CA2288528C - Preparation and stabilization of food-grade marine oils - Google Patents
Preparation and stabilization of food-grade marine oils Download PDFInfo
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- CA2288528C CA2288528C CA002288528A CA2288528A CA2288528C CA 2288528 C CA2288528 C CA 2288528C CA 002288528 A CA002288528 A CA 002288528A CA 2288528 A CA2288528 A CA 2288528A CA 2288528 C CA2288528 C CA 2288528C
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- A—HUMAN NECESSITIES
- A21—BAKING; EDIBLE DOUGHS
- A21D—TREATMENT, e.g. PRESERVATION, OF FLOUR OR DOUGH, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS; PRESERVATION THEREOF
- A21D2/00—Treatment of flour or dough by adding materials thereto before or during baking
- A21D2/08—Treatment of flour or dough by adding materials thereto before or during baking by adding organic substances
- A21D2/14—Organic oxygen compounds
- A21D2/16—Fatty acid esters
- A21D2/165—Triglycerides
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
- A23C11/00—Milk substitutes, e.g. coffee whitener compositions
- A23C11/02—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins
- A23C11/04—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins containing non-milk fats but no non-milk proteins
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
- A23C9/00—Milk preparations; Milk powder or milk powder preparations
- A23C9/12—Fermented milk preparations; Treatment using microorganisms or enzymes
- A23C9/13—Fermented milk preparations; Treatment using microorganisms or enzymes using additives
- A23C9/1315—Non-milk proteins or fats; Seeds, pulses, cereals or soja; Fatty acids, phospholipids, mono- or diglycerides or derivatives therefrom; Egg products
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/001—Spread compositions
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/015—Reducing calorie content; Reducing fat content, e.g. "halvarines"
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/02—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation containing fruit or vegetable juices
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
- C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B5/00—Preserving by using additives, e.g. anti-oxidants
- C11B5/0092—Mixtures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/02—Food
- G01N33/03—Edible oils or edible fats
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Microbiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Medicinal Chemistry (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Biophysics (AREA)
- Edible Oils And Fats (AREA)
- Fats And Perfumes (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- General Preparation And Processing Of Foods (AREA)
- Meat, Egg Or Seafood Products (AREA)
Abstract
Marine oil is stabilized by treatment with silica in the presence or absence of carbon, vacuum steam deodorisation at a temperature between about 140° C and about 210° C in the presence of 0.1-0.4% deodorised rosemary or sage extract. If desired 0.01-0.03% ascorbyl palmitate and 0.05-- 0.2% mixed tocopherol can be added.
Description
PREPARATION AND STABILISATION OF FOOD-GRADE MARINE OILS
The present invention relates to the preparation and stabilisation of food-grade marine oils.
Marine oils have attracted substantial interest as a source of n-3 long-chain polyunsaturated fatty acids (LCPUFA), particularly eicosapentaenoic acid (EPA) and docohexaenoic acid (DHA), which are of dietary significance .
These LCPUFA contain 5 or 6 double bonds which render them prone to atmospheric oxidation accompagnied by a fishy taste and smell. The increasing interest in LCPUFA has prompted a research into methods of stabilizing fish oils against oxidation and off-flavor development.
It has been known for a long time that refined marine oils are initially free from a taste and smell of fish but that reversion through oxidation occurs rapidly. Many attempts have been made to stabilize the oils by the addition of different anti-oxidants or mixtures thereof. However, all these attempts failed so far, cf. R.J. Hamilton et al., Journal of American Oil and Chemist's Society (JAOCS), Vol. 75, no. 7, p. 813-822, (1998). Accordingly, there has been and still is a need for a process by means of which such marine oils can be stabilized over a long period of time in a simple and economical way whereby even after a long period of storage no fishy taste and smell occur.
Refined marine oil which has been treated with silica and stabilised with a mixture of lecithin, ascorbyl palmitate and alpha tocopherol in accordance with the procedure described in European Patent Publication 612 346 shows excellent rancimat stability and good application performance mainly for health food supplements. In dairy applications such as yoghurts and milk drinks, however, this oil develops a strong fish smell and taste.
Kbr/vs/16.09.1999 Refined marine oil which has been treated with an adsorbent such as silica and stabilised with 0.1% deodorised rosemary extract (HERBALOX "0", Kalsec, Incorporated of Kalamazoo, Michigan) and, respectively, sage extract in accordance with and, respectively, an analogous manner to the procedure described in European Patent Publication 340 635 has a herby taste and smell which can be detected in food applications. This herby taste and smell supresses the taste and smell of fish. In dairy applications, the use of as little as 0.03% of HERBALOX "0" and, respectively, sage extract in the marine oil results in a very strong herby taste and smell which prevents the use of this oil in these applications.
It has now surprisingly been found in accordance with the present invention that marine oil which has been treated with silica in accordance with the procedure described in European Patent Publication 612 346 can be stabilized over a long period of time without the occurrence of fishy taste and smell by vacuum steam deodorization at a temperature between about 140 C
and about 210 C in the presence of 0.1-0.4% of deodorised rosmary or sage extract.
The fully refined marine oil used in the present invention is one which has been neutralised, bleached and deodorised in a conventional manner. The oil can be, for example, menhaden oil, herring oil, sardine oil, anchovy oil, pilchard oil, tuna oil, hake oil etc. or a blend of one or more of these oils.
Factors associated with or even responsible for the fishy taste and smell of a marine oil are not-well defined. In order to get more information which factors are responsible for the fishy taste and smell, 21 oil samples were analyzed in detail as shown and discussed below. Samples 1-10 used in these analytical proceedings are commercially available standard fish oils from suppliers throughout the world which are regarded as "aged" because of the delays in refining them once more in accordance with the procedure described in European Patent Publication 612 346, whereas samples 11-15 are refined fish oils where it is known that both the extraction and refining have been done immediately after the fish have been caught or with mimimum delay only. Samples 16-17 are oils of fungal origin. Samples 18-21 have been produced from commercially available fish oils in accordance with the proce-dure described in European Patent Publication 612 346 in which, however, a special short path distillation step has been included at the start of the process to trap smell molecules for use as described below. The purpose to this wide trawl is to have as representative a range as possible of refined oils containing EPA and DHA.
Table 1 records the influence of the acid value, the EPA and, respectively, DHA content, the color and the pro-oxidant iron and copper levels on sensory responses of a trained panel to the above described 21 oil samples.
The analysis for the determination of the EPA and DHA content and, respectively, the pro-oxidant iron and copper levels were performed according to analytical methods known in the art. For determining the acid value, i.e.
the number of milligrams of potassium hydroxide required to neutralize the free fatty acids in 1 gram of oil, the oil sample is titrated with 0.1N
aqueous potassium hydroxide solution using a 1% phenolphthalein indicator. The size of the sample was determined as folllows:
Expected acid value Test sample (g) >0.5 40 0.5 to 1 20 lto5 5 5 to 10 2.5 lOto20 1 >20 0.5 The color is determined by means of a Lovibond tintometer Model E AF
900 by matching the color of light transmitted through a specified depth of oil to the color of the lght originating from the same source, transmitted through standard color slides. The results are expressed in terms of the red (R), yellow(Y) and blue (B) units to obtain the match and the size of the cell used.
Taste and smell are sensorically evaluated by a trained panel comprising 12-15 persons. The panelist are asked to rank the samples in terms of perceiption of fishy taste and smell. A hedonic scale of 1 to 5 is used to express the extent of fishiness in which 1 represents no fishy taste or smell, while 5 stands for a very strong fishy taste or smell. The samples are coded using a three-digit code and 10 - 15 ml are submitted to the panel in a plastic beaker at 22 C. The products are evaluated after processing and after 4 weeks and, respectively, weeks storage at 22 C in aluminium containers.
Table 2 shows the effect of primary and secondary oxidation levels on the taste and smell of the same marine oils as in Table 1. Primary oxidation is measured as the peroxide value of the oils in milliequivalent (meq)/kg of oil.
Secondary oxidation is measured in two ways: first by the reaction of unsatu-rated aldehydes in the oil with anisidine and by the reaction of alkanals, alkenals and alkadienals in the oil with N,N-dimethyl-p-phenylenediamine.
For determining the peroxide value the oil is treated in a solution of acetic acid and chloroform with a solution of iodide and subsequently the free iodine is titrated with a solution of sodium thiosulphate. The size of the sample was determined as folllows:
Expected peroxide value Test sample () <1 10 lto5 2 5 to 10 1 >10 0.5 7771 The p-anisidine value is defined as 100 times the absorbence measured at 350 nm in a 1 cm cell of a solution containing 1.Og of the oil in 100 ml of a mixture of hexane and a solution of p-anisidine in glacial acetic acid (0.025g/
100 ml of glacial acetic acid). The size of the sample was determined as folllows:
Expected p-anisidine value Test sample () The aldehyde values werde determined based on a method described by K. Miyashita et al., JAOCS, Vol. 68 (1991), according to which N,N-dimethyl-p-phenylenediamine is reacted with aldehydes in the presence of acetic acid.
The three aldehyde classes (alkanal, alkenal and alkadienal) are determined by visible absorption at 400, 460 and, respectively, 500 nm. The aldehyde values are expressed in mmole/kg.
Furthermore, the level of smell molecules in each of these oils has been measured by static headspace coupled to GC/MS. The oil to be measured (samples of 1g each) is crimp sealed into a headspace vial (22ml) in an nitrogen atmosphere and heated at 120 C for 15 minutes in a headspace autosampler.
A measured volume of the headspace is automatically injected onto a GC(MS
using a heated transfer line. The gas chromatograph is used to separate the molecules and the mass spectrometer is used to identify and quantify the separated molecules. The results obtained are shown in Table 3.
, -5 Table 1 Acid EPA DHA Colour Copper Iron Taste Smell Value (%) (%) (Ppb) (Ppb) Standard fish 1 0.07 17.4 10.1 3.5R 23Y 13 39 2.3 0.7 2 0.06 18.8 9.1 1.1R 20Y 9 10 3.2 1.5 3 0.02 15.7 6.3 2.411 24Y 6 16 2.8 1.2 4 0.04 11.6 12.1 2.6113 1Y 12 22 4.0 3.0 0.17 17.6 10.3 2.5R 20Y 17 24 2.1 0.8 6 0.08 16.9 11.7 3.1R30Y 31 29 2.8 1.6 7 0.04 6.7 27.7 1.6R 20Y 14 25 1.2 0.6 8 0.20 6.7 27.5 3.6R 32Y 37 9 1.2 0.5 9 0.04 6.6 27.3 1.5R 23Y 13 18 2.7 1.6 0.08 6.7 28.0 1.211 31Y 12 12 3.6 2.0 Fresh fish 11 0.32 6.9 13.0 0.8R 15Y 3 27 2.2 0.6 12 0.30 8.7 7.5 2.OR 25Y 7 24 2.4 0.8 13 0.20 11.8 13.3 1.6R 20Y 6 13 1.5 1.0 14 0.23 10.3 11.8 0.5R 5.4Y 8 26 2.6 1.3 0.23 8.6 12.6 1.5R 15Y 6 29 2.8 1.0 Single cell 16 0.02 2.3 36.9 1.5R 32Y 7 10 1.7 0.9 17 0.77 0.4 31.0 1.2R 14Y 22 34 2.5 0.9 Standard fish distilled 18 0.2 18.0 10.5 2.2R 20Y 3 24 0.7 0.7 19 0.23 18.0 10.4 2.2R 20 Y 5 24 0.6 0.7 0.22 18.1 10.5 2.2R 23Y 8 30 0.6 0.6 21 0.19 17.9 10.4 2.3R 22Y 7 24 1.0 0.5 5 The above table shows that there is no correlation between the acid value, the EPA and, repectively DHA content, the color and pro-oxidant iron and copper levels and the taste and smell of these marine oils.
