EP1737806A1 - Hydrogenation selective de groupes fonctionnels dans des substrats et acides gras partiellement hydrogenes et derives d'acides gras - Google Patents

Hydrogenation selective de groupes fonctionnels dans des substrats et acides gras partiellement hydrogenes et derives d'acides gras

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Publication number
EP1737806A1
EP1737806A1 EP05722305A EP05722305A EP1737806A1 EP 1737806 A1 EP1737806 A1 EP 1737806A1 EP 05722305 A EP05722305 A EP 05722305A EP 05722305 A EP05722305 A EP 05722305A EP 1737806 A1 EP1737806 A1 EP 1737806A1
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EP
European Patent Office
Prior art keywords
fatty acids
process according
catalyst
hydrogenation
trans
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP05722305A
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German (de)
English (en)
Inventor
Magnus Härröd
André HOLMQVIST
Sander Van Den Hark
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Harrod Research AB
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Harrod Research AB
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Publication date
Priority claimed from SE0400868A external-priority patent/SE527229C2/sv
Application filed by Harrod Research AB filed Critical Harrod Research AB
Publication of EP1737806A1 publication Critical patent/EP1737806A1/fr
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds

Definitions

  • the present invention concerns a process for the hydrogenation of functional groups in hydrogenatable substrates especially in the form of lipids, primarily fatty acids and fatty acid derivatives, e.g. triglycerides and methyl fatty acids, wherein hydrogen gas is mixed with a solvent and the substrate in the presence of a catalyst, and the reaction is carried out under predetermined conditions of pressure, time, temperature and concentration, so that the reaction reaches maximum selectivity.
  • Selectivity is obtained under substantially homogeneous conditions by reaching a very favourable balance between mass transport (addition of substrate and removal of product) and reaction rate.
  • supercritical solvents are especially suitable.
  • fatty acids we can, for example, selectively hydrogenate fatty acids with 3 double bonds, with reduced formation of trans- and no formation of saturated fatty acids.
  • Another example is to hydrogenate fatty acids with 2 and 3 double bonds without hydrogenating monounsaturated fatty acids and simultaneously obtain very low amounts of trans-fatty acids.
  • the invention also concerns partially hydrogenated fatty acids and fatty acid derivatives produced according to this process.
  • the reaction rate of various catalytic reactions depends on the type of catalyst, temperature, concentrations (substrate, products), time, adsorption coefficients and equilibrium constants. Transport mechanisms between bulk and catalysts are often important for the result of the reaction (Moulijn et al. 1993). One can control the reaction by influencing these fundamental factors in different ways.
  • Triglycerides are very large (MW ca. 900) non- polar molecules. The diffusivity decreases with increasing molecular weight. This means that the mass transport of triglycerides becomes low, and it is extra hard to obtain selective hydrogenation of the different fatty acids in the molecule. Together, our molecules cover a very large range of molecules. Hydrogenation of fatty acids, methyl fatty acids, triglycerides and other fatty acid derivatives.
  • trans-fatty are usually desirable (Swern 1982).
  • the health effects of trans-fatty acids are being questioned to a very rapidly expanding extent (Wahle & James 1993).
  • K 1 f K 2 , K 3 are reaction rate constants in the process.
  • the literature provides the equations which are needed to calculate these constants from the concentrations of the various fatty acids (Hui, 1996). One tends to describe the selectivity between these reactions with S n and S o , which are defined in eq. 2 and 3. When these parameters are larger than 1 , one begins to indicate selective processes (Hui, 1996)
  • a typical traditional hydrogenation reactor is a large tank (5 - 20m 3 ) filled with oil and hydrogen, together with finely-divided catalyst (nickel metal powder).
  • the reaction is carried out at low pressure, just above atmospheric pressure (0.5 - 5bar), and high temperature (130 - 210°C). Much care is taken in mixing the hydrogen in the oil, as this is a factor which limits the reaction rate (Grau et al., 1988).
  • the amount of trans-fatty acids is normally between 30 and 50%.
  • the concentration of the activated H-atoms on the catalyst surface determines how much of the double bounds are hydrogenated or deactivated without hydrogenating.
  • a deficiency of activated H-atoms causes trans- and positional isomerisation (Allen, 1956; Allen, 1986). Deficiency of activated H-atoms arises through low solubility of H 2 in the oil.
  • the "half hydrogenation” theory and empirical results thus agree very well (Allen, 1956; Allen, 1986; Hsu et al., 1989).
  • Copper is a catalyst which can selectively hydrogenate polyunsaturated fatty acids or fatty esters to monounsaturated fatty acids. It gives almost no saturated fatty acids, but it provides a lot of trans-fatty acids.
  • GB670906 (Miyake, 1952), it is described how a copper-chrome catalyst, free from activators, selectively hydrogenates polyunsaturated oils, fats or esters to monounsaturated, but that monounsaturated are not further hydrogenated to saturated (100-230°C, 1-80 bar H 2 ).
  • activators are defined as more active metals, such as Ni, Co, Pd, Pt. No ratio between cis/trans is given.
