resin, and in which water or lower alcohol produced by the reaction are removed to maximum from the reaction system to increase the ester synthesis yield and reduce the amount of monoglycerides . 1, 3-selective lipases are selected among the ones originating from microorganisms of Rhizopus, Mucor and Aspergillus species, more specifically from Rhizopus delemar, Rhizopus japonicus, Rhizopus niveus, Aspergillus niger, Mucor javanicus and Mucor miehei.
The process for producing diacylglycerols described in the US document 2007/0148745 involves the use of an immobilized 1 , 3-selective lipase in the presence of water to promote the hydrolysis of triacylglycerols found in oils and fats. Said document teaches a controlled hydrolysis with dehydration at the end of the process, using various vegetable oils, including palm oil. Furthermore, lipases are used as catalysts, preferably lipases immobilized with ion exchange resins. Temperatures between 20 and 90 °C are applied and the amount of water ranges from 20 to 180 parts of water per 100 parts of oil. The amount of enzyme used in the reactions is not specified; however, the examples suggest 10% by weight of enzyme to oil. At the end of the process, the diacylglycerol is purified and 0.5% to 25% by weight of phytosterols and ferulic acid esters are added in relation to the weight of diacylglycerol.
In the present invention, the reactions are catalyzed by Amano PS and Amano IM enzymes. Nevertheless, the amount of water used in the process of the present invention is four times less than the amount of water added in the process disclosed by document US 2007/0148745, since the minimum percentage used in such document was 20% by weight, while in the present invention only 5% by weight was used.
Additionally, interesting results were obtained with the teachings of the present invention with only 1% by weight of enzyme to palm oil and with 0.5% by weight to palm olein, whereas in said US document the percentage of enzyme is not mentioned, but suggesting 10% by weight in its examples, as was previously mentioned.
Document O2008/018147 Al teaches the composition of certain oils and identifies the relationship that should exist among free fatty acids, 1,2 and 1, 3-diacylglycerols and triacylglycerols .
The process described in document WO2008/003314 Al involves the formation of glycosides derived from mono- and diacylglycerols of plant material. Said document describes in details the process of extracting glycosides derived from mono and diacylglycerols without any enzymatic process involved.
The process described in document WO2007/097160 Al involves the use of microorganisms of Moritella sp. species in the production of monoacylglycerols.
The process disclosed in the Japanese document JP 330289/1992 describes glycerolysis reactions wherein stoichiometric amounts of glycerol are used for the formation of diacylglycerol . In this process, a number of phospholipases for the production of diacylglycerol by transesterification reaction of vegetable oils with glycerol is used.
Document WO03/094634 Al relates to the beneficial effects of using diacylglycerols in food and beverages. Said document discloses the physical-chemical changes obtained by adding different amounts of diacylglycerols in food, thus leading to new organoleptic properties.
Document WO2005/048722 Al relates to the beneficial effects of regular ingestion of diacylglycerols. In the same manner as the process described above, said document shows the influence of using diacylglycerols as additives in food and supplements.
The process disclosed in document WO2006/022356 Al describes the formation of diacylglycerols catalyzed by microorganisms. In this process, the microorganisms lead to the formation of a mixture of diacylglycerols, monoacylglycerols and free fatty acids.
SUMMARY OF THE INVENTION
The object of the present invention relates to the production of diacylglycerols by heterogeneous catalysis. In the process of the present invention, Amano PS and Amano IM commercial enzymes are used to catalyze the production of diacylglycerols by the hydrolysis reaction of refined palm oil.
DETAILED DESCRIPTION OF THE INVENTION
The object of the present invention comprises a process for the production of diacylglycerols by the hydrolysis of refined palm oil catalyzed by Amano PS and
Amano IM commercial lipases.
In the present invention, Amano PS and Amano IM commercial lipases are used as lipase sources to catalyze the hydrolysis of refined palm oil.
In order to obtain diacylglycerol conversions from refined palm oil, the reactions should be conducted under optimal conditions for lipase activity, or as near as possible of such conditions. The optimal conditions involve temperature, reactant concentration and stirring.
The enzymatic hydrolysis under reference is carried out in aqueous medium during a period of time within the range of 1 to 24 hours, thus resulting in a mixture of diacylglycerols, fatty acids and glycerol.
The reaction catalyzed by lipases should be operated in batch.
After the end of the reaction, an apolar organic solvent is added to the reaction medium (for example, t- butanol, hexane, heptane or isooctane alone or associated with 10 to 90% by weight of water) and then the reaction mixture is filtered and washed with sodium chloride saturated solution. The organic phases are separated, dried with anhydrous sodium sulfate and the solvent is evaporated at reduced pressure.
The examples presented below are only intended to illustrate the invention and facilitate its understanding, and are not intended to limit it in any manner.
EXAMPLES
Example 1 : Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 60°C for 24h under stirring (1300 rpm) .
Example 2 : Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 60°C for 24h under stirring (1300 rpm) .
Example 3 : Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano PS lipase at 60°C for 24h under stirring (1300 rpm) .
Example 4 : Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano IM lipase at 60°C for 24h under stirring (1300 rpm) .
Example 5: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano PS lipase at 60°C for 24h under stirring (1300 rpm) .
Example 6: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano IM lipase at 60°C for 24h under stirring (1300 rpm) .
Example 7 : Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 40°C for 24h under stirring (1300 rpm) .
Example 8 : Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 40°C for 24h under stirring (1300 rpm) .
Example 9: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 50°C for 24h under stirring (1300 rpm) .
Example 10: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 50°C for 24h under stirring (1300 rpm) .
Example 11: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 55°C for 24h under stirring (1300 rpm) .
Example 12 : Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 55°C for 24h under stirring (1300 rpm) .
Example 13: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (700 rpm) .
Example 14: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (700 rpm) .
Example 15: Hydrolysis of palm oil by Amano PS lipase. The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (700 rpm) .
Example 16: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (700 rpm) .
Example 17: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (700 rpm) .
Example 18: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (700 rpm) .
Example 19: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 40°C for 24 hours under stirring (700 rpm) .
Example 20: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 40°C for 24 hours under stirring (700 rpm) .
Example 21: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 50°C for 24 hours under stirring (700 rpm) .
Example 22: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 50°C for 24 hours under stirring (700 rpm) . Example 23: Hydrolysis of palm oil by 7Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 55°C for 24 hours under stirring (700 rpm) .
Example 24: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 55°C for 24 hours under stirring (700 rpm) .
Example 25: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 60 °C for 24 hours under stirring (100 rpm).
Example 26: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (100 rpm) .
Example 27: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (100 rpm) .
Example 28: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 2.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (100 rpm) .
Example 29: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano PS lipase at 60°C for 24 hours under stirring (100 rpm) .
Example 30: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 3.0% w/w of Amano IM lipase at 60°C for 24 hours under stirring (100 rpm) .
Example 31: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 40°C for 24 hours under stirring (100 rpm) .
Example 32 : Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 40°C for 24 hours under stirring (100 rpm) .
Example 33: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 50 °C for 24 hours under stirring (100 rpm) .
Example 34 : Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 50°C for 24 hours under stirring (100 rpm) .
Example 35: Hydrolysis of palm oil by Amano PS lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano PS lipase at 55°C for 24 hours under stirring (100 rpm) .
Example 36: Hydrolysis of palm oil by Amano IM lipase.
The reaction was carried out by incubating 2.0 g of palm oil, 0.1 mL of water and 1.0% w/w of Amano IM lipase at 55°C for 24 hours under stirring (100 rpm) .
Table 2 below shows the results of the hydrolysis reactions of the examples above.
TABLE 2
Water % by weight of Temp. Yield
Example rpm Enzyme
(mL) enzyme (°C) (%)
1 1300 0.1 1 Amano PS 60 36 1300 0.1 1 Amano IM 60 52
1300 0.1 2 Amano PS 60 30
1300 0.1 2 Amano IM 60 45
1300 0.1 3 Amano PS 60 32
1300 0.1 3 Amano IM 60 42
1300 0.1 1 Amano PS 40 24
1300 0.1 1 Amano IM 40 31
1300 0.1 1 Amano PS 50 34
1300 0.1 1 Amano IM 50 42
1300 0.1 1 Amano PS 55 30
1300 0.1 1 Amano IM 55 32
700 0.1 1 Amano PS 60 32
700 0.1 1 Amano IM 60 55
700 0.1 2 Amano PS 60 27
700 0.1 2 Amano IM 60 41
700 0.1 3 Amano PS 60 29
700 0.1 3 Amano IM 60 45
700 0.1 1 Amano PS 40 20
700 0.1 1 Amano IM 40 21
700 0.1 1 Amano PS 50 36
700 0.1 1 Amano IM 50 48
700 0.1 1 Amano PS 55 34
700 0.1 1 Amano IM 55 43
100 0.1 1 Amano PS 60 29
100 0.1 1 Amano IM 60 37
100 0.1 2 Amano PS 60 29
100 0.1 2 Amano IM 60 33
100 0.1 3 Amano PS 60 26
100 0.1 3 Amano IM 60 36
100 0.1 1 Amano PS 40 21 32 100 0.1 1 Amano IM 40 23
33 100 0.1 1 Amano PS 50 24
34 100 0.1 1 Amano IM 50 33
35 100 0.1 1 Amano PS 55 25
36 100 0.1 1 Amano IM 55 33
The results shown in the comparative table above summarize the reaction conditions studied for this process as well as the product yields (diacylglycerol) found in different reaction conditions. The obtained results show that Amano IM enzyme presents superior results in comparison with Amano PS enzyme, regardless of reaction conditions used. However, when temperatures in the range of 60°C are used, better yields are obtained. Such result was not expected for these enzymes, since they are not known for their hydrolytic capacity but by their ability to perform esterification reactions.
Thus, Amano PS and Amano IM enzymes are an alternative to the use of other commercial enzymes, showing that their results depend on the reaction temperature, concentration of the enzyme and stirring speed.
The above description of the present invention was presented for illustration and description purposes. Thus, the description does not intend to limit the invention to the form revealed herein. Therefore, variations and modifications consistent with the teachings above which are based on the skill or knowledge of the relevant art are within the scope of the present invention. The present invention intends to include all modifications and variations thereof which are within the scope described in the present specification, as well as in the attached claims .

Claims

1. A process for the production of diacylglycerols by hydrolysis reaction of palm oil characterized by being catalyzed by 0.1 to 5.0% by weight of lipases at temperatures ranging from 25 to 80°C in aqueous solution, under stirring and in the presence of an apolar organic solvent .
2. The process according to claim 1, wherein the lipase is selected from Amano PS and Amano IM enzymes.
3. The process according to claim 1, wherein the solvent can be selected from t-butanol, hexane, heptane or isooctane, either alone or associated with 10 to 90% by weight of water.
4. The process according to claim 1, wherein the reaction time ranges from 1 to 24 hours.
5. The process according to claim 1, wherein the stirring speed ranges from 100 to 1300 rpm.
PCT/BR2010/000384 2009-12-24 2010-11-24 Production of diacylglycerols by lipase - catalyzed hydrolysis of palm oil WO2011075802A1 (en)

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