EP0246366B1 - Procédé d'hydrogénation pour la préparation de graisses à fusion rapide - Google Patents

Procédé d'hydrogénation pour la préparation de graisses à fusion rapide Download PDF

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Publication number
EP0246366B1
EP0246366B1 EP86200903A EP86200903A EP0246366B1 EP 0246366 B1 EP0246366 B1 EP 0246366B1 EP 86200903 A EP86200903 A EP 86200903A EP 86200903 A EP86200903 A EP 86200903A EP 0246366 B1 EP0246366 B1 EP 0246366B1
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Prior art keywords
oil
process according
hydrogenated
catalyst
temperature
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EP86200903A
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German (de)
English (en)
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EP0246366A1 (fr
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Robert Lee White
Joseph Mcgrady
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE8686200903T priority Critical patent/DE3673815D1/de
Priority to EP86200903A priority patent/EP0246366B1/fr
Priority to AT86200903T priority patent/ATE56042T1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates

Definitions

  • the present invention relates to a process for hydrogenating a liquid oil to provide a product with a unique melt profile.
  • Textural characteristics, and particularly mouthmelt, of products containing hydrogenated oils depend to a great extent on the solids content index (SCI) of the hydrogenated oils.
  • SCI solids content index
  • Margarine products should melt readily in the mouth to avoid a sensation of waxiness or stickiness.
  • Baked products such as cookies and cakes should also have fats which melt readily in the mouth to avoid the sensation of graininess or toughness.
  • the presence of some solid fat gives a slightly crispy or cake-like texture initially.
  • most hydrogenation processes known in the art produce fats having an SCI at 10 ° C (50 ° F) of from approximately 40 to 70, an SCI at 21 ° C (70 ° F) of from approximately 45 to approximately 65, and an SCI at 33°C (92°F) of from approximately 10 to approximately 30. Therefore, a new hydrogenation process had to be developed to efficiently produce a fat having the desired melt characteristics.
  • hydrogenation is a means of converting liquid oils to semisolid, plastic fats suitable for shortening or margarine manufacture.
  • it also accomplishes various other desirable purposes, including enhancement of the stability and the improvement of the color of the fat.
  • Hydrogenation is the addition of hydrogen to the double bonds (unsaturated or ethylenic bonds) of an oil or fat by reaction with hydrogen in the presence of a metal catalyst. It is a means of saturating oils. However, the hydrogenation reaction is complicated by the simultaneous isomerization, both positional and geometrical of the unsaturated bonds. The position of the fatty acid on the glycerol as well as the degree of unsaturation determines the physical properties of the molecule, particularly the melting point of the fat or oil. In general, there is a stepwise conversion of the most unsaturated fatty acid form to the saturated state, i.e., linolenic to linoleic, then to oleic, and finally to stearic.
  • trans acids e.g., trans-isomers of octadecenoic acid
  • Trans acids are generally higher melting than the corresponding cis-isomer, although this may not always be the case, since melting point is also dependent upon the position of the double bonds.
  • the trans fatty acid triglycerides contribute to increased levels of intermediate melting triglycerides in a hydrogenated oil. With conventional hydrogenation techniques an equilibrium is ultimately reached in the final stages in which the monounsatu- rated acids comprise approximately two-thirds trans-isomers and one-third cis-isomers. This level of trans acid content is not sufficient to permit the hydrogenated oil to have the melting range preferred herein.
  • the product usually contains less than 10% stearate, less than 7% diene fatty acid glycerides, and greater than 60% trans-isomers of unsaturated fatty acid glycerides.
  • the Snyder process uses a mixture of a conventional nickel catalyst and a sulfur-poisoned nickel catalyst.
  • the SCI values of the hydrogenated fats are 57 to 67 at 10 ° C (50°F); 44 to 59 at 21 °C (70 ° F): and 13 to 19 at 33 ° C (92 ° F).
  • US Patent 3 459 777 discloses a process for catalytically hydrogenating vegetable oils and margaine oils at a temperature of between 180 ° C (356 ° F) and 240 ° C (464 ° F) and a pressure between 0 psig (0 kPa) and 100 psig (690 kPa).
  • This process includes the steps of adding catalyst at the beginning of the reaction in an amount sufficient only to start the hydrogenation and subsequently incrementally adding catalyst at a minimum prescribed frequency designed to cause the reaction to follow a predetermined refractive index/time curve.
  • Example 1 discloses a batch process for partially hydrogenating Canbra oil to an SCI of 46.78 at 10 ° C (50°F), 23.0 at 21°C (70 ° F) and 0.0 at 33 ° C (92 ° F). and states that a conventional hydrogenated product would have an SCI of 39.8 at 50 ° F, 21.2 at 21 ° C (70 ° F), and 0.5 at 33 ° C (92°F).
  • US Patent 3 856 831 Tateishi et al, issued Dec. 24, 1974, discloses a process for hydrogenating an oil having an initial IV between 60 and 78 utilizing a sulfur-poisoned nickel catalyst, preferably carried out at a temperature between about 160°C (320°F) and 220°C (428°F), which produces a fat with an SCI at 10°C (50°F) of approximately 40; at 21 °C (70°F) of approximately 20; and at 33 ° C (92 ° F) of approximately 6.
  • US Patent 4 134 905 Hassman. issued January 16, 1979. discloses a two-step hydrogenation process utilizing a copper chromate catalyst in the first step and a nickel catalyst in the second step, which produces a fat having an SCI at 10 ° C (50°F) of 62 to 64; at 70 ° F (21 "0) of 49 to 53; and at 33 ° C (92 ° F) of 22 to 29.
  • this product is beta-prime stable.
  • Hydrogenation of an oil having an initial iodine value (IV) of from about 95 to about 145 is carried out in the presence of a partially deactivated nickel catalyst present at a concentration of from about 0.01% to about 0.2% nickel by weight of oil and which is added in a single step at a temperature which is increased gradually from a starting temperature of from about 160°C (320°F) to about 200 ° C (392 ° F) to a final temperature of from about 210 ° C (410 ° F) to about 250 ° C (482 ° F).
  • the pressure exerted during the hydrogenation ranges from about 0 psig (0 kPa) to about 100 psig (690 kPa).
  • the reaction is terminated when the iodine value (IV) reaches a value of from about 65 to about 91.
  • This invention relates to the hydrogenation of oils and more particularly to partial and selective hydrogenation of animal, marine and vegetable oils having fatty acid chains comprising 14 or more carbon atoms.
  • the process provides hydrogenated oils having a specific solids content which gives sharper melting point ranges.
  • the products have particular utility in the formulation of margarines, cookie products, ice cream coating fats, hard butters, frostings, and in other similar applications in which quick melting and improved eating qualities of the product are required.
  • gaseous hydrogen, liquid oil, and the solid catalyst must be brought together at a suitable temperature.
  • the hydrogen is first brought into contact with the oil, with the hydrogen-laden oil then brought into contact with the catalyst by mechanical means.
  • a suspension of catalyst and oil is agitated in a closed vessel in an atmosphere of hydrogen. Agitation of the catalyst-oil mixture promotes dissolution of hydrogen in the oil and continuously renews the oil at the catalyst surface.
  • the solubility of hydrogen and other gases in oil increases linearly with temperature and pressure.
  • the rate of hydrogenation under the conditions just outlined depends on the temperature, the nature of the oil, the activity of the catalyst, the concentration of the catalyst, and the rate at which hydrogen and unsaturated oil are mixed at the active catalyst surface.
  • the composition and the character of the hydrogenated product can vary according to the positions of the double bonds which are hydrogenated, as well as certain isomerizing influences accompanying the reaction, and are highly dependent on the conditions of hydrogenation.
  • the analytical method which reflects or indicates a comparison percentage solid phase at a given temperature is the solids content index (SCI). This indicates the melting behavior of hydrogenated products and becomes a useful target for process control and product formulation.
  • the starting oil for the process of the present invention can be any liquid vegetable, animal or marine oil or blend of oils which is low in saturated fatty acids and has an iodine value of from about 95 to about 145.
  • the preferred oil is a polyunsaturated vegetable oil having fatty acid chains containing at least 14 carbon atoms.
  • Preferred vegetable oils include soybean, cottonseed, sunflowerseed, safflower, olive, peanut, coconut, palm, palm oil olein, and Canola oil. More preferred oils include soybean, sunflowerseed and corn oil. The most preferred oil Is soybean oil.
  • Preferred marine oils include menhaden, pilchard, sardine and herring oil.
  • oils are used to obtain the desired initial IV values and the desired beta-prime stability in the hydrogenated oil.
  • the oils may be blended either prior to or following hydrogenation.
  • Preferred blends contain soybean, sunflowerseed or corn oil, which contain many unsaturated fatty acids, both mono- unsaturated fatty acids and di- and tri-unsaturated fatty acids.
  • Oils with high iodine values are useful in limited amounts when blended with an oil low in saturated fatty acids, and therefore having a low iodine value, such as soybean oil.
  • beta-prime stable is meant the oil eventually crystallizes into and remains predominantly in the crystalline form known as beta-prime. This is in contrast to oils which remain predominantly in the alpha crystalline form or quickly crystallize into the beta crystalline form.
  • Oils which contribute to beta-prime stability are oils high in palmitic acid in the 1 and 3 position of the glycerol, such as cottonseed oil, palm oil, and palm oil olein.
  • the oil is mixed with a hydrogenation catalyst which is partially deactivated.
  • the deactivated catalyst is necessary to control the reaction rate.
  • Finely divided metallic nickel catalysts are well known for use in the hydrogenation of vegetable oils. Such catalysts are usually deposited on carriers such as Kieselguhr, aluminum oxide, silicate and the like.
  • Nickel catalysts lose their activity, or are deactivated, during the reaction due to the poisoning action of certain chemical substances, such as sulfur, phosphorus, chlorine, zinc, and compounds of the same, and more particularly due to the formation of soaps or fatty acid compounds of nickel.
  • Use of a partially deactivated catalyst is necessary in the present process to control the rate of the reaction, and thereby the relative proportions of 2 ig and trans fatty acid triglycerides in the products formed.
  • the preferred catalyst is a sulfur-poisoned deactivated nickel catalyst.
  • Sulfur-poisoned nickel catalysts useful in the catalyst system of the present invention contain from about 5% to about 20% sulfur based on the nickel present in the sulfur-poisoned catalyst portion of the catalyst system.
  • Commercially prepared catalysts are available.
  • One method for preparing sulfur-poisoned catalyst is described in U.S. Patent No. 3,856,831 of Tateishi et al (Dec. 24, 1974).
  • a conventional reduced nickel hydrogenation catalyst is subjected to an atmosphere containing hydrogen sulfide for sufficient time to obtain the desired sulfur content.
  • a deactivated nickel catalyst include reducing a nickel compound, such as the oxides, hydroxides or carbonates, and then reacting the nickel catalyst with a mixed gas stream containing hydrogen and hydrogen sulfide until the desired sulfur content is obtained.
  • reducing a nickel compound such as the oxides, hydroxides or carbonates
  • a mixed gas stream containing hydrogen and hydrogen sulfide containing hydrogen and hydrogen sulfide until the desired sulfur content is obtained.
  • Either wet-reduced nickel catalyst or dry-reduced nickel catalyst can be used.
  • a preferred method for preparing the sulfur-poisoned catalyst is to mix from about 5% to about 25% nickel catalyst into melted hardened coconut oil (IV less than 1). The mixture is then heated to a temperature in the range of from about 70 ° C (174 ° F) to about 90 ° C (194 ° F), elemental sulfur is added and the mass is quickly heated to a temperature of about 180 ° C (356 ° F) while being stirred in a nitrogen atmosphere. The liquid mass is maintained at a temperature of from about 180 ° C (356 ° F) to 210°C (410 ° F) for about 1 hour. Thereafter, the mass is cooled while being stirred to provide a uniform catalyst mixture.
  • the partially deactivated nickel catalyst used in the present invention is utilized at a concentration of from about 0.01% to about 0.2%, preferably from about 0.03% to about 0.1%, and most preferably from about 0.05% to about 0.08% by weight of nickel/weight of oil and is added in a single step.
  • the amount of catalyst used is dependent upon the rate of reaction to be attained and other variables such as temperature and pressure, and the starting oil.
  • Certain oils. particularly mustard seed and Canola oils contain organic sulfur compounds which act as catalyst poisons.
  • the primary volatile sulfur compounds found in Canola oil include allyl isothiocyanate, 3-butinyl isothiocyanate, 4-pentenyl isothiocyanate, and 2-phenethyl isothiocyanate.
  • Recycled catalyst is often combined with fresh catalyst to obtain the desired activity level.
  • any type of commercially acceptable processing operation including batch hydrogenation, continuous processing, recirculation systems, and "dead-end" systems, may be utilized with the process described herein.
  • the process described herein is a single-stage process. The hydrogen, oil, and catalyst are contacted or mixed in a single step, and the reaction the proceeds to completion.
  • the process is carried out for from about 30 minutes to about 8 hours, and preferably from about 1 hour to about 4 hours.
  • the pressure ranges from about 0 psig (0 kPa) to about 100 psig (690 kPa), and preferably from about 0 psig (0 kPa) to about 40 psig (275 kPa).
  • the pressure can remain constant throughout the hydrogenation process or can be changed during the reaction. It is often desirable to control the rate of reaction by manipulating the pressure in the reaction vessel.
  • the pressure should be manipulated in such a way as to maintain a rate of reaction high enough to allow completion of the hydrogenation within a reasonable time period, but not so high as to significantly decrease the selectivity of the reaction. It may be desirable to decrease the pressure, thereby decreasing the rate of reaction, toward the end of the hydrogenation to allow adequate control of the termination point.
  • Pressure is controlled by valves which release hydrogen from the reactor or add additional hydrogen to the reaction vessel.
  • the temperature of the reaction is gradually increased from a starting termperature of from about 160°C (320°F) to about 200 ° C (392 ° F), and preferably about 180°C (356°F), to a final temperature of from about 210 ° C (410 ° F) to about 250 ° C (482 ° F), and preferably about 240 ° C (464 ° F).
  • the method used to control the temperature of the reactor varies with the processing equipment. Since hydrogenation is an exothermic reaction, it may be necessary to cool the reaction by some suitable means, such as a heat exchanger.
  • the system may lose heat quickly enough that the heat generated by the exothermic reaction will not be sufficient to maintain the reaction temperature or to allow for the gradual rise required by the process herein.
  • it is necessary to apply additional heat by some suitable means, such as heating coils or external heating means such as heating jacket or heat exchangers. Heat may be applied either continuously or periodically, depending on the requirements of the system.
  • the temperature increase of the process is preferably controlled by the gradual rise occurring through the exothermic reaction. However, in those cases where additional heat is required, the temperature increase is a gradual or a step-wise increase over the reaction period.
  • the reaction is terminated when the iodine value (IV) reaches a value of from about 65 to about 91, and preferably from about 70 to about 88. This is just before any significant amount ( 6%) of the mono-unsaturated fatty acid is converted to saturated.
  • IV iodine value
  • the IV at which this point is reached depends upon the initial fatty acid content of the oil or blend of oils which are hydrogenated. It is very important to terminate hydrogenation at the proper point, since continuation beyond this point will result in a fat having undesirably high SCI values and a narrower SCI spread.
  • the fats produced have an SCI spread of at least about 17, and preferably at least 33, between 21 °C (70 ° F) and 33 ° C (92 ° F) and an SCI of not higher than about 6, and preferably not higher than about 2, at 33 ° C (92 ° F).
  • a conventional margarine product should melt readily in the mouth to avoid a sensation of waxiness or stickiness and to have a satisfactory flavor. This means there should be little or no fatty material in the solid state at or near mouth temperatures during mastication (about 32 ° C (90°F) to 35 ° C (95 ° F). However, at temperatures of use (about 18°C (65°F) to 29°C (85°F), it must be capable of being spread and this requires that some portion of the fatty material be in the solid state, but not so much that the margarine is hard and difficult to spread and not so little that the margarine will slump or lose its shape. In addition, the margarine should have good stability to permit storage of the product in the refrigerator or at room temperature.
  • the solid content referred to hereinabove is expressed at different temperatures, in terms of a 'Solids Contents Index" (SCI) which is measured by what is essentially the test described in the Journal of the American Oil Chemists' Society, March 1954, Vol. XXXI, pp. 98-103.
  • the test involves a dilato- metric measurement of the amount by which a fat expands when heated from a specific temperature to complete melting. Since this expansion is due to both a volume increase when solids change to liquids without a temperature change and a volume increase due to thermal expansion without change in phase from solid to liquid, allowance is made for the thermal expansion so that the change in volume gives a measure of the amount of solid phase present at the temperature of measurement.
  • the test has been modified so that readings are taken after 30 minutes at the temperature of measurement. SCI data for an oil are often presented in a graph from wherein the abscissa is Temperature and the ordinant is SCI.
  • the Iodine Value is the number of grams of iodine absorbed by 100 g of oil from an iodine bromine mixture.
  • the Iodine Value may be determined by titration or calculated from the fatty acid composition data of the sample. Approximate iodine values may be determined by measurement of the refractive index of the oil, since for each given oil a linear correlation between iodine value and refractive index can be determined. This method allows a relatively quick and easy determination of the proper endpoint of the hydrogenation. The larger the iodine value, the more unsaturated the fat.
  • Example II To 185.972 kg (410 Ibs) of a 80% soybean/20% cottonseed oil blend was added 550 g of recycled sulfur-deactivated nickel (20% Ni) catalyst. The hydrogenation was carried out in a single step as in Example I according to the following table:

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  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Fats And Perfumes (AREA)
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Claims (16)

1. Procédé d'hydrogénation catalytique d'huiles liquides dans lequel on fait réagir une huile liquide ayant un indice d'iode d'environ 95 à 145 avec de l'hydrogène en présence d'un catalyseur à base de nickel partiellement désactivé, à une pression allant de 0 kPa à 690 kPa, et à un intervalle de température où la température s'accroit à partir d'une température de départ d'environ 160°C à environ 200°C à une température finale d'environ 210°C à environ 250°C, jusqu'à ce que l'indice d'iode de l'huile liquide soit d'environ 65 à environ 91, caractérisé en ce qu'on ajoute le catalyseur en une seule étape, en une quantité allant de 0,01 % à 0,2% de nickel en poids d'huile.
2. Procédé selon la revendication 1 dans lequel le catalyseur à base de nickel partiellement désactivé est présent à une concentration de nickel allant de 0,03% à 0,1% en poids d'huile.
3. Procédé selon la revendication 1 ou 2 dans lequel le catalyseur à base de nickel partiellement désactivé est un catalyseur à base de nickel empoisonné au soufre.
4. Procédé selon la revendication 3 dans lequel le catalyseur à base de nickel empoisonné au soufre est présent à une concentration d'environ 0,05% à 0,08% de nickel en poids d'huile.
5. Procédé selon l'une quelconque des revendications précédentes dans lequel on accroit graduellement la température de la réaction d'une température de départ de 180°C à une température finale de 240°C.
6. Procédé selon l'une quelconque des revendications précédentes, dans lequel la pression de la réaction est de 0 kPa à 276 kPa.
7. Procédé selon l'une quelconque des revendications précédentes dans lequel la réaction est terminée lorsque l'indice d'iode atteint une valeur allant de 70 à 88.
8. Procédé selon l'une quelconque des revendications précédentes dans lequel la réaction est terminée en une durée allant de 30 minutes à 8 heures après le début.
9. Procédé selon la revendication 8 dans lequel la réaction est terminée en une durée allant d'une heure à 4 heures après le début.
10. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'huile à hydrogéner est une huile végétale ou un mélange d'huiles ayant des chaînes d'acides gras contenant au moins 14 atomes de carbone.
11. Procédé selon la revendication 10 dans lequel l'huile ou le mélange d'huiles à hydrogéner est choisi(e) dans le groupe constitué par l'huile de soja, l'huile de tournesol, l'huile de carthame, l'huile de maïs, l'huile de coton, l'huile d'olive, l'huile d'arachide, l'huile de coprah, l'huile de palme, l'oléine d'huile de palme et l'huile de Canola, et leurs mélanges.
12. Procédé selon la revendication 11 dans lequel l'huile à hydrogéner est choisie dans le groupe constitué par l'huile de soja, l'huile de tournesol et l'huile de maïs, et leurs mélanges.
13. Procédé selon la revendication 11, dans lequel l'huile à hydrogéner est un mélange d'huiles contenant une huile choisie dans le groupe constitué par l'huile de soja, l'huile de tournesol et l'huile de maïs.
14. Procédé selon la revendication 12 dans lequel l'huile à hydrogéner est l'huile de soja.
15. Procédé selon la revendication 11 dans lequel l'huile à hydrogéner est un mélange d'huiles contenant une huile choisie dans le groupe constitué par l'huile de coton, l'huile de palme et l'oléine d'huile de palme.
16. Procédé selon la revendication 13 dans lequel l'huile à hydrogéner est un mélange d'huile de soja et d'huile de coton.
EP86200903A 1986-05-23 1986-05-23 Procédé d'hydrogénation pour la préparation de graisses à fusion rapide Expired EP0246366B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE8686200903T DE3673815D1 (de) 1986-05-23 1986-05-23 Hydrogenierungsverfahren zur herstellung von schnell schmelzenden fetten.
EP86200903A EP0246366B1 (fr) 1986-05-23 1986-05-23 Procédé d'hydrogénation pour la préparation de graisses à fusion rapide
AT86200903T ATE56042T1 (de) 1986-05-23 1986-05-23 Hydrogenierungsverfahren zur herstellung von schnell schmelzenden fetten.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP86200903A EP0246366B1 (fr) 1986-05-23 1986-05-23 Procédé d'hydrogénation pour la préparation de graisses à fusion rapide

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EP0246366A1 EP0246366A1 (fr) 1987-11-25
EP0246366B1 true EP0246366B1 (fr) 1990-08-29

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EP86200903A Expired EP0246366B1 (fr) 1986-05-23 1986-05-23 Procédé d'hydrogénation pour la préparation de graisses à fusion rapide

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2230020A (en) * 1989-01-27 1990-10-10 Unilever Plc Hydrogenation method
US7585990B2 (en) 2003-07-31 2009-09-08 Cargill, Incorporated Low trans-fatty acid fat compositions; low-temperature hydrogenation, e.g., of edible oils
EP1656439A4 (fr) 2003-07-31 2010-11-10 Cargill Inc Compositions a faible teneur en acides gras trans- hydrogenation basse temperature p. ex. d'huiles comestibles

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Publication number Priority date Publication date Assignee Title
FR1429975A (fr) * 1964-04-20 1966-02-25 Unilever Nv Hydrogénation catalytique de composés d'acides gras non saturés
US3459777A (en) * 1967-03-13 1969-08-05 Procter & Gamble Catalytic hydrogenation of oils for edible products

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ATE56042T1 (de) 1990-09-15
EP0246366A1 (fr) 1987-11-25

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