Table 2 Description Primary oxidation Secondary oxidation Peroxide value p-Anisidine value Aldehydes Taste Smell Standard fish A B C
1 0.4 19.8 2.41 0.3 0.9 2.3 0.7 2 0.5 12.62 1.46 0.15 0.54 3.2 1.5 3 0.8 8.7 0.54 0.08 0.34 2.8 1.2 4 0.7 15.31 1.87 0.29 0.68 4.0 3.0 0 3.77 0.6 0.09 0.17 2.1 0.8 6 0 4.24 1.02 0.11 0.23 2.8 1.6 7 0.4 8.24 1.94 0.24 0.66 1.2 0.8 8 0.4 6.81 1.09 0.15 0.35 1.2 0.5 9 0.5 6.81 1.06 0.14 0.32 2.7 1.6 2.1 9.42 0.97 0.18 0.36 3.6 2.0 Fresh fish 11 0 0.46 0.35 0.04 0.03 2.2 0.6 12 0 1.58 2.6 0.05 0.06 2.4 0.8 13 0 1.17 0.08 0.03 0.04 1.5 1.0 14 0 1.19 0.16 0.02 0.04 2.6 1.3 0 0.6 0.09 0.02 0.03 2.8 1.0 Single cell 16 4 6.58 1.13 0.26 0.3 1.7 0.9 17 0 1.45 0.45 0.03 0.04 2.5 0.9 Standard fish distilled 18 0 6.12 0.9 0.14 0.27 0.7 0.7 19 0 4.96 0.85 0.12 0.25 0.6 0.7 0 4.84 0.83 0.12 0.25 0.6 0.6 21 0 5.04 0.76 0.12 0.24 1.0 0.5 5 A = alkanals, B alkenals, C= alkadienals The above results show again that these oxidation indicators are not capable of distinguishing oils with a good taste and smell from those with bad ones.
Smell t- Lq ry O oo cc oo to ec o co o0 o r~ O a~ al ~ ~ cc u~
Taste M N co O .i m N N l- cp N v U,3 to ap ~ O h O O O
N M CV e}~ N GV .-i .-i CV c'M CV N ~-i Gy Cj r4 N G O O .-~
O O O O O O O O O O O O O O O
Heptadienal õ~ ,~ õ~ ,~ 0 Q ~ ~ ~o ~o ~o Lo ko Lo io v v v v v v.-+ v v v v v vv v~~~
Octenal ~ o d , o o a ~o o ~ o d , o 0 0 0 0 o O o 0 0 0 v v v v v v v v v v c~ rn c~ O~ c~ c~ c~ c~ a~ a~ c~
V V V v v v v v v v v Hexadienal o 0 0 0 0 0 0 0 0 0 0 0 (D 0 0 0 0 o O o 0 v v v v v v ~ v v v ~ to o ~ tO ~ tO ~ tD o~
MMrn a)M c)rn MMrn M
V V V V v v v v V v v Nonanal o 0 0 o O O o O o o O o 0 0 0 0 o O o O o .~ .~ . ~ .~ ~ '. .. .. r, ., ~ .. ~ .~ -4 ~ 1.4 r, ..+ ., '4 a~ o~ a~ c~ c~ c~ a~ c~ c~ c~ c~ rn c~ c~ m c~ m m m m on v v V v v v V v v v V V V v v v v V v v v Heptenal C D = o 0 0 o O o 0 0 0 0 0 0 0 0 c~ O a~ G~ Q~ O O rn O O O a~ a) rn a) c] 6n (MMO M
vv lr IV .r 10 IV
v v v v v v v v v V V V v v V v v v v v [- t- N N l- l- ~ t- h [- t- t- [- N [- l- l~ N L-Octanal o 0 0 0 0 o O 0 0 0 0 JIVc-IV, 0 0 o O o 0 o O
'V' '~' eM 'V' ~}' '~" er e!' '~i' V V V V V v V V V V V V V V V V V V V
Hexenal o 0 o O O o 0 0 0 0 0 0 0 0 o O o 0 0 0 0 r= E- t- t- r, L-v v V v V v V v V V V V V V V V V V v v v He tanal o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 o O o 0 P 0 0 0 0 0 o O o 0 0 0 0 0 o O o 0 0 0 0 0 ., ,H .y ., ,ti 11 ,H .1 .-q r, r, .1 .~ ,1 ., -4 -4 .1 r+ -4 ,ti ~ V V V V V V V V V V V V V V V V V V V V V
~ Penten-3-ol ~ oo ~r n N rn o o a~ o~ o 0 0 0 o N.-~
LO o ~ ao c~ C) LO c~ rn a~ a~ c~ ~ c~
N ~ er ~ ' ~ .~ V V M ,LõO,~ ~,Oõ4 V V V V V ilN V
Hexanal CD oo N o 0 o O o 0 0 0 0 0 0 0 o c~ oo co N O
tC~ ~fJ et' -4 H 4 .-i ~ .--i .-i .-i -4 .ti M M
V v V V V V V V V V V V V N o r~ r1 '-1 Penten-3- o 0 0.-+ ~~ o u~ ~~ ~~ N o O o 0 0 .-+ M O o O O
G~ G1 G) LO O M CV l- O Lo m G7 C7i m G) L7 n+ C7i G") m m one V V V - v V er er er V V V V V -4 N V V V V
Pentanal O o 0 0 0 0 o O o O o 0 0 0 o O O o 0 0 0 C7 to c7 t7 CD to CJ c7 = C.7 to c7 U CO Cn ;~ ~p c'~ c7 c7 c7 'r V .r ~ v c v lw I-r a v ~r -I:r c ~r ~ er rr w V V V V v v v v v V V V V v V V V v v V V
Ethyl Furan --4 N00 ~ o) ul co o~ o 0 0 ,_, ,n o 0 0 0 N 'r v v ~ O LO V 1" V V V v m V V V V
Butanal O O O O O O O O O O O O O O O O
C eM ~4' 'V" v 'V ef' e1' C' e!' et' V v V V V V v V V V V v V V v v Propenal o~ o ~~o M~~ A A A Ca A o ~l ~7 M Co ~ O O M ~ 7-. 7, 7-. 2- Z 'T-. N ~ O N
Propanal ~ ov en~ O co 00 Fcv, 0 0 ~~ C7 o G~ G~ v N -+ v L n c~ L M o . - 4 v v v N V V V V
.U
o rA .C CC
Q, d e,rA~, v ~
-~
--~ N M Q' ~7 C7 t- 00 m O Ll C) CD L~ vi 00 n 0 -i G) C/] p C~7 a3 ~
Again, the above data show that static headspace cannot distinguish between good and bad tasting marine oils.
Tables 1 - 3 also show that marine oils which have been, refined very soon after the oil has been extracted from freshly caught fish do not show better sensory response than oils which have been refined from aged crude fish oil. However, levels of secondary anisidine reactives and aldehydes are extre-mely low in these fresh oils. These results suggest that whatever is responsi-ble in the marine oil for the fishy taste and smell is present at extremely low lo levels below the detection limits of static headspace GCIMS. The data also show that neither anisidine nor aldehyde measurements are very useful in predicting the sensory quality of the oil - they are too insensitive.
Tables 1 - 3 show sensory data for single cell oils which demonstrate that they too can become fishy in both taste and smell. Table 1 also shows that when using specially refined oils it is possible to produce marine oils with excellent taste and smell but with quality parameters such as anisidine, peroxide, iron, copper, color and static headspace values which are not different from those of oils with poor taste and smell.
In order to have some understanding of the extent of the problem of the occurrence of fishy taste and smell in marine oils, efforts have been made to try and identify and quantify the molecules being responsible for the fishy taste and smell. Marine oils (1 kg each) rich in EPA and/or DHA which had a strong fishy smell were passed slowly through a short path still at 120 C and under reduced pressure (0.005 mbar). Two vacuum traps were connected in series each cooled with liquid nitrogen to collect the fishy volatiles which were removed by this process. These oils were then deodorised at 190 C and are the four specially refined oils recorded in Table 1 -3 as samples 18 - 21.
Even though their traditional quality parameters are not different from those oils which were deemed fishy they had only little or no fishy taste. The condensa-tes in the vacuum traps were dissolved in methyl tertiary butyl ether and subjected to olfactory detector GC/MS to identify fishy molecules which had been removed by this process. According to olfactory detector GC/MS the outlet stream from a gas chromatograph is split and routed to two different detectors.
In the present case, the detectors used were the mass spectrometer and the human nose. Such a system allows peaks to be identified by the MS and assigned smell comments by an operator.
A number of very potent smell molecules were identified in the distillates and are recorded in Table 4.
Table 4 Target molecule Characteristic according to prior art 4-heptenal Fish oil 1-octen-3-one Mushroom 1,5(Z)-octadien-3-ol Mushroom 1,5(Z)-octadien-3-one Metallic/fresh fish (E,E)-2,4-heptadienal Oxidized oil (E)-2-octenal Oxidized oil (Z)-6-nonenal Oxidized oil/putty/linseed oil (E,Z)-2,6-nonadienal Cucumber/fresh fish (E)-2-nonenal Oxidized oil (E,Z)-1,3,5-undecatriene Cod liver oil (E,E)-2,4-decadienal Fish/oxidized oil As can be seen from Table 3, only a few of the above molecules could be identified using static headspace and, thus, a more sensitive method was needed to remove headspace molecules from the oils. The detection limits for e.g. 2-octenal and, respectively, 2,4-hexadienal were 940 ppb and, respectively, 500 ppb. In order to improve the sensitivity of detection, the technique of dynamic headspace has been used. According to this technique, 2 g aliquots of oil have been heated to 75 C in a water bath purged with helium (150 ml/min) through a Tekmar purge glass apparatus onto Perkin Elmer cartridges contai-ning TENAX adsorbent (Enka Research Institute, Arnheim). The dynamic headspace has been measured by GC/MS using a 30m column of DB5-MS (l m film thickness).
Table 5 shows the taste panel response to a number of blends of mixtu-res of marine oils and the dynamic headspace profile of a number of molecules.
They have been identified by GUIVIS and olfactory detector GC(MS. As can be seen, some of these molecules can be detected to single figure ppb level using dynamic headspace. The importance of the data in Table 5 is that they explain why the data in Table 1 - 3 cannot possibly correlate with marine oil taste and smell and they also demonstrate the very small amount of oxidation which is required before the oil deteriorates to a unacceptable quality from the point of its taste and smell.
The present invention relates to the preparation and stabilisation of food-grade marine oils.
Marine oils have attracted substantial interest as a source of n-3 long-chain polyunsaturated fatty acids (LCPUFA), particularly eicosapentaenoic acid (EPA) and docohexaenoic acid (DHA), which are of dietary significance .
These LCPUFA contain 5 or 6 double bonds which render them prone to atmospheric oxidation accompagnied by a fishy taste and smell. The increasing interest in LCPUFA has prompted a research into methods of stabilizing fish oils against oxidation and off-flavor development.
It has been known for a long time that refined marine oils are initially free from a taste and smell of fish but that reversion through oxidation occurs rapidly. Many attempts have been made to stabilize the oils by the addition of different anti-oxidants or mixtures thereof. However, all these attempts failed so far, cf. R.J. Hamilton et al., Journal of American Oil and Chemist's Society (JAOCS), Vol. 75, no. 7, p. 813-822, (1998). Accordingly, there has been and still is a need for a process by means of which such marine oils can be stabilized over a long period of time in a simple and economical way whereby even after a long period of storage no fishy taste and smell occur.
Refined marine oil which has been treated with silica and stabilised with a mixture of lecithin, ascorbyl palmitate and alpha tocopherol in accordance with the procedure described in European Patent Publication 612 346 shows excellent rancimat stability and good application performance mainly for health food supplements. In dairy applications such as yoghurts and milk drinks, however, this oil develops a strong fish smell and taste.
Kbr/vs/16.09.1999 Refined marine oil which has been treated with an adsorbent such as silica and stabilised with 0.1% deodorised rosemary extract (HERBALOX "0", Kalsec, Incorporated of Kalamazoo, Michigan) and, respectively, sage extract in accordance with and, respectively, an analogous manner to the procedure described in European Patent Publication 340 635 has a herby taste and smell which can be detected in food applications. This herby taste and smell supresses the taste and smell of fish. In dairy applications, the use of as little as 0.03% of HERBALOX "0" and, respectively, sage extract in the marine oil results in a very strong herby taste and smell which prevents the use of this oil in these applications.
It has now surprisingly been found in accordance with the present invention that marine oil which has been treated with silica in accordance with the procedure described in European Patent Publication 612 346 can be stabilized over a long period of time without the occurrence of fishy taste and smell by vacuum steam deodorization at a temperature between about 140 C
and about 210 C in the presence of 0.1-0.4% of deodorised rosmary or sage extract.
The fully refined marine oil used in the present invention is one which has been neutralised, bleached and deodorised in a conventional manner. The oil can be, for example, menhaden oil, herring oil, sardine oil, anchovy oil, pilchard oil, tuna oil, hake oil etc. or a blend of one or more of these oils.
Factors associated with or even responsible for the fishy taste and smell of a marine oil are not-well defined. In order to get more information which factors are responsible for the fishy taste and smell, 21 oil samples were analyzed in detail as shown and discussed below. Samples 1-10 used in these analytical proceedings are commercially available standard fish oils from suppliers throughout the world which are regarded as "aged" because of the delays in refining them once more in accordance with the procedure described in European Patent Publication 612 346, whereas samples 11-15 are refined fish oils where it is known that both the extraction and refining have been done immediately after the fish have been caught or with mimimum delay only. Samples 16-17 are oils of fungal origin. Samples 18-21 have been produced from commercially available fish oils in accordance with the proce-dure described in European Patent Publication 612 346 in which, however, a special short path distillation step has been included at the start of the process to trap smell molecules for use as described below. The purpose to this wide trawl is to have as representative a range as possible of refined oils containing EPA and DHA.
Table 1 records the influence of the acid value, the EPA and, respectively, DHA content, the color and the pro-oxidant iron and copper levels on sensory responses of a trained panel to the above described 21 oil samples.
The analysis for the determination of the EPA and DHA content and, respectively, the pro-oxidant iron and copper levels were performed according to analytical methods known in the art. For determining the acid value, i.e.
the number of milligrams of potassium hydroxide required to neutralize the free fatty acids in 1 gram of oil, the oil sample is titrated with 0.1N
aqueous potassium hydroxide solution using a 1% phenolphthalein indicator. The size of the sample was determined as folllows:
Expected acid value Test sample (g) >0.5 40 0.5 to 1 20 lto5 5 5 to 10 2.5 lOto20 1 >20 0.5 The color is determined by means of a Lovibond tintometer Model E AF
900 by matching the color of light transmitted through a specified depth of oil to the color of the lght originating from the same source, transmitted through standard color slides. The results are expressed in terms of the red (R), yellow(Y) and blue (B) units to obtain the match and the size of the cell used.
Taste and smell are sensorically evaluated by a trained panel comprising 12-15 persons. The panelist are asked to rank the samples in terms of perceiption of fishy taste and smell. A hedonic scale of 1 to 5 is used to express the extent of fishiness in which 1 represents no fishy taste or smell, while 5 stands for a very strong fishy taste or smell. The samples are coded using a three-digit code and 10 - 15 ml are submitted to the panel in a plastic beaker at 22 C. The products are evaluated after processing and after 4 weeks and, respectively, weeks storage at 22 C in aluminium containers.
Table 2 shows the effect of primary and secondary oxidation levels on the taste and smell of the same marine oils as in Table 1. Primary oxidation is measured as the peroxide value of the oils in milliequivalent (meq)/kg of oil.
Secondary oxidation is measured in two ways: first by the reaction of unsatu-rated aldehydes in the oil with anisidine and by the reaction of alkanals, alkenals and alkadienals in the oil with N,N-dimethyl-p-phenylenediamine.
For determining the peroxide value the oil is treated in a solution of acetic acid and chloroform with a solution of iodide and subsequently the free iodine is titrated with a solution of sodium thiosulphate. The size of the sample was determined as folllows:
Expected peroxide value Test sample () <1 10 lto5 2 5 to 10 1 >10 0.5 7771 The p-anisidine value is defined as 100 times the absorbence measured at 350 nm in a 1 cm cell of a solution containing 1.Og of the oil in 100 ml of a mixture of hexane and a solution of p-anisidine in glacial acetic acid (0.025g/
100 ml of glacial acetic acid). The size of the sample was determined as folllows:
Expected p-anisidine value Test sample () The aldehyde values werde determined based on a method described by K. Miyashita et al., JAOCS, Vol. 68 (1991), according to which N,N-dimethyl-p-phenylenediamine is reacted with aldehydes in the presence of acetic acid.
The three aldehyde classes (alkanal, alkenal and alkadienal) are determined by visible absorption at 400, 460 and, respectively, 500 nm. The aldehyde values are expressed in mmole/kg.
Furthermore, the level of smell molecules in each of these oils has been measured by static headspace coupled to GC/MS. The oil to be measured (samples of 1g each) is crimp sealed into a headspace vial (22ml) in an nitrogen atmosphere and heated at 120 C for 15 minutes in a headspace autosampler.
A measured volume of the headspace is automatically injected onto a GC(MS
using a heated transfer line. The gas chromatograph is used to separate the molecules and the mass spectrometer is used to identify and quantify the separated molecules. The results obtained are shown in Table 3.
, -5 Table 1 Acid EPA DHA Colour Copper Iron Taste Smell Value (%) (%) (Ppb) (Ppb) Standard fish 1 0.07 17.4 10.1 3.5R 23Y 13 39 2.3 0.7 2 0.06 18.8 9.1 1.1R 20Y 9 10 3.2 1.5 3 0.02 15.7 6.3 2.411 24Y 6 16 2.8 1.2 4 0.04 11.6 12.1 2.6113 1Y 12 22 4.0 3.0 0.17 17.6 10.3 2.5R 20Y 17 24 2.1 0.8 6 0.08 16.9 11.7 3.1R30Y 31 29 2.8 1.6 7 0.04 6.7 27.7 1.6R 20Y 14 25 1.2 0.6 8 0.20 6.7 27.5 3.6R 32Y 37 9 1.2 0.5 9 0.04 6.6 27.3 1.5R 23Y 13 18 2.7 1.6 0.08 6.7 28.0 1.211 31Y 12 12 3.6 2.0 Fresh fish 11 0.32 6.9 13.0 0.8R 15Y 3 27 2.2 0.6 12 0.30 8.7 7.5 2.OR 25Y 7 24 2.4 0.8 13 0.20 11.8 13.3 1.6R 20Y 6 13 1.5 1.0 14 0.23 10.3 11.8 0.5R 5.4Y 8 26 2.6 1.3 0.23 8.6 12.6 1.5R 15Y 6 29 2.8 1.0 Single cell 16 0.02 2.3 36.9 1.5R 32Y 7 10 1.7 0.9 17 0.77 0.4 31.0 1.2R 14Y 22 34 2.5 0.9 Standard fish distilled 18 0.2 18.0 10.5 2.2R 20Y 3 24 0.7 0.7 19 0.23 18.0 10.4 2.2R 20 Y 5 24 0.6 0.7 0.22 18.1 10.5 2.2R 23Y 8 30 0.6 0.6 21 0.19 17.9 10.4 2.3R 22Y 7 24 1.0 0.5 5 The above table shows that there is no correlation between the acid value, the EPA and, repectively DHA content, the color and pro-oxidant iron and copper levels and the taste and smell of these marine oils.
Table 2 Description Primary oxidation Secondary oxidation Peroxide value p-Anisidine value Aldehydes Taste Smell Standard fish A B C
1 0.4 19.8 2.41 0.3 0.9 2.3 0.7 2 0.5 12.62 1.46 0.15 0.54 3.2 1.5 3 0.8 8.7 0.54 0.08 0.34 2.8 1.2 4 0.7 15.31 1.87 0.29 0.68 4.0 3.0 0 3.77 0.6 0.09 0.17 2.1 0.8 6 0 4.24 1.02 0.11 0.23 2.8 1.6 7 0.4 8.24 1.94 0.24 0.66 1.2 0.8 8 0.4 6.81 1.09 0.15 0.35 1.2 0.5 9 0.5 6.81 1.06 0.14 0.32 2.7 1.6 2.1 9.42 0.97 0.18 0.36 3.6 2.0 Fresh fish 11 0 0.46 0.35 0.04 0.03 2.2 0.6 12 0 1.58 2.6 0.05 0.06 2.4 0.8 13 0 1.17 0.08 0.03 0.04 1.5 1.0 14 0 1.19 0.16 0.02 0.04 2.6 1.3 0 0.6 0.09 0.02 0.03 2.8 1.0 Single cell 16 4 6.58 1.13 0.26 0.3 1.7 0.9 17 0 1.45 0.45 0.03 0.04 2.5 0.9 Standard fish distilled 18 0 6.12 0.9 0.14 0.27 0.7 0.7 19 0 4.96 0.85 0.12 0.25 0.6 0.7 0 4.84 0.83 0.12 0.25 0.6 0.6 21 0 5.04 0.76 0.12 0.24 1.0 0.5 5 A = alkanals, B alkenals, C= alkadienals The above results show again that these oxidation indicators are not capable of distinguishing oils with a good taste and smell from those with bad ones.