  • Cu/Zn is a catalyst which is even more selective for monounsaturated fatty acids, DE 4103 490 (Gritz, G ⁇ bel, 1992).
  • the elaidic acid/stearic acid ratio is very high (0.82) (100- 250°C, 1-50bar H 2 ).
  • the amount of monounsaturated fatty acid is very high (ca. 80%), while the amount of trans is also very high (ca. 40%) (200-300°C, 20-35bar H 2 , 3-8h).
  • the mixture of hydrogen, substrate and solvent preferably forms a substantially homogeneous phase which is brought into contact with the catalyst.
  • the substantially homogeneous mixture of hydrogen, substrate, product and solvent is in a near-critical or critical state.
  • the functional group which shows the lower reactivity first begins to be hydrogenated when at least 75%, preferably at least 80% and most preferably at least 90% of the functional group which shows the higher reactivity has been hydrogenated.
  • the hydrogenatable functional groups are - according to one aspect of the invention - of the same type but show different reactivities.
  • the hydrogenatable functional groups are of the same type but show different, yet similar, reactivities.
  • the substrate is a mixture of different molecules and that the hydrogenatable functional groups of the same of different type occur in different molecules.
  • the hydrogenatable functional groups of the same or different type occur in the same molecule.
  • the substrate according to one aspect of the invention is lipids, primarily fatty acids and fatty acid derivatives, such as triglycerides and methyl fatty acids.
  • the substrate is fatty acids and/or fatty acid derivatives which are hydrogenated to a degree of reduction of 18:3, i.e. ccc-fatty acids of at least 85%, characterised in that the process conditions are adapted so that the hydrogenated final product comprises an amount of trans-fatty acids in the form of Sn- number of highest 50, and a selectivity in the form of S Ln -number of at least 1.5.
  • the solvent is suitable selected so that it can dissolve at least 2 % w/w, preferably at least 5% w/w and most preferably at least 10 % w/w of the substrate at the process conditions in question.
  • the solvent is suitably selected from the group: carbon dioxide, ethane, propane, butane, pentane, hexane, heptane, tetrahydrofuran (THF), dioxane, dimethylether (DME), methanol, ethanol, acetone and mixtures thereof.
  • the solvent is selected from the group: propane, butane, pentane, hexane, heptane, dimethylether (DME), ethanol, acetone and mixtures thereof.
  • the solvent is selected from the group: propane, butane, dimethylether (DME), ethanol, acetone and mixtures thereof.
  • the solvent is selected from the group: butane and dimethylether (DME).
  • the reaction is carried out in the absence of ammonia and diamines.
  • the concentration of the substrate is at least 2% w/w, preferably at least 5 and most preferably at least 10% w/w.
  • catalysts which are used in the process of the invention are suitably solid-bed catalysts.
  • the reaction temperature of the process is suitably at most 200°C, preferably at most 100°C, and most preferably at most 75°C.
  • the hydrogen pressure in the substantially homogeneous mixture should suitably be at least 1 bar, preferably at least 2 bar and most preferably at least 5 bar.
  • the reaction time is suitably at least 1 sec, preferably at least 2 sec and most preferably at least 5 sec.
  • the hydrogenation activity should be at the most 2.5 mmol H 2 /I.s, preferably at most 1.5 mmol H 2 /I.s and most preferably at most 1 mmol H 2 /I.s.
  • the hydrogenation activity should be at least 0.05 mmol H 2 /I.s.
  • the hydrogenation reaction is carried out in sequential steps, so that the majority of a certain type of a selected functional group with a certain reactivity is selectively hydrogenated in each step.
  • the different sequential hydrogenation steps are - according to one embodiment - carried out in different reactors with different reaction conditions with regard to one or more factors such as catalyst, temperature or pressure.
  • the invention concerns a partially-hydrogenated product in the form of fatty acids or fatty acid derivatives which have a reduction level of 18:3, i.e. ccc-fatty acids, of at least 85% characterized in that it has a trans-fatty acid content in the form of S M -number of at most 50, and a selectivity in the form of S Ln -number of at least 1.5.
  • the invention further concerns a partially-hydrogenated product in the form of fatty acids or fatty acid derivatives which have a reduction level of 18:3, i.e. ccc-fatty acids, under 100%, characterized in that it has a trans-fatty acid content in the form of Sn-number of at most 40, preferably at most 30 and a selectivity in the form of S L ⁇ -number of at least 3.5, preferably at least 4.
  • the invention further concerns a partially-hydrogenated product in the form of fatty acids or fatty acid derivatives which have a reduction level of 18:2+, i.e. ccc + cc fatty acids, of at least 35%, characterized in that it has a content of trans-fatty acids in the form of Sn- number of at most 50, and a selectivity in the form of S Lo -number of at least 3.5.
  • a partially-hydrogenated product is considered, characterized in that it has a reduction level of 18:2+, i.e.
  • ccc + cc fatty acids of at least 20%, an amount of trans-fatty acids in the form of Sn-number of at most 40, preferably at most 30 and a selectivity in the form of S Lo -number of at least 4, preferably at least 8.
  • the key to good selectivity is that the mass transport to and from the catalyst is sufficiently large that it does not limit the reaction rate.
  • This invention 1. we maximise the mass transport by adding a solvent with high diffusivity, low viscosity and high solvating ability of the substrate 2.
  • 3. we minimise the reaction rate by lowering the temperature and by choosing catalysts with low activities.
  • the catalysts react primarily with the bond which reacts most easily. When this bond cannot be transported sufficiently quickly to the catalyst surface, the catalyst takes the next most reactive bond. In this way, selectivity is worsened.
  • concentration of that functional group which is to be hydrogenated on the catalyst surface should be controlled so that the selectivity is maximised and not limited by mass transport of this group.
  • the mass transport of the substrate and product must be so large that it does not limit the reaction rate; i.e. we must both provide the catalysts with reagents (both substrate with the correct type of binding and hydrogen) and transport the product away from the catalyst so rapidly that the next bond does not have a chance to react. • All measures which increase mass transport are good for selectivity • All measures which minimize the reaction rate are good for selectivity
  • Reaction rates tend to be more temperature-dependent that transport rates. This is a further reason for minimizing the temperature in order to maximize the desired selectivity. If the activation energy for hydrogenation of the various bonds is favourable, lowering the temperature can increase the selectivity further, and vice versa.
  • Transport rates The transport rate is determined by the product of diffusivity and the difference in concentration between bulk and the catalyst surface.
  • concentration of the substrate on the catalyst surface i.e. that bond which we wish to react
  • a solvent with good transport properties i.e. high diffusivity and low viscosity and partly through reactor design, fixed bed reactor and small catalyst particles.
  • the reaction rate may be controlled by the choice of catalyst, temperature, substrate concentration and amount of hydrogen on the catalyst.
  • Each catalyst has its own optimal temperature for a given reaction.
  • a more active catalyst requires a lower temperature to reach the same activity.
  • One usually ranks the normal metals which hydrogenate C C bonds according to: Cu ⁇ Ni ⁇ Pt ⁇ Pd.
  • Cu ⁇ Ni ⁇ Pt ⁇ Pd With different support material, pore structures, metal concentrations and different additives, one can modify catalyst activity in different ways. One can, for instance, lower the concentration of Pd and obtain the same reactivity per unit volume with this catalyst as for a Cu-catalyst with the high concentration. Hydrogenation reactions are - as a rule - strongly exothermic. Heat is released, and the temperature of the catalytic site rises sharply.
  • a solvent which creates a substantially homogeneous phase with good thermal diffusivity, good mass diffusivity and a catalyst with a uniform and low activity are crucial to obtain perfect results.
  • substantially homogeneous means that the majority of the hydrogen exists in the continuous phase which covers the surface of the catalyst.
  • the majority of the hydrogen should in this patent be interpreted such that sufficient hydrogen exists in the phase which covers the surface of the catalyst, so that there is not a shortage of hydrogen on the surface of the catalyst.
  • One way of checking that one has a substantially homogeneous mixture is to observe the reaction rate, which increases dramatically when the continuous phase covering the catalyst surface is substantially homogeneous. See also the description of Figures 1-6 below.
  • Hydrogen consumption is a very important parameter for how the mixtures reacts in a solid-bed reactor.
  • Figure 2 illustrates the substantially homogeneous region in which the hydrogen requirement is maximal. All double bonds can be hydrogenated to saturated bonds at the given process conditions.
  • the dashed line between "Need” and “Butane” shows where the stoichiometric limit lies. To the right of the line, an excess of hydrogen is prevalent. In the smaller portion of the dark area lying to the right of the dashed line, stoichiometric excess and single-phase conditions (c.f. with Figure 1 ) prevail. In the slightly larger white area to the right of the dashed line, substantially homogeneous conditions prevail.
  • Figure 4 illustrates a situation in which the hydrogen requirement is very low due to the selected process conditions. It is only ccc-fatty acids which are hydrogenated to cc-fatty acids. At this very low hydrogen requirement, mass transport of hydrogen is not the limiting factor in the system, but rather mass transport of the correct substrate from the bulk to the catalyst surface.
  • Figure 5 describes the result of flash-point calculations under constant composition and different temperatures and pressures.
  • the single-phase area "Single Phase” is above and to the right of the continuous line. Multiple phases exist under the continuous curves.
  • the area is designated “Multi-Phase” in the figures.
  • the composition of the reaction mixture is given in the box in the upper right-hand side of the figure and is expressed in mol%.
  • One continuous line is calculated for propane and the other for dimethyl ether (DME). DME requires slightly lower pressure than propane to obtain single-phase conditions.
  • the points in the figures are measured limits for propane and the triangles are measured limits for DME.
  • the squares are the critical points for propane and DME.
  • the substantially homogeneous area is illustrated in the figure with the pale grey area (single-phase area plus a small amount of the multiphase area).
  • the single-phase area at low pressure and high temperature is the traditional gas-phase area.
  • the complex mixtures we deal with lack a clear definition of the critical point. Conventional definitions of supercritical and near-critical conditions are lacking. One can however say that the substantially homogeneous mixