EP0126168B1 - Réduction sélective continue d'huiles et de graisses comestibles - Google Patents

Réduction sélective continue d'huiles et de graisses comestibles Download PDF

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Publication number
EP0126168B1
EP0126168B1 EP83104898A EP83104898A EP0126168B1 EP 0126168 B1 EP0126168 B1 EP 0126168B1 EP 83104898 A EP83104898 A EP 83104898A EP 83104898 A EP83104898 A EP 83104898A EP 0126168 B1 EP0126168 B1 EP 0126168B1
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Prior art keywords
oil
hydrogenation
less
fats
catalyst
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EP83104898A
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German (de)
English (en)
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EP0126168A1 (fr
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Bruce Irvin Rosen
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Honeywell UOP LLC
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UOP LLC
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Priority to AT83104898T priority Critical patent/ATE24332T1/de
Priority to EP83104898A priority patent/EP0126168B1/fr
Priority to DE8383104898T priority patent/DE3368439D1/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
    • C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates

Definitions

  • fatty materials which are the subject of this invention, hereinafter collectively referred to as fatty materials, are triglycerides of fatty acids, some of which are saturated and some of which are unsaturated.
  • the major saturated fatty acids are lauric (12:0), myristic (14:0), palmitic (16:0), stearic (18:0), arachidic (20:0), and behenic (22:0) acids.
  • the notation, "18:0" for example, means an unbranched fatty acid containing 18 carbon atoms and 0 double bonds.
  • the major unsaturated fatty acids of vegetable oils may be classified as monounsaturated, chief of which are oleic (18:1) and erucic (22:1) acids, and polyunsaturated, chief of which are the diene, linoleic acid (18:2) and the triene, linolenic acid (18:3).
  • Unhardened vegetable fats and oils contain virtually exclusively cis-unsaturated acids.
  • the ultimate goal is the reduction of triene to diene without attendant trans acid formation or saturate formation.
  • partial reduction results in lowering both triene and diene and increasing the monoene, saturate, and trans levels.
  • the product of partial hydrogenation itself be a liquid oil relatively free of sediment or even cloudiness upon storage at, for example, 10°C
  • the formation of saturated and trans acids in such hydrogenation is a vexing problem. Removal of these solids, whose relative amount is measured by the Solid Fat Index (SFI), is a relatively costly and inefficient process attended by large losses associated with the separation of gelatinous solids from a viscous liquid.
  • SFI Solid Fat Index
  • the solubility in the soybean oil of disaturated triglycerides is much less than twice the amount of monounsaturated triglycerides, and the solubility of monounsaturated triglycerides may depend upon whether the other fatty acid moieties of the triclyceride are monounsaturated, diunsaturated, etc., and may also depend upon whether the saturated portion is at the one-or two-position of the triglyceride.
  • hydrogenation of edible fats and oils is largely an empirical process, whose analytical tools include Solid Fat Index (SFI) supported by fatty acid analysis.
  • SFI Solid Fat Index
  • the difficulty of achieving desirable results, in the context of selectivity. in Solid Fat Index has largely limited such hydrogenation to a batch type process. Although the transition from a batch to a continuous process, especially of the fixed bed type, is conceptually facile, it will be recognized by the skilled worker that impediments have been substantial.
  • FR-A-2,175,223 discloses a continuous process for hydrogenating fatty acids by contacting them at a pressure of 6,9 to 69 bars and at a temperature of 93 to 232°C with a fixed mass of catalyst consisting essentially of palladium on alpha-alumina. The surface area and micropore volume of the alumina are not mentioned.
  • US ⁇ A ⁇ 2,971,016 describes the vapor-phase hydrogenation of unsaturated fatty acids and esters in a fluidized bed, which enables the disadvantages of liquid phase hydrogenation and the use of solid bed catalysts to be avoided. It will be recognized that vapor-phase hydrogenation is unfeasible for oils and fats.
  • a continuous process based on a mixture of oil and suspended catalyst flowing along a turtuous path on the top surface of a series of perforated plates, with hydrogen admitted through the bottom face countercurrent to the oil flow and minimum mixing along the various plates, is the subject of US-A-3,634,471.
  • US-A-3,792,067 which has had limited commercial application, is based on a turbulent two-phase gas-liquid flow with minimal back mixing, the liquid phase consisting of oil containing catalyst suspended therein.
  • Both US-A-3,823,172 and US-A-3,988,329 describe continuous hydrogenation processes where the flowing mass of oil containing suspended catalyst is subject to high shear forces.
  • US-A-3,444,221 describes a continuous process which requires a high ratio of liquid (catalyst suspended in oil) to gas phase using a plurality of reaction chambers.
  • a method of hydrogenation of edible oils is selective if it is capable of reducing the iodine value of soybean oil from about 10 to about 30 units with a concomitant increase in saturates of less than about 1.5% and a decrease in triene level to at least 3%, and where the Solid Fat Index of the partially hydrogenated product is less than about 5 ⁇ 1 at 10°C, less than about 2 ⁇ 0.5 at 21°C, less than 1.0 ⁇ 0.5 at 27°C, and 0 ⁇ 0.2 at 32°C.
  • selective hydrogenation utilizes a specific decrease in iodine value of a particular edible oil
  • a selective hydrogenation may cause a greater decrease in iodine value and/or be effected with a different edible oil. That is to say, the definition of selective hydrogenation does not restrict a selective hydrogenation to the conditions of its definition.
  • the object of this invention is to provide a continuous method of hydrogenation of edible oils and fats which method is highly selective.
  • the inventive method which comprises contacting a flowing mass of edible oils and fats at a temperature from about 150 to about 260°C in the presence of hydrogen at a pressure up to about 150 psig (1000 kPa gauge) with a fixed mass of catalyst consisting essentially of a catalytically active metal selected from Group VIII of the Periodic Table supported on alpha-alumina and recovering the resultant hydrogenated product is characterized in that the alpha-alumina support has a surface area less than 10 m 2 /g and a micropore volume less than 0,1 ml/g.
  • alpha-alumina of low surface area and low porosity functions at hydrogenation conditions as an effective support for catalytically active zerovalent metals selected from Group VIII of the Periodic Table including iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum in a fixed bed hydrogenation of edible fats and oils, affording partially hydrogenated product with the desired selectivity.
  • catalytically active zerovalent metals selected from Group VIII of the Periodic Table including iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum in a fixed bed hydrogenation of edible fats and oils, affording partially hydrogenated product with the desired selectivity.
  • the metal selected from Group VIII of the Periodic Table is present at a level from about 25% based on alpha-alumina.
  • the catalytically active zerovalent metal selected from Group VIII of the Periodic Table is iron, cobalt, nickelt, ruthenium, rhodium, palladium, osmium, iridium, or platinum. Preferred is cobalt or nickel. Nickel is especially preferred.
  • the vegetable oil is passed upflow over the fixed bed.
  • the method described herein is generally applicable to edible oils and fats. Because the partial hydrogenation of liquid oils to afford hardened, but still liquid, oils occupies a prominent part within the domain of hydrogenation of edible oils and fats, the method of this invention is particularly applicable to such partial hydrogenation. Thus, the described method of hydrogenation is especially useful to partially harden edible liquid oils whereby the iodine value (IV) is lowered from about 10 to about 30 units by hydrogenation, whereby the increase in saturates attending hydrogenation is less than about 1.5%, and whereby the triene level is reduced to about 3% or less.
  • IV iodine value
  • Such a partially hydrogenated product preferably has an SFI of less than about 5 ⁇ 1 at 10°C, less than about 2 ⁇ 0.5 at about 21°C, less than about 1.0 ⁇ 0.5 at 27°C, and 0 + 0.2 at 33°C.