Smell t- Lq ry O oo cc oo to ec o co o0 o r~ O a~ al ~ ~ cc u~
Taste M N co O .i m N N l- cp N v U,3 to ap ~ O h O O O
N M CV e}~ N GV .-i .-i CV c'M CV N ~-i Gy Cj r4 N G O O .-~
O O O O O O O O O O O O O O O
Heptadienal õ~ ,~ õ~ ,~ 0 Q ~ ~ ~o ~o ~o Lo ko Lo io v v v v v v.-+ v v v v v vv v~~~
Octenal ~ o d , o o a ~o o ~ o d , o 0 0 0 0 o O o 0 0 0 v v v v v v v v v v c~ rn c~ O~ c~ c~ c~ c~ a~ a~ c~
V V V v v v v v v v v Hexadienal o 0 0 0 0 0 0 0 0 0 0 0 (D 0 0 0 0 o O o 0 v v v v v v ~ v v v ~ to o ~ tO ~ tO ~ tD o~
MMrn a)M c)rn MMrn M
V V V V v v v v V v v Nonanal o 0 0 o O O o O o o O o 0 0 0 0 o O o O o .~ .~ . ~ .~ ~ '. .. .. r, ., ~ .. ~ .~ -4 ~ 1.4 r, ..+ ., '4 a~ o~ a~ c~ c~ c~ a~ c~ c~ c~ c~ rn c~ c~ m c~ m m m m on v v V v v v V v v v V V V v v v v V v v v Heptenal C D = o 0 0 o O o 0 0 0 0 0 0 0 0 c~ O a~ G~ Q~ O O rn O O O a~ a) rn a) c] 6n (MMO M
vv lr IV .r 10 IV
v v v v v v v v v V V V v v V v v v v v [- t- N N l- l- ~ t- h [- t- t- [- N [- l- l~ N L-Octanal o 0 0 0 0 o O 0 0 0 0 JIVc-IV, 0 0 o O o 0 o O
'V' '~' eM 'V' ~}' '~" er e!' '~i' V V V V V v V V V V V V V V V V V V V
Hexenal o 0 o O O o 0 0 0 0 0 0 0 0 o O o 0 0 0 0 r= E- t- t- r, L-v v V v V v V v V V V V V V V V V V v v v He tanal o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 o O o 0 P 0 0 0 0 0 o O o 0 0 0 0 0 o O o 0 0 0 0 0 ., ,H .y ., ,ti 11 ,H .1 .-q r, r, .1 .~ ,1 ., -4 -4 .1 r+ -4 ,ti ~ V V V V V V V V V V V V V V V V V V V V V
~ Penten-3-ol ~ oo ~r n N rn o o a~ o~ o 0 0 0 o N.-~
LO o ~ ao c~ C) LO c~ rn a~ a~ c~ ~ c~
N ~ er ~ ' ~ .~ V V M ,LõO,~ ~,Oõ4 V V V V V ilN V
Hexanal CD oo N o 0 o O o 0 0 0 0 0 0 0 o c~ oo co N O
tC~ ~fJ et' -4 H 4 .-i ~ .--i .-i .-i -4 .ti M M
V v V V V V V V V V V V V N o r~ r1 '-1 Penten-3- o 0 0.-+ ~~ o u~ ~~ ~~ N o O o 0 0 .-+ M O o O O
G~ G1 G) LO O M CV l- O Lo m G7 C7i m G) L7 n+ C7i G") m m one V V V - v V er er er V V V V V -4 N V V V V
Pentanal O o 0 0 0 0 o O o O o 0 0 0 o O O o 0 0 0 C7 to c7 t7 CD to CJ c7 = C.7 to c7 U CO Cn ;~ ~p c'~ c7 c7 c7 'r V .r ~ v c v lw I-r a v ~r -I:r c ~r ~ er rr w V V V V v v v v v V V V V v V V V v v V V
Ethyl Furan --4 N00 ~ o) ul co o~ o 0 0 ,_, ,n o 0 0 0 N 'r v v ~ O LO V 1" V V V v m V V V V
Butanal O O O O O O O O O O O O O O O O
C eM ~4' 'V" v 'V ef' e1' C' e!' et' V v V V V V v V V V V v V V v v Propenal o~ o ~~o M~~ A A A Ca A o ~l ~7 M Co ~ O O M ~ 7-. 7, 7-. 2- Z 'T-. N ~ O N
Propanal ~ ov en~ O co 00 Fcv, 0 0 ~~ C7 o G~ G~ v N -+ v L n c~ L M o . - 4 v v v N V V V V
.U
o rA .C CC
Q, d e,rA~, v ~
-~
--~ N M Q' ~7 C7 t- 00 m O Ll C) CD L~ vi 00 n 0 -i G) C/] p C~7 a3 ~
Again, the above data show that static headspace cannot distinguish between good and bad tasting marine oils.
Tables 1 - 3 also show that marine oils which have been, refined very soon after the oil has been extracted from freshly caught fish do not show better sensory response than oils which have been refined from aged crude fish oil. However, levels of secondary anisidine reactives and aldehydes are extre-mely low in these fresh oils. These results suggest that whatever is responsi-ble in the marine oil for the fishy taste and smell is present at extremely low lo levels below the detection limits of static headspace GCIMS. The data also show that neither anisidine nor aldehyde measurements are very useful in predicting the sensory quality of the oil - they are too insensitive.
Tables 1 - 3 show sensory data for single cell oils which demonstrate that they too can become fishy in both taste and smell. Table 1 also shows that when using specially refined oils it is possible to produce marine oils with excellent taste and smell but with quality parameters such as anisidine, peroxide, iron, copper, color and static headspace values which are not different from those of oils with poor taste and smell.
In order to have some understanding of the extent of the problem of the occurrence of fishy taste and smell in marine oils, efforts have been made to try and identify and quantify the molecules being responsible for the fishy taste and smell. Marine oils (1 kg each) rich in EPA and/or DHA which had a strong fishy smell were passed slowly through a short path still at 120 C and under reduced pressure (0.005 mbar). Two vacuum traps were connected in series each cooled with liquid nitrogen to collect the fishy volatiles which were removed by this process. These oils were then deodorised at 190 C and are the four specially refined oils recorded in Table 1 -3 as samples 18 - 21.
Even though their traditional quality parameters are not different from those oils which were deemed fishy they had only little or no fishy taste. The condensa-tes in the vacuum traps were dissolved in methyl tertiary butyl ether and subjected to olfactory detector GC/MS to identify fishy molecules which had been removed by this process. According to olfactory detector GC/MS the outlet stream from a gas chromatograph is split and routed to two different detectors.
In the present case, the detectors used were the mass spectrometer and the human nose. Such a system allows peaks to be identified by the MS and assigned smell comments by an operator.
A number of very potent smell molecules were identified in the distillates and are recorded in Table 4.
Table 4 Target molecule Characteristic according to prior art 4-heptenal Fish oil 1-octen-3-one Mushroom 1,5(Z)-octadien-3-ol Mushroom 1,5(Z)-octadien-3-one Metallic/fresh fish (E,E)-2,4-heptadienal Oxidized oil (E)-2-octenal Oxidized oil (Z)-6-nonenal Oxidized oil/putty/linseed oil (E,Z)-2,6-nonadienal Cucumber/fresh fish (E)-2-nonenal Oxidized oil (E,Z)-1,3,5-undecatriene Cod liver oil (E,E)-2,4-decadienal Fish/oxidized oil As can be seen from Table 3, only a few of the above molecules could be identified using static headspace and, thus, a more sensitive method was needed to remove headspace molecules from the oils. The detection limits for e.g. 2-octenal and, respectively, 2,4-hexadienal were 940 ppb and, respectively, 500 ppb. In order to improve the sensitivity of detection, the technique of dynamic headspace has been used. According to this technique, 2 g aliquots of oil have been heated to 75 C in a water bath purged with helium (150 ml/min) through a Tekmar purge glass apparatus onto Perkin Elmer cartridges contai-ning TENAX adsorbent (Enka Research Institute, Arnheim). The dynamic headspace has been measured by GC/MS using a 30m column of DB5-MS (l m film thickness).
Table 5 shows the taste panel response to a number of blends of mixtu-res of marine oils and the dynamic headspace profile of a number of molecules.
They have been identified by GUIVIS and olfactory detector GC(MS. As can be seen, some of these molecules can be detected to single figure ppb level using dynamic headspace. The importance of the data in Table 5 is that they explain why the data in Table 1 - 3 cannot possibly correlate with marine oil taste and smell and they also demonstrate the very small amount of oxidation which is required before the oil deteriorates to a unacceptable quality from the point of its taste and smell.
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d ' l- CO O eM M O eN N 00 e!~ to CD M Q~ m O ~
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Table 6 shows the excellent agreement between the level of 6 specially selected molecules in the headspace of the oils and the ranking by the taste panel by using a multiple discriminant analysis. Multiple discriminant analysis (MDA) is a statistical test used to determine whether a given classification of cases into groups is a likely one. It will report whether the group assignment of a case is true or false. The final data are presented in a table with rows and columns corresponding to actual and estimated group membership respectively. In the frame of the present invention the classifica-tion obtained from the sensorical evaluation by the taste panel was the taste factor. The MDA analysis was done through a statistical package called UNISTAT version 4.51.
Table 6 Group 1 Group 2 Group 3 Grou 4 Group 5 Group 1 22 0 0 0 0 100% 0% 0% 0% 0%
Group 2 0 5 0 0 0 0% 100% 0% 0% 0%
Group 3 0 0 6 0 0 0% 0% 100% 0% 0%
Group 4 0 0 0 2 0 0% 0% 0% 100% 0%
Group 5 0 0 0 0 1 0% 0% 0% 0% 100%
Group 1 Not fishy 2 Slight fishy 3 Middle fishy 4 Strong fishy 5 V strong fishy Molecule Retention Comparison Mass Index to standard spectrum retension time (E)-2-hexenal 861 Yes Yes (Z)-4-heptenal 903 Yes Yes 1,5-(Z)- 986 Yes Yes octadien-3-one (E,E)- 2,4 1004 Yes Yes heptadienal 3,6-nonadienal 1109 No Yes (E,Z)-2,6- 1159 Yes Yes nonadienal The retention index of a compound is calculated from injections of C5-C15 saturated straight chain hydrocarbons under the same chromatographic conditions as the analysis of interest and is similar to its retention time in that the longer it is retained on a GC column the greater is its retention index/time.
The use of the retention indices rather than retention times makes the information more rigorous and transferable although the retention indices are still dependant on the column phase and chromatographic conditions but minimise instrument dependant variables.
In order for a peak on a GC trace to be accepted as having a certain identity certain conditions must be met. The traditional one with GC is that it should have the same retention index/time as an authentic standard. Of the 6 molecules listed standards were obtained for 5 of them. Alternatively, mass spectra can be used as an additional tool to confirm peak identity.
Table 7 shows the effect of increasing concentration of deodorised rosemary extract on the rancimat stability of a marine oil by adding it after deodorisation.
Table 7 Deodorised HERBALOX "O" added Rancimat Induction Time (100 C) (%) (hours) 0 1.70 0.25 3.02 0.5 3.87 0.75 4.93 1.0 5.45 1.5 5.73 2.0 6.98 2.5 7.65 3.0 8.23 3.5 9.28 4.0 10.7 Table 7 shows that between 0 and 4% addition of rosemary extract, the rancimat induction time and, thus, the rancimat stability of marine oil, increa-ses with an increasing the amount of rosemary extract. Nevertheless, the use of rosemary extract as a stabiliser of marine oil in accordance with the prior art, i.e.after deodorisation, is - even at the low amount of 0.2% - disadvan-tageous due to the powerful herby smell of the commercial deodorised rosemary extract, particularly if it is put into dairy food applications. This makes it impossible to use the dose benefits shown in Table 7.
It has now surprisingly been found in accordance with the present invention that adding the rosemary extract to the oil before deodorisation removes the powerful smell without removing or destroying the anti-oxidant activity. The results of the relevant experiments are set forth in Tables 8 and 9.
Table 8 shows a range of headspace molecules which describe the headspace of deodorised rosemary extract at a concentration of 0.2% added to deodorised marine oil after deodorisation and, respectively, 0.2% and 0.4%
added before deodorisation. In the latter case, two deodorisation temperatures are given.
Table 8 HERBALOX "O" 0.2% 0.4% 0.4% 0.2% 0.2%
Addition After Before Before Before Before Deodorisation deodorisation deodorisation deodorisation deodorisation Temperature - 150 C 190 C 150 C 190 C
% normalised/relative % removed % removed % removed % removed Limonene 100 /4.7 17 20 50 50 Eucalyptol 100 /3.5 100 100 100 100 Linalool 100 /1.5 100 100 100 100 Linalyl propanoate 100 /3.8 100 100 100 100 Camphor 100 /20.3 97 99 100 100 Iso-Borneol 100 /3.8 100 100 93 90 Fenchyl acetate 100 /27.3 100 100 100 100 Vebenone 100 / 3.0 100 100 100 100 Bornyl acetate 100 / 1.2 100 100 100 100 Copaene (1) 100 / 1.8 100 100 100 100 Ioscaryophyllene 100 / 0.6 20 20 20 20 Caryophyllene 100 /27.9 84.8 100 100 100 Copaene 100 /0.5 100 100 100 100 The relative values given in column 2 were derived from the analysis of marine oil with 0.2% HERBALOX "O" added after deodorising. When the oils are deodorised it is necessary to have a concentration against which it is possi-ble to measure removal of the headspace molecules. Therefore, the concentra-tion of each compound found in the experiment in which the rosemary extract was added after removal was taken as 100% and the effects of deodorising measured against this level.
Table 6 Group 1 Group 2 Group 3 Grou 4 Group 5 Group 1 22 0 0 0 0 100% 0% 0% 0% 0%
Group 2 0 5 0 0 0 0% 100% 0% 0% 0%
Group 3 0 0 6 0 0 0% 0% 100% 0% 0%
Group 4 0 0 0 2 0 0% 0% 0% 100% 0%
Group 5 0 0 0 0 1 0% 0% 0% 0% 100%
Group 1 Not fishy 2 Slight fishy 3 Middle fishy 4 Strong fishy 5 V strong fishy Molecule Retention Comparison Mass Index to standard spectrum retension time (E)-2-hexenal 861 Yes Yes (Z)-4-heptenal 903 Yes Yes 1,5-(Z)- 986 Yes Yes octadien-3-one (E,E)- 2,4 1004 Yes Yes heptadienal 3,6-nonadienal 1109 No Yes (E,Z)-2,6- 1159 Yes Yes nonadienal The retention index of a compound is calculated from injections of C5-C15 saturated straight chain hydrocarbons under the same chromatographic conditions as the analysis of interest and is similar to its retention time in that the longer it is retained on a GC column the greater is its retention index/time.
The use of the retention indices rather than retention times makes the information more rigorous and transferable although the retention indices are still dependant on the column phase and chromatographic conditions but minimise instrument dependant variables.
In order for a peak on a GC trace to be accepted as having a certain identity certain conditions must be met. The traditional one with GC is that it should have the same retention index/time as an authentic standard. Of the 6 molecules listed standards were obtained for 5 of them. Alternatively, mass spectra can be used as an additional tool to confirm peak identity.
Table 7 shows the effect of increasing concentration of deodorised rosemary extract on the rancimat stability of a marine oil by adding it after deodorisation.
Table 7 Deodorised HERBALOX "O" added Rancimat Induction Time (100 C) (%) (hours) 0 1.70 0.25 3.02 0.5 3.87 0.75 4.93 1.0 5.45 1.5 5.73 2.0 6.98 2.5 7.65 3.0 8.23 3.5 9.28 4.0 10.7 Table 7 shows that between 0 and 4% addition of rosemary extract, the rancimat induction time and, thus, the rancimat stability of marine oil, increa-ses with an increasing the amount of rosemary extract. Nevertheless, the use of rosemary extract as a stabiliser of marine oil in accordance with the prior art, i.e.after deodorisation, is - even at the low amount of 0.2% - disadvan-tageous due to the powerful herby smell of the commercial deodorised rosemary extract, particularly if it is put into dairy food applications. This makes it impossible to use the dose benefits shown in Table 7.
It has now surprisingly been found in accordance with the present invention that adding the rosemary extract to the oil before deodorisation removes the powerful smell without removing or destroying the anti-oxidant activity. The results of the relevant experiments are set forth in Tables 8 and 9.
Table 8 shows a range of headspace molecules which describe the headspace of deodorised rosemary extract at a concentration of 0.2% added to deodorised marine oil after deodorisation and, respectively, 0.2% and 0.4%
added before deodorisation. In the latter case, two deodorisation temperatures are given.
Table 8 HERBALOX "O" 0.2% 0.4% 0.4% 0.2% 0.2%
Addition After Before Before Before Before Deodorisation deodorisation deodorisation deodorisation deodorisation Temperature - 150 C 190 C 150 C 190 C
% normalised/relative % removed % removed % removed % removed Limonene 100 /4.7 17 20 50 50 Eucalyptol 100 /3.5 100 100 100 100 Linalool 100 /1.5 100 100 100 100 Linalyl propanoate 100 /3.8 100 100 100 100 Camphor 100 /20.3 97 99 100 100 Iso-Borneol 100 /3.8 100 100 93 90 Fenchyl acetate 100 /27.3 100 100 100 100 Vebenone 100 / 3.0 100 100 100 100 Bornyl acetate 100 / 1.2 100 100 100 100 Copaene (1) 100 / 1.8 100 100 100 100 Ioscaryophyllene 100 / 0.6 20 20 20 20 Caryophyllene 100 /27.9 84.8 100 100 100 Copaene 100 /0.5 100 100 100 100 The relative values given in column 2 were derived from the analysis of marine oil with 0.2% HERBALOX "O" added after deodorising. When the oils are deodorised it is necessary to have a concentration against which it is possi-ble to measure removal of the headspace molecules. Therefore, the concentra-tion of each compound found in the experiment in which the rosemary extract was added after removal was taken as 100% and the effects of deodorising measured against this level.
Table 8 shows that when a mineral oil to which 0.2% of rosemary oil was added before deodorisation is deodorised at 150 C or 190 C virtually all of these spicey molecules are removed from the oil. With 0.4% addition, remo-val of most of the spicey molecules is low, whereby particularly two of the main components, i.e. camphor and caryophyllene, are not completely removed.
The herby smell in an oil deodorised at 150 C with 0.4% addition of rosemary extract before deodorisation is still strong whereas an oil with only 0.2% rosemary extract added does not have any herby smell.
Table 9 shows the effect on the anti-oxidant system depending on the deodorisation temperature, anti-oxidant mixture and whether the rosemary is added before or after the deodorisation.
Table 9 Addition HERBALOX Sage Ascorbyl Mixed Deodorisation Rancimat "O" Extract Palmitate Tocopherol Temperature Induction Time (%) (%) (%) (%) ( C) (hours) - - - - - - 1.7 After 0.2 - - - - 3.0 After 0.2 - - - 150 3.0 After 0.2 - - - 190 2.9 Before 0.2 - - - 150 3.3 Before 0.2 - - - 190 4.1 Before 0.2 - 0.02 0.1 150 5.4 Before 0.2 - 0.02 0.1 190 6.2 After - 0.2 - - 190 2.3 Before - 0.2 - - 190 3.4 Before - 0.2 0.02 0.1 190 5.3 Adding 0.2% rosemary extract to the marine oil without deodorising, increases the rancimat stability from 1.7 to 3.0 hours at 100 C. The same or about the same rancimat stability is seen when the rosemary extract is added to the oil after deodorising at 150 C and 190 C. An only slightly increased rancimat stability in seen when sage extract is added to the oil after deodori-sing at 190 C. If the rosemary extract is added to the oil before the deodori-sation at 150 C there is a slightly increased rancimat stability but by deodorising at 190 C in the presence of rosmary and, respectively, sage extract the rancimat stability of the oil is increased substantially to 4.1 and, respectively, 3.4 hours. Addition of 0.02% ascorbyl palmitate and 0.1% mixed tocopherol after deodorisation further enhances the rancimat stability of the oil. Thus, by deodorising the oil at 190 C and adding 0.2% rosemary and, respectively, sage extract before the deodorisation followed by 0.02 %
ascorbyl palmitate and 0.1% mixed tocopherol after the deodorisation it is possible to increase the rancimat stability of the oil from 1.7 to 6.2 and, respectively, 5.3 hours.
Accordingly, an object of the present invention is a process for the preparation and stabilizaion of food-grade marine oil by treating marine oil with silica in the presence or absence of carbon, vacuum steam deodorising at a temperature between about 140 C and about 210 C in the presence of 0.1-0.4% rosemary or sage extract and, if desired, adding 0.01-0.03% ascorbyl palmitate and 0.05-0.2% mixed tocopherol, as well as the use of the oil thus obtained in food applications. A further object of the present invention is a method of determining the sensory quality of a unknown marine oil by measu-ring the dynamic headspace profile of the marine oil with regard to the 6 following compounds:
(Z)-4-heptenal (E)-2-hexenal 1,5-(Z)-octadien-3-one (E,E)-2,4-heptadienal 3,6-nonadienal (E,Z)-2,6-nonadienal and evaluating the results abtained against the results of the oils given in Table 5 by multiple discriminant analysis.
Preferably, the silica treatment is performed in the presence of carbon.
The preferred temperature for the deodorisation step lies between 150 C and 190 C, more preferred at about 190 C. The preferred amount of deodorised rosemary or sage extract present during deodorisation is 0.2%. Furthermore, it is preferred to add after deodorisation 0.01-0.03%, preferably 0.02%, ascorbyl palmitate and 0.05-0.2%, preferably 0.1%, mixed tocopherol.
The following examples illustrate the invention, but do not limit its scope in any manner. The silica and carbon used in the present invention has been described in detail in European Patent Publication 612 346. All oils used had been mixed with 5% silica and 2% activated carbon at 80 C and then filtered as described in European Patent Publication 612 346. The filtered product is called "adsorbed oil" in the examples.
Example 1 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots to have additions of HERBALOX "0" up to 4% and was used to provide the rancimat stabilities recorded in Table 7. To a separate aliquot of this oil, 0.2% HERBALOX "0" was added. Results of this study are recorded in Table 9. Samples of this oil were also dynamically purged to measure the content of spicey headspace molecules from the HERBALOX "O" "
addition. These results are recorded in Table 8.
Example 2 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were deodorised at 150 C for 2 hours then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. 0.2% HERBALOX "0"
was added to this oil. Results of this study are recorded in Table 9. Samples of this oil were also dynamically purged to measure the content of spicey head-space molecules from the HERBALOX "O" " addition. These results are recorded in Table 8.
Example 3 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were mixed with 0.2% HERBALOX "0", then deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots to have no addition of further anti-oxidant and, respectively, addition of 0.02% ascorbyl palmitate and 0.1% mixed tocopherol. Rancimat stabilites are recorded in Table 9.
Samples of this oil were also dynamically purged to measure the content of spicey headspace molecules from the HERBALOX "0" addition. The results are recorded in Table 8.
The herby smell in an oil deodorised at 150 C with 0.4% addition of rosemary extract before deodorisation is still strong whereas an oil with only 0.2% rosemary extract added does not have any herby smell.
Table 9 shows the effect on the anti-oxidant system depending on the deodorisation temperature, anti-oxidant mixture and whether the rosemary is added before or after the deodorisation.
Table 9 Addition HERBALOX Sage Ascorbyl Mixed Deodorisation Rancimat "O" Extract Palmitate Tocopherol Temperature Induction Time (%) (%) (%) (%) ( C) (hours) - - - - - - 1.7 After 0.2 - - - - 3.0 After 0.2 - - - 150 3.0 After 0.2 - - - 190 2.9 Before 0.2 - - - 150 3.3 Before 0.2 - - - 190 4.1 Before 0.2 - 0.02 0.1 150 5.4 Before 0.2 - 0.02 0.1 190 6.2 After - 0.2 - - 190 2.3 Before - 0.2 - - 190 3.4 Before - 0.2 0.02 0.1 190 5.3 Adding 0.2% rosemary extract to the marine oil without deodorising, increases the rancimat stability from 1.7 to 3.0 hours at 100 C. The same or about the same rancimat stability is seen when the rosemary extract is added to the oil after deodorising at 150 C and 190 C. An only slightly increased rancimat stability in seen when sage extract is added to the oil after deodori-sing at 190 C. If the rosemary extract is added to the oil before the deodori-sation at 150 C there is a slightly increased rancimat stability but by deodorising at 190 C in the presence of rosmary and, respectively, sage extract the rancimat stability of the oil is increased substantially to 4.1 and, respectively, 3.4 hours. Addition of 0.02% ascorbyl palmitate and 0.1% mixed tocopherol after deodorisation further enhances the rancimat stability of the oil. Thus, by deodorising the oil at 190 C and adding 0.2% rosemary and, respectively, sage extract before the deodorisation followed by 0.02 %
ascorbyl palmitate and 0.1% mixed tocopherol after the deodorisation it is possible to increase the rancimat stability of the oil from 1.7 to 6.2 and, respectively, 5.3 hours.
Accordingly, an object of the present invention is a process for the preparation and stabilizaion of food-grade marine oil by treating marine oil with silica in the presence or absence of carbon, vacuum steam deodorising at a temperature between about 140 C and about 210 C in the presence of 0.1-0.4% rosemary or sage extract and, if desired, adding 0.01-0.03% ascorbyl palmitate and 0.05-0.2% mixed tocopherol, as well as the use of the oil thus obtained in food applications. A further object of the present invention is a method of determining the sensory quality of a unknown marine oil by measu-ring the dynamic headspace profile of the marine oil with regard to the 6 following compounds:
(Z)-4-heptenal (E)-2-hexenal 1,5-(Z)-octadien-3-one (E,E)-2,4-heptadienal 3,6-nonadienal (E,Z)-2,6-nonadienal and evaluating the results abtained against the results of the oils given in Table 5 by multiple discriminant analysis.
Preferably, the silica treatment is performed in the presence of carbon.
The preferred temperature for the deodorisation step lies between 150 C and 190 C, more preferred at about 190 C. The preferred amount of deodorised rosemary or sage extract present during deodorisation is 0.2%. Furthermore, it is preferred to add after deodorisation 0.01-0.03%, preferably 0.02%, ascorbyl palmitate and 0.05-0.2%, preferably 0.1%, mixed tocopherol.
The following examples illustrate the invention, but do not limit its scope in any manner. The silica and carbon used in the present invention has been described in detail in European Patent Publication 612 346. All oils used had been mixed with 5% silica and 2% activated carbon at 80 C and then filtered as described in European Patent Publication 612 346. The filtered product is called "adsorbed oil" in the examples.
Example 1 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots to have additions of HERBALOX "0" up to 4% and was used to provide the rancimat stabilities recorded in Table 7. To a separate aliquot of this oil, 0.2% HERBALOX "0" was added. Results of this study are recorded in Table 9. Samples of this oil were also dynamically purged to measure the content of spicey headspace molecules from the HERBALOX "O" "
addition. These results are recorded in Table 8.
Example 2 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were deodorised at 150 C for 2 hours then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. 0.2% HERBALOX "0"
was added to this oil. Results of this study are recorded in Table 9. Samples of this oil were also dynamically purged to measure the content of spicey head-space molecules from the HERBALOX "O" " addition. These results are recorded in Table 8.
Example 3 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were mixed with 0.2% HERBALOX "0", then deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots to have no addition of further anti-oxidant and, respectively, addition of 0.02% ascorbyl palmitate and 0.1% mixed tocopherol. Rancimat stabilites are recorded in Table 9.
Samples of this oil were also dynamically purged to measure the content of spicey headspace molecules from the HERBALOX "0" addition. The results are recorded in Table 8.
Example 4 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were mixed with 0.2% HERBALOX "0", then deodorised at 150 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots to have no addition of further anti-oxidant and, respectively, addition of 0.02% ascorbyl palmitate and 0.1% mixed tocopherol. Rancimat stabilites are recorded in Table 9.
lo Samples of this oil were also dynamically purged to measure the content of spicey headspace molecules from the HERBALOX "0" addition. The results are recorded in Table 8.
Example 5 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were mixed with 0.4% HERBALOX "0", then deodorised at 150 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots which were dyna-mically purged to measure the content of spicey headspace molecules from the HERBALOX "0" addition. The results are recorded in Table 8.
Example 6 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA were mixed with 0.4% HERBALOX "0", then deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots which were dynamically purged to measure the content of spicey headspace molecules from the HERBALOX "0" addition. The results are recorded in Table 8.
Example 7 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA were deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. 0.2% sage extract was added to this oil. Results of this study are recorded in Table 9.
were mixed with 0.2% HERBALOX "0", then deodorised at 150 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots to have no addition of further anti-oxidant and, respectively, addition of 0.02% ascorbyl palmitate and 0.1% mixed tocopherol. Rancimat stabilites are recorded in Table 9.
lo Samples of this oil were also dynamically purged to measure the content of spicey headspace molecules from the HERBALOX "0" addition. The results are recorded in Table 8.
Example 5 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA
were mixed with 0.4% HERBALOX "0", then deodorised at 150 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots which were dyna-mically purged to measure the content of spicey headspace molecules from the HERBALOX "0" addition. The results are recorded in Table 8.
Example 6 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA were mixed with 0.4% HERBALOX "0", then deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots which were dynamically purged to measure the content of spicey headspace molecules from the HERBALOX "0" addition. The results are recorded in Table 8.
Example 7 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA were deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. 0.2% sage extract was added to this oil. Results of this study are recorded in Table 9.
Example 8 950 g of adsorbed marine oil containing 11.0% EPA and 17.8% DHA were mixed with 0.2% sage extract, then deodorised at 190 C for 2 hours and then cooled to 60 C. The steam was stopped and replaced by a nitrogen purge for 5 minutes. The oil was then divided into aliquots to have no addition of further anti-oxidant and, respectively, addition of 0.02% ascorbyl palmitate and 0.1%
mixed tocopherol. Rancimat stabilites are recorded in Table 9.
The following examples illustrate the use of marine oil obtained in accor-dance with the present invention in practical food applications. The oil used is hake oil containing 11.0% EPA and 17.8% DHA which was deodorised at 190 C in the presence of 0.2% HERBALOX "0" and will be named in the examples as "ROPUFA '30' n-3 Food Oil".
Example 9 Soft Drink with 30% juice Typical serving: 300 ml n-3 LCPUFA content: 75 mg/serving [g]
Part I
Orange concentrate 60.3 Brix, 5.15% acidity 657.99 Lemon concentrate 43.5 Brix, 32.7% acidity 95.96 Orange flavour, water soluble 13.43 Apricot flavour, water soluble 6.71 3o Water 26.46 Part II
O-Carotene 10% CWS 0.89 Water 67.65 Part III
Ascorbic acid 4.11 Citric acid anhydrous 0.69 Water 43.18 Part IV
Stabiliser 1.37 Sodium benzoate 2.74 Water 64.43 Part V
Orange flavour, oil soluble 0.34 Orange oil distilled 0.34 ROPUFA '30' n-3 Food Oil 13.71 Bottling syrup Softdrink compound 74.50 Water 50.00 Sugar syrup 60 Brix 150.00 The bottling syrup was diluted with water to 11 ready to drink beverage.
Part I: All ingredients were mixed together without incorporation of air.
Part II: (3-Carotene was dissolved in water.
Part III: Ascorbic acid and citric acid were dissolved in water.
Part IV: Sodium benzoate was dissolved in water. The stabiliser was added under stirring and swollen for 1 hour.
mixed tocopherol. Rancimat stabilites are recorded in Table 9.
The following examples illustrate the use of marine oil obtained in accor-dance with the present invention in practical food applications. The oil used is hake oil containing 11.0% EPA and 17.8% DHA which was deodorised at 190 C in the presence of 0.2% HERBALOX "0" and will be named in the examples as "ROPUFA '30' n-3 Food Oil".
Example 9 Soft Drink with 30% juice Typical serving: 300 ml n-3 LCPUFA content: 75 mg/serving [g]
Part I
Orange concentrate 60.3 Brix, 5.15% acidity 657.99 Lemon concentrate 43.5 Brix, 32.7% acidity 95.96 Orange flavour, water soluble 13.43 Apricot flavour, water soluble 6.71 3o Water 26.46 Part II
O-Carotene 10% CWS 0.89 Water 67.65 Part III
Ascorbic acid 4.11 Citric acid anhydrous 0.69 Water 43.18 Part IV
Stabiliser 1.37 Sodium benzoate 2.74 Water 64.43 Part V
Orange flavour, oil soluble 0.34 Orange oil distilled 0.34 ROPUFA '30' n-3 Food Oil 13.71 Bottling syrup Softdrink compound 74.50 Water 50.00 Sugar syrup 60 Brix 150.00 The bottling syrup was diluted with water to 11 ready to drink beverage.
Part I: All ingredients were mixed together without incorporation of air.
Part II: (3-Carotene was dissolved in water.
Part III: Ascorbic acid and citric acid were dissolved in water.
Part IV: Sodium benzoate was dissolved in water. The stabiliser was added under stirring and swollen for 1 hour.
Part V: All ingredients were mixed together.
All parts were mixed together before homogenisation using first a Turrax and then a high pressure homogenizer (pl = 200 bar, p2 = 50 bar).
Instead of using sodium benzoate, the beverage may be pasteurised. The beverage may also be carbonised.
Example 10 5 cereal bread Typical serving: 100 g n-3 LCPUFA content: 90 mg/serving [%]
5 cereal flour 100.00 Water 70.00 Yeast 4.00 Salt 2.00 ROPUFA '30' n-3 Food Oil 0.56 The yeast was dissolved in a part of the water. All ingredients including ROPUFA '30' n-3 Food Oil were mixed together to form a dough. Salt was added at the end of the kneading time. After fermentation, the dough was reworked and divided before a loaf was formed. Before baking, the surface of the loaf was brushed with water and sprinkled with flour.
Parameters:
= Kneading:
Spiral kneading system 4 min 1 ' gear 5 min 2 d gear Dough proofing: 60 min Dough temperature: 22 - 24 C
Proofing time: 30 min Baking:
Oven: Dutch type oven Baking temperature: 250/2200 C
Baking time: 50 - 60 min Estimated baking loss: 10 %.
Example 11 Table Margarine 1o 60% fat Typical serving: 30 g n-3 LCPUFA content: 225 mg/serving [%]
Fat phase:
Sunflower oil 25.220 Mixture of hardened rapeseed, soy, coconut and palm fat 31.175 ROPUFA '30' n-3 Food Oil 3.000 Emulsifier 0.600 Beta-Carotene 30% FS 0.004 Butter flavour, oil soluble. 0.001 Water phase:
Water 39.858 Salt 0.100 Citric Acid 0.042 Fat phase:
The fats were melted, but not exceeding 60 C. The oil was added and kept at the same temperature. Shortly before processing, the ROPUFA '30' n-3 Food Oil was added. Then all other oil soluble ingredients were added to the fat/oil mixture.
Water phase:
All water soluble ingredients were dissolved in water and pasteurised.
The water phase was added slowly to the oil phase (50 C) and mixed with a high shear mixer to form a homogeneous emulsion. The emulsion was crystallised in a margarine plant, equipped with a mutator, pinworker and resting tube. The margarine was filled into cups at 20 C and kept cool.
Example 12 Table Margarine 80% fat Typical serving: 30 g n-3 LCPUFA content: 225 mg/serving [%]
2o Fat phase:
Sunflower oil 30.850 Mixture of hardened rapeseed, soy, coconut and palm fat 45.800 ROPUFA '30' n-3 Food Oil 3.000 Emulsifier 0.250 Beta-Carotene 30% FS 0.008 Butter flavour, oil soluble. 0.090 Water phase:
Water 19.910 Salt 0.100 Citric Acid 0.005 Butter flavour, water soluble. 0.005 Fat phase:
The fats were melted, but not exceeding 60 C. The oil was added and kept at the same temperature. Shortly before processing, the ROPUFA '30' n-3 Food Oil was added. Then all other oil soluble ingredients were added to the fat-oil mixture.
Water phase:
All water soluble ingredients were dissolved in water and pasteurised.
The water phase was added slowly to the oil phase (50 C) and mixed with a high shear mixer to form a homogeneous emulsion. The emulsion was crystallised in a margarine plant, equipped with a mutator, pinworker and resting tube. The margarine was filled into cups at 15 C and kept cool.
Example 13 Cookies Type Mailander Typical serving: 25 g n-3 LCPUFA content: 62.5 mg/serving [g]
Wheat Flour, type 550 410.0 Sugar 205.0 Fat/Butter 195.9 ROPUFA '30' n-3 Food Oil 9.1 Whole egg (liquid) 180.0 Lemon Flavour q.s.
Baking agent q.s.
All parts were mixed together before homogenisation using first a Turrax and then a high pressure homogenizer (pl = 200 bar, p2 = 50 bar).
Instead of using sodium benzoate, the beverage may be pasteurised. The beverage may also be carbonised.
Example 10 5 cereal bread Typical serving: 100 g n-3 LCPUFA content: 90 mg/serving [%]
5 cereal flour 100.00 Water 70.00 Yeast 4.00 Salt 2.00 ROPUFA '30' n-3 Food Oil 0.56 The yeast was dissolved in a part of the water. All ingredients including ROPUFA '30' n-3 Food Oil were mixed together to form a dough. Salt was added at the end of the kneading time. After fermentation, the dough was reworked and divided before a loaf was formed. Before baking, the surface of the loaf was brushed with water and sprinkled with flour.
Parameters:
= Kneading:
Spiral kneading system 4 min 1 ' gear 5 min 2 d gear Dough proofing: 60 min Dough temperature: 22 - 24 C
Proofing time: 30 min Baking:
Oven: Dutch type oven Baking temperature: 250/2200 C
Baking time: 50 - 60 min Estimated baking loss: 10 %.
Example 11 Table Margarine 1o 60% fat Typical serving: 30 g n-3 LCPUFA content: 225 mg/serving [%]
Fat phase:
Sunflower oil 25.220 Mixture of hardened rapeseed, soy, coconut and palm fat 31.175 ROPUFA '30' n-3 Food Oil 3.000 Emulsifier 0.600 Beta-Carotene 30% FS 0.004 Butter flavour, oil soluble. 0.001 Water phase:
Water 39.858 Salt 0.100 Citric Acid 0.042 Fat phase:
The fats were melted, but not exceeding 60 C. The oil was added and kept at the same temperature. Shortly before processing, the ROPUFA '30' n-3 Food Oil was added. Then all other oil soluble ingredients were added to the fat/oil mixture.
Water phase:
All water soluble ingredients were dissolved in water and pasteurised.
The water phase was added slowly to the oil phase (50 C) and mixed with a high shear mixer to form a homogeneous emulsion. The emulsion was crystallised in a margarine plant, equipped with a mutator, pinworker and resting tube. The margarine was filled into cups at 20 C and kept cool.
Example 12 Table Margarine 80% fat Typical serving: 30 g n-3 LCPUFA content: 225 mg/serving [%]
2o Fat phase:
Sunflower oil 30.850 Mixture of hardened rapeseed, soy, coconut and palm fat 45.800 ROPUFA '30' n-3 Food Oil 3.000 Emulsifier 0.250 Beta-Carotene 30% FS 0.008 Butter flavour, oil soluble. 0.090 Water phase:
Water 19.910 Salt 0.100 Citric Acid 0.005 Butter flavour, water soluble. 0.005 Fat phase:
The fats were melted, but not exceeding 60 C. The oil was added and kept at the same temperature. Shortly before processing, the ROPUFA '30' n-3 Food Oil was added. Then all other oil soluble ingredients were added to the fat-oil mixture.
Water phase:
All water soluble ingredients were dissolved in water and pasteurised.
The water phase was added slowly to the oil phase (50 C) and mixed with a high shear mixer to form a homogeneous emulsion. The emulsion was crystallised in a margarine plant, equipped with a mutator, pinworker and resting tube. The margarine was filled into cups at 15 C and kept cool.
Example 13 Cookies Type Mailander Typical serving: 25 g n-3 LCPUFA content: 62.5 mg/serving [g]
Wheat Flour, type 550 410.0 Sugar 205.0 Fat/Butter 195.9 ROPUFA '30' n-3 Food Oil 9.1 Whole egg (liquid) 180.0 Lemon Flavour q.s.
Baking agent q.s.
The ROPUFA '30' n-3 Food Oil was added to the melted fat. All other ingredients were added slowly under mixing to form a sweet short pastry.
Afterwards, the pastry was kept cool (4 C) for at least 2 hours before flattening the pastry to a thickness of approx. 5 mm. Pieces were cut out and brushed with egg yolk on the surface before baking.
= Baking:
Oven: fan oven Baking temperature: 180 C
Baking time: 15 min Example 14 Toast Typical serving: 100 g n-3 LCPUFA content: 90 mg/serving [%]
Wheat Flour, type 550 100.00 Water 60.00 Yeast 5.00 Salt 2.00 Fat/Butter 9.43 ROPUFA '30' n-3 Food Oil 0.57 Malt 1.00 Emulsifier baking agent 2.50 The yeast was dissolved in a part of the water. All ingredients were mixed together to form a dough including ROPUFA '30' n-3 Food Oil. Salt was added at the end of the kneading time. Afterwards, the dough was reworked, divided and placed in a baking tin for fermentation. After baking, the loaf was unmoulded directly.
Afterwards, the pastry was kept cool (4 C) for at least 2 hours before flattening the pastry to a thickness of approx. 5 mm. Pieces were cut out and brushed with egg yolk on the surface before baking.
= Baking:
Oven: fan oven Baking temperature: 180 C
Baking time: 15 min Example 14 Toast Typical serving: 100 g n-3 LCPUFA content: 90 mg/serving [%]
Wheat Flour, type 550 100.00 Water 60.00 Yeast 5.00 Salt 2.00 Fat/Butter 9.43 ROPUFA '30' n-3 Food Oil 0.57 Malt 1.00 Emulsifier baking agent 2.50 The yeast was dissolved in a part of the water. All ingredients were mixed together to form a dough including ROPUFA '30' n-3 Food Oil. Salt was added at the end of the kneading time. Afterwards, the dough was reworked, divided and placed in a baking tin for fermentation. After baking, the loaf was unmoulded directly.
Parameters:
= Kneading:
Spiral kneading system 5 - 6 min 1" gear 3 - 4 min 2 d gear Dough proofing: none Dough temperature: 22 - 24 C
Proofing time: 40 min = Bakintz:
Oven: Dutch type oven Baking temperature: 220 C
Baking time: 35 - 40 min Example 15 Whole flour biscuits Typical serving: 25 g n-3 LCPUFA content: 125 mg/serving [g]
Whole wheat flour 355.0 2o Fat 195.3 ROPUFA '30' n-3 Food Oil 18.2 Cane sugar 177.5 Almond, ground 118.0 Whole egg (liquid) 130.0 Salt 1.0 Baking agent 2.5 Cinnamon 2.5 Lemon Peel flavour q.s.
Lemon Juice q.s.
The ROPUFA '30' n-3 Food Oil was added to the melted fat. Then all other ingredients were added slowly under mixing to form a sweet short pastry.
. ' , -26-Afterwards the pastry was kept cool (4 C) for at least 2 hours before flattening the pastry to a thickness of approx. 6 mm. Pieces were cut out and brushed with egg yolk on the surface and sprinkled with cane sugar before baking.
Parameters:
Baking:
Oven: fan oven Baking temperature: 200 C
Baking time: 10 min Estimated baking loss 10 %.
Example 16 Yoghurt cake Typical serving: 100 g n-3 LCPUFA content: 250 mg/serving [g]
Wheat flour 310.0 Sugar incl. Vanilla sugar 240.0 Whole egg (liquid) 200.0 Yoghurt 170.0 Fat/Oil 60.9 Baking agent 10.0 ROPUFA '30' n-3 Food Oil 9.1 ROPUFA '30' n-3 Food Oil was added to the fat/oil. The yoghurt was mixed with sugar, vanilla sugar and eggs before the addition of the fat/oil containing ROPUFA '30' n-3 Food Oil, the flour and baking agent. The dough was beaten for at least 5 min. at medium speed. The batter was then spread into cake tins and baked in an oven.
Parameters:
Baking:
Oven: Fan oven Baking temperature: 190 C
Baking time: 40 min Example 17 UHT Milk Drink 1.7% fat Typical serving: 300 ml n-3 LCPUFA content: 150 mg/serving C%]
Part I
ROPUFA '30' n-3 Food Oil 0.200 Milk 1.5 % fat 2.580 Part II
Part I 2.780 Sodium ascorbate 0.025 Milk 1.5 % fat 97.195 Pre-emulsion Part I was mixed together and homogenised in high pressure homogenizer (p, = 150 bar, p2 = 50 bar) to reach an homogeneous emulsion.
UHT-Procedure:
Part I was added together with sodium ascorbate to the rest of the milk without incorporation of air. The mix was homogenised in a high pressure homogenizer (pl = 150 bar, p2 = 50 bar) and preheated in a tubular heat exchanger before thermal processing in a direct heat exchanger at 140 C for 4 sec, vacuum-cooling and aseptically packaging.
Example 18 Yoghurt - set type 3.5% fat Typical serving: 150 g n-3 LCPUFA content: 225 mg/serving [%]
Full fat milk (3.8% fat) 75.0 Skimmed milk (0.1% fat) 14.9 Skimmed milk powder 2.0 Sugar 5.0 Yoghurt 2.5 ROPUFA '30' n-3 Food Oil 0.6 The milk was heated to 35 C before addition of milk powder and sugar. This mixture was heated to 65 C to dissolve all ingredients. ROPUFA '30' n-3 Food Oil was added to the mixture before the homogenisation in a high pressure homogenizer (p1 = 150 bar, p2 = 50 bar) at 65 C. This emulsion was then pasteurised at 80 C for 20 minutes. After cooling to 45 C natural yoghurt/culture was added and mixed. Then this mixture was filled into cups and fermented at 45 C for 3-4 hours until a pH of 4.3 was reached and then stored at 4 C.
Example 19 Yoghurt - stirred type 3.5% fat Typical serving: 150 g n-3 LCPUFA content: 225 mg/serving in yoghurt ~~ = . *
1%]
Full fat milk (3.8% fat) 78.8 Skimmed milk (0.1% fat) 10.8 Skimmed milk powder 2.0 Stabiliser 0.3 Sugar 5.0 Yoghurt 2.5 ROPUFA '30' n-3 Food Oil 0.6 The milk was heated to 35 C before addition of milk powder, stabiliser and sugar. This mixture was heated to 65 C to dissolve all ingredients before homogenisation in a high pressure homogenizer (pl = 150 bar, pz = 50 bar) at 65 C. This emulsion was then pasteurised at 80 C for 20 minutes. After cooling to 45 C natural yoghurt/culture was added and mixed, followed by a fermentation at 45 C for 3-4 hours until a pH of 4.3 was reached. After cooling and stirring vigorously, the yoghurt was filled in cups and stored at 4 C.
Method A:
Addition of ROPUFA '30' n-3 Food Oil before homogenisation.
Method B:
Addition of ROPUFA '30' n-3 Food Oil after fermentation while stirring.
= Kneading:
Spiral kneading system 5 - 6 min 1" gear 3 - 4 min 2 d gear Dough proofing: none Dough temperature: 22 - 24 C
Proofing time: 40 min = Bakintz:
Oven: Dutch type oven Baking temperature: 220 C
Baking time: 35 - 40 min Example 15 Whole flour biscuits Typical serving: 25 g n-3 LCPUFA content: 125 mg/serving [g]
Whole wheat flour 355.0 2o Fat 195.3 ROPUFA '30' n-3 Food Oil 18.2 Cane sugar 177.5 Almond, ground 118.0 Whole egg (liquid) 130.0 Salt 1.0 Baking agent 2.5 Cinnamon 2.5 Lemon Peel flavour q.s.
Lemon Juice q.s.
The ROPUFA '30' n-3 Food Oil was added to the melted fat. Then all other ingredients were added slowly under mixing to form a sweet short pastry.
. ' , -26-Afterwards the pastry was kept cool (4 C) for at least 2 hours before flattening the pastry to a thickness of approx. 6 mm. Pieces were cut out and brushed with egg yolk on the surface and sprinkled with cane sugar before baking.
Parameters:
Baking:
Oven: fan oven Baking temperature: 200 C
Baking time: 10 min Estimated baking loss 10 %.
Example 16 Yoghurt cake Typical serving: 100 g n-3 LCPUFA content: 250 mg/serving [g]
Wheat flour 310.0 Sugar incl. Vanilla sugar 240.0 Whole egg (liquid) 200.0 Yoghurt 170.0 Fat/Oil 60.9 Baking agent 10.0 ROPUFA '30' n-3 Food Oil 9.1 ROPUFA '30' n-3 Food Oil was added to the fat/oil. The yoghurt was mixed with sugar, vanilla sugar and eggs before the addition of the fat/oil containing ROPUFA '30' n-3 Food Oil, the flour and baking agent. The dough was beaten for at least 5 min. at medium speed. The batter was then spread into cake tins and baked in an oven.
Parameters:
Baking:
Oven: Fan oven Baking temperature: 190 C
Baking time: 40 min Example 17 UHT Milk Drink 1.7% fat Typical serving: 300 ml n-3 LCPUFA content: 150 mg/serving C%]
Part I
ROPUFA '30' n-3 Food Oil 0.200 Milk 1.5 % fat 2.580 Part II
Part I 2.780 Sodium ascorbate 0.025 Milk 1.5 % fat 97.195 Pre-emulsion Part I was mixed together and homogenised in high pressure homogenizer (p, = 150 bar, p2 = 50 bar) to reach an homogeneous emulsion.
UHT-Procedure:
Part I was added together with sodium ascorbate to the rest of the milk without incorporation of air. The mix was homogenised in a high pressure homogenizer (pl = 150 bar, p2 = 50 bar) and preheated in a tubular heat exchanger before thermal processing in a direct heat exchanger at 140 C for 4 sec, vacuum-cooling and aseptically packaging.
Example 18 Yoghurt - set type 3.5% fat Typical serving: 150 g n-3 LCPUFA content: 225 mg/serving [%]
Full fat milk (3.8% fat) 75.0 Skimmed milk (0.1% fat) 14.9 Skimmed milk powder 2.0 Sugar 5.0 Yoghurt 2.5 ROPUFA '30' n-3 Food Oil 0.6 The milk was heated to 35 C before addition of milk powder and sugar. This mixture was heated to 65 C to dissolve all ingredients. ROPUFA '30' n-3 Food Oil was added to the mixture before the homogenisation in a high pressure homogenizer (p1 = 150 bar, p2 = 50 bar) at 65 C. This emulsion was then pasteurised at 80 C for 20 minutes. After cooling to 45 C natural yoghurt/culture was added and mixed. Then this mixture was filled into cups and fermented at 45 C for 3-4 hours until a pH of 4.3 was reached and then stored at 4 C.
Example 19 Yoghurt - stirred type 3.5% fat Typical serving: 150 g n-3 LCPUFA content: 225 mg/serving in yoghurt ~~ = . *
1%]
Full fat milk (3.8% fat) 78.8 Skimmed milk (0.1% fat) 10.8 Skimmed milk powder 2.0 Stabiliser 0.3 Sugar 5.0 Yoghurt 2.5 ROPUFA '30' n-3 Food Oil 0.6 The milk was heated to 35 C before addition of milk powder, stabiliser and sugar. This mixture was heated to 65 C to dissolve all ingredients before homogenisation in a high pressure homogenizer (pl = 150 bar, pz = 50 bar) at 65 C. This emulsion was then pasteurised at 80 C for 20 minutes. After cooling to 45 C natural yoghurt/culture was added and mixed, followed by a fermentation at 45 C for 3-4 hours until a pH of 4.3 was reached. After cooling and stirring vigorously, the yoghurt was filled in cups and stored at 4 C.
Method A:
Addition of ROPUFA '30' n-3 Food Oil before homogenisation.
Method B:
Addition of ROPUFA '30' n-3 Food Oil after fermentation while stirring.
Claims (14)
1. A process for the preparation and stabilisation of food-grade marine oil, which process comprises treating marine oil with silica in the presence or absence of carbon, vacuum steam deodorising at a temperature between about 140°C
and about 210°C in the presence of 0.1% - 0.4% rosemary or sage extract.
and about 210°C in the presence of 0.1% - 0.4% rosemary or sage extract.
2. The process according to claim 1, wherein the process further comprises adding 0.01 - 0.03% ascorbyl palmitate and 0.05 - 0.2% mixed tocopherol.
3. The process according to claim 1 or 2, wherein the vacuum steam deodorisation is performed in the presence of rosemary extract.
4. The process according to any one of claims 1 to 3, wherein the silica treatment is performed in the presence of carbon.
5. The process according to any one of claims 1 to 4, wherein the temperature for the deodorisation step lies between 150°C and 190°C.
6. The process according to claim 5, wherein the temperature is at 190°C.
7. The process according to any one of claim 1 to 6, wherein the amount of deodorised rosemary extract present during deodorisation is 0.2%.
8. The process according to claim 1, wherein 0.01 - 0.03% ascorbyl palmitate and 0.05 - 0.2% mixed tocopherol is added after deodorisation.
9. The process according to claim 8, wherein 0.02% of ascorbyl palmitate is added.
10. The process according to claim 8 or 9, wherein 0.1% mixed tocopherol is added.
11. Use of a marine oil obtained according to any one of claims 1 to 10 for the preparation of food applications.
12. A dairy product comprising a stabilized food-grade marine oil obtained according to the process as defined in any one of claims 1 to 10.
13. The dairy product according to claim 12, wherein the dairy product is a yoghurt.
14. The dairy product according to claim 12, wherein the dairy product is a milk drink.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98120888 | 1998-11-04 | ||
| EP98120888.7 | 1998-11-04 | ||
| EP99118426 | 1999-09-17 | ||
| EP99118426.8 | 1999-09-17 |
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| Publication Number | Publication Date |
|---|---|
| CA2288528A1 CA2288528A1 (en) | 2000-05-04 |
| CA2288528C true CA2288528C (en) | 2008-08-05 |
Family
ID=26149767
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002288528A Expired - Lifetime CA2288528C (en) | 1998-11-04 | 1999-11-01 | Preparation and stabilization of food-grade marine oils |
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| Country | Link |
|---|---|
| US (1) | US6623774B2 (en) |
| EP (1) | EP0999259B1 (en) |
| JP (1) | JP4129344B2 (en) |
| KR (1) | KR100628608B1 (en) |
| CN (1) | CN1127561C (en) |
| AT (1) | ATE265514T1 (en) |
| AU (1) | AU765721B2 (en) |
| CA (1) | CA2288528C (en) |
| DE (1) | DE69916746T2 (en) |
| DK (1) | DK0999259T3 (en) |
| ES (1) | ES2218935T3 (en) |
| NO (1) | NO324197B1 (en) |
| NZ (1) | NZ500703A (en) |
| PT (1) | PT999259E (en) |
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| CN105876597A (en) * | 2016-04-15 | 2016-08-24 | 浙江大学 | Fishy smell removing liquid and surimi fishy smell removing method by using the fishy smell removing liquid |
| TW201900160A (en) | 2017-05-19 | 2019-01-01 | 愛爾蘭商艾瑪琳製藥愛爾蘭有限公司 | Compositions and Methods for Lowering Triglycerides in a Subject Having Reduced Kidney Function |
| US11058661B2 (en) | 2018-03-02 | 2021-07-13 | Amarin Pharmaceuticals Ireland Limited | Compositions and methods for lowering triglycerides in a subject on concomitant statin therapy and having hsCRP levels of at least about 2 mg/L |
| FI4056176T3 (en) | 2018-09-24 | 2024-05-30 | Amarin Pharmaceuticals Ie Ltd | Methods of reducing the risk of cardiovascular events in a subject |
| CN113528237A (en) * | 2020-04-22 | 2021-10-22 | 华中农业大学 | Process for deodorizing edible oil by steam distillation with nonionic surfactant |
| AU2022263358A1 (en) | 2021-04-21 | 2023-11-30 | Amarin Pharmaceuticals Ireland Limited | Methods of reducing the risk of heart failure |
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|---|---|---|---|---|
| AU552068B2 (en) * | 1981-09-21 | 1986-05-22 | Asama Chemical Co. Ltd. | Preservation of edible oils |
| US5006281A (en) * | 1985-03-26 | 1991-04-09 | Century Laboratories, Inc. | Process for the production of a marine animal oil |
| US4877635A (en) * | 1985-12-20 | 1989-10-31 | Kalamazoo Holdings, Inc. | Herb flavoring and/or antioxidant composition and process |
| US4874629A (en) * | 1988-05-02 | 1989-10-17 | Chang Stephen S | Purification of fish oil |
| US5023100A (en) * | 1988-05-02 | 1991-06-11 | Kabi Vitrum Ab | Fish oil |
| KR910004884B1 (en) * | 1989-02-01 | 1991-07-15 | 한국식품개발연구원 | Against oxidation of oils |
| US5077069A (en) * | 1991-01-07 | 1991-12-31 | Kabi Pharmacia Ab | Composition of natural antioxidants for the stabilization of polyunsaturated oils |
| JP2956909B2 (en) * | 1991-11-15 | 1999-10-04 | エフ・ホフマン−ラ ロシユ アーゲー | Stabilization of marine oil |
| US5855944A (en) * | 1991-11-15 | 1999-01-05 | Roche Vitamins Inc. | Stabilization of marine oils |
| KR19990048287A (en) * | 1997-12-09 | 1999-07-05 | 홍종만 | Operation alarm sound generating circuit of power window and its control method |
| ATE417090T1 (en) * | 2003-10-21 | 2008-12-15 | Dsm Ip Assets Bv | STABILIZATION OF ESTER CONCENTRATES OF POLYUNSATURATED FATTY ACIDS |
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- 1999-11-01 CA CA002288528A patent/CA2288528C/en not_active Expired - Lifetime
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- 1999-11-02 DE DE69916746T patent/DE69916746T2/en not_active Expired - Lifetime
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- 1999-11-02 ES ES99121655T patent/ES2218935T3/en not_active Expired - Lifetime
- 1999-11-02 PT PT99121655T patent/PT999259E/en unknown
- 1999-11-02 JP JP31175499A patent/JP4129344B2/en not_active Expired - Lifetime
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| JP2000144168A (en) | 2000-05-26 |
| PT999259E (en) | 2004-08-31 |
| US20030161918A1 (en) | 2003-08-28 |
| CN1262875A (en) | 2000-08-16 |
| DK0999259T3 (en) | 2004-08-16 |
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