  • the term "iodine value" is a measure of the total extent of unsaturation in an edible oil or fat as performed by a standard test. In the context of soybean oil, which is a particularly important liquid vegetable oil, partial hardening is continued to an IV drop of from about 15 to about 25 units, with the product having less than about 6% stearate and about 3% linolenate or less.
  • the method claimed herein is especially valuable when applied to the partial hydrogenation of liquid vegetable oils, it must be explicitly recognized that the selectivity of the claimed method is also manifested in more extensive hydrogenations.
  • the claimed method may be used generally in hydrogenating edible oils whenever selective hydrogenation is desired.
  • the method of this invention is especially applicable to liquid vegetable oils.
  • oils include soybean oil, cottonseed oil, sunflower oil, safflower oil, rapeseed oil, corn oil, and liquid fractionations from palm oil.
  • the application of this method to soybean oil is especially important.
  • partial hydrogenation of liquid oils to afford partially hardened liquid oils is especially demanding, hence it is to be expected that a method suitable for this task also is suitable for more extensive hydrogenation.
  • the method described herein also is suitable for more extensive hydrogenation, where the IV of the product may be as low as about 70.
  • Oils and fats which can be so hydrogenated include those above, their partially hydrogenated products, and also such feedstocks as palm oil.
  • the hydrogenation catalyst used in this method is essentially a catalytically active zerovalent metal selected from Group VIII of the Periodic Table deposited on low surface area alpha-alumina. It is to be understood that by alpha-alumina is meant alumina whose crystallinity as measured by X-ray diffraction corresponds to that characterized in ASTM file number 10-173. Although zerovalent Group VIII metals are widely used in this art area, they are generally used on supports, such as kieselguhr and alumina, of high surface area and large porosity. A discovery of this invention is that continuous hydrogenation using zerovalent Group VIII metal in a fixed bed mode can be successfully performed, in the context of the criteria elaborated above, only on an alpha-alumina support characterized by relatively low surface area and porosity.
  • the hydrogenation catalyst of this method consists essentially of catalytically active zerovalent Group VIII metal on alpha-alumina with a surface area less than about 10 m 2 per gram, with a surface area less than about 5 m 2 per gram preferred.
  • the micropore volume of the support must be less than about 0.1 ml/g, with those supports having a micropore volume less than about 0.05 ml/g, being advantageous.
  • the macropore volume of the supports used in this invention is related to the surface area of the support. Consequently the supports used herein are further characterized by a macropore volume less than about 0,6 ml/g, with a macropore volume under about 0,3 ml/g being preferred.
  • micropore volume is meant the total volume of pores under about 11,7 nm (117 angstroms) in size; by macropore volume is meant the total volume of pores greater than 11,7 nm (117 angstroms) in size.
  • the concentration of Group VIII metal may range from 1 to about 25 percent by weight of alumina.
  • the choice of metal loading will depend, inter alia, on the degree of selectivity and catalyst life desired in a particular operation.
  • Metals selected from Group VIII of the Periodic Table include iron, cobalt, nickel, . ruthenium, rhodium, palladium, osmium, iridium, and platinum. Of these Group VIII metals, cobalt and nickel are preferred catalytically active components of-the hydrogenation catalyst. Nickel is most especially preferred.
  • the cobalt catalyst used in the method of this invention typically is prepared by reducing a suitable cobalt salt impregnated on the support. Such reduction is most conveniently effected by a stream of hydrogen at a temperature between about 400 and about 600°C. Other methods are also satisfactory, as for example, the methods commonly employed to prepare Raney-type cobalt.
  • the cobalt catalysts used in this invention are effete in amounts from about 0.01 to about 5% cobalt, based on edible oil hydrogenated, with the range from about 0.01 to about 1% being preferred, and with the lower end of this range being particularly preferred.
  • hydrogenations are conducted at a temperature from about 150 to about 250°C, with the range of 175 to 225°C being preferred. Hydrogenations may be conducted at pressures up to about 11 bar. Freqyently there is some advantage to conducting such hydrogenations at a pressure less than about 4 bar and a pressure from about 1,5 to about 4 bar often is preferred.
  • the catalyst bed may be in the form of pellets, granules, spheres, extrudate, and so forth.
  • the reactor is heated to the desired reaction temperature in a hydrogen atmosphere, often with a small hydrogen flow. After attainment of the desired temperature, the feedstock of edible fats and oils is made to flow over the fixed bed.
  • the flow rate of the oil may be from about 0,2 to about 20 liquid hourly spaced velicity (LHSV) depending upon the degree of hydrogenation sought.
  • LHSV liquid hourly spaced velicity
  • the flow may be either downflow, as in a trickle bed operation, or upflow, as in a flooded bed operation.
  • downflow is meant that the feedstock flows with gravity, that is, a trickle bed operation.
  • upflow is meant that the feedstock is made to flow against gravity, as in a flooded bed operation. Upflow is generally thought to be preferred to downflow because of a demonstrated enhanced selectivity of hydrogenation.
  • S LN is termed the linolenate selectivity; a high value is characterized by relatively high yields of dienoic acid in the reduction of an unsaturated triglyceride containing thienoic acids.
  • S LO is the linoleate selectivity; a high value is characterized by relatively high yields of monoenoic acid in a reduction of an unsaturated triglyceride containing dienoic acids.
  • An oil such as soybean oil contains both trienoic and dienoic acids, thus S LN and S LO may be measured simultaneously.
  • S LN usually is greater than about 2
  • S LO usually is greater than 10
  • Iodine values were determined by AOCS method CD1-25 or were calculated from the measured fatty acid distribution.
  • Solid fat index was determined by AOCS method CD10-57.
  • Fatty acid distribution was determined by AOCS method CE2-66.
  • Macropore volume was determined by the mercury intrusion method as described in ANSI/ASTM D 2873-10 using the porosimeter of US ⁇ A ⁇ 3,158,020.
  • the catalyst used in all runs consisted of 5% nickel on alpha-alumina, of surface area 3 m 2 /g in the form of 1,6 mm spheres. It was prepared by mixing the alumina with an aqueous solution of nickel nitrate hexahydrate, evaporating the water while mixing, calcining the resulting solid at 450°C in air for 3-4 hours, then reducing the material in hydrogen for 2-4 hours at the same temperature.
  • the alpha-alumina had the following macropore volume characteristics (in ml/g): 11,7-50 nm, 0.0000; 50-100 nm, 0.0003; 100-350 nm, 0.0000; 350-1750 nm, 0.2037; 17 50-58 33,3 nm, 0.0000.
  • the micropore volume was less than about 0.03 ml/g.
  • Results of some typical hydrogenations are given in Table 1. Each period of an example corresponds to a four hour time interval.
  • the SFI of some representative samples from upflow hydrogenation are given in Table 2. Values of S LN' S LO were calculated using a computer program furnished by the U.S. Department of Agriculture, Northern Regional Laboratories, as described in J. Amer. Oil Chemists Soc., 56, 664 (1979).
  • the cobalt catalyst was prepared in the following general way. Material used as the support was mixed with an aqueous solution of Co(N0 3 ) 2 ⁇ 6H 2 0 containing an amount of cobalt sufficient to provide the desired catalyst loading. Water was removed by evaporation with mixing, and the resulting solid was calcined in air at 450°C for about 2 hours followed by reduction in a stream of hydrogen at about 450°C for about 2 hours.
  • Hydrogenations were conducted in a reactor of conventional design containing a fixed bed of 15 to about 70 ml catalyst.
  • the reactor had a preheater section for bringing feedstock to temperature and a heater for the reaction zone.
  • the feedstock which was soybean oil in these samples, was passed upflow by a metering pump and mixed with hydrogen before the preheater stage. In all cases there was a net excess of hydrogen, that is, hydrogen in excess of that necessary for reaction was introduced into the reaction zone and excess hydrogen was vented so as to maintain a constant pressure.
  • Iodine values were determined by AOCS method CD1-25 or were calculated from the measured fatty acid distribution. Solid fat index was determined by AOCS method CD1D-57. Fatty acid distribution was determined by AOCS method CE2-66.

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  • Chemical & Material Sciences (AREA)
  • 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)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)

Claims (10)

1. Procédé continu pour l'hydrogénation sélective d'huiles et graisses comestibles qui comprend la mise en contact d'une masse en écoulement d'huiles et graisses comestibles à une température de 150 à 260°C en présence d'hydrogène à une pression allantjusqu'à 1000 kPa au manomètre (150 livres par pouce carré au manomètre) avec une masse fixe de catalyseur consistant essentiellement en un métal catalytiquement actif choisi dans le groupe VIII du Tableau Périodique sur support d'alpha-alumine et la récupération du produit hydrogéné résultant, procédé caractérisé en ce que le support d'alpha-alumine a une surface spécifique inférieur à 10 m2/g et un volume de micropores inférieur à 0,1 ml/g.
2. Procédé selon la revendication 1, dans lequel lesdites huiles et graisses comestibles sont des huiles végétales liquides.
3. Procédé selon la revendication 2, dans lequel ladite huile végétale liquide est choisie dans le groupe constitué par l'huile de soja, l'huile de graines de coton, l'huile de colza, l'huile de tournesol, l'huile de maïs, l'huile de carthame, et des fractions liquides d'huile de palme.
4. Procédé selon la revendication 2, dans lequel ladite huile est de l'huile de soja, et sa mise en contact avec ledit catalyseur a une durée suffisante pour abaisser l'indice d'iode de 10 à 30 unités.
5. Procédé selon la revendication 1, dans lequel le métal catalytiquement actif choisi parmi le groupe VIII est le nickel ou le cobalt.
6. Procédé selon la revendication 1, dans lequel le catalyseur contient d' 1 à 25% de métal catalytiquement actif à valence nulle choisi dans le Groupe VIII du Tableau Périodique.
7. Procédé selon la revendication 1, dans lequel la surface spécifique est inférieur à 5 m2/g, de préférence de 3 m 2 /g.
8. Procédé selon la revendication 1, dans lequel le volume des micropores est inférieur à 0,05 ml/g.
9. Procédé selon la revendication 1, dans lequel l'alpha-alumine est encore caractérisée par un volume de macropores inférieur à 0,6 ml/g, de préférence inférieur à 0,3 ml/g.
10. Procédé selon la revendication 1, dans lequel la mise en contact est effectuée dans le mode d'écoulement ascendant.
EP83104898A 1983-05-18 1983-05-18 Réduction sélective continue d'huiles et de graisses comestibles Expired EP0126168B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT83104898T ATE24332T1 (de) 1983-05-18 1983-05-18 Kontinuierliche selektive reduzierung von essbaren oelen und fetten.
EP83104898A EP0126168B1 (fr) 1983-05-18 1983-05-18 Réduction sélective continue d'huiles et de graisses comestibles
DE8383104898T DE3368439D1 (en) 1983-05-18 1983-05-18 Continuous selective reduction of edible oils and fats

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP83104898A EP0126168B1 (fr) 1983-05-18 1983-05-18 Réduction sélective continue d'huiles et de graisses comestibles

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EP0126168A1 EP0126168A1 (fr) 1984-11-28
EP0126168B1 true EP0126168B1 (fr) 1986-12-17

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Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565830A (en) * 1963-02-07 1971-02-23 Engelhard Min & Chem Coated film of catalytically active oxide on a refractory support
US3489809A (en) * 1968-04-17 1970-01-13 Engelhard Min & Chem Selective hydrogenation with a catalyst on a honeycomb support
IT979638B (it) * 1972-03-09 1974-09-30 Chemetron Corp Processo continuo per la idroge nazione di acidi grassi insaturi

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EP0126168A1 (fr) 1984-11-28
ATE24332T1 (de) 1987-01-15
DE3368439D1 (en) 1987-01-29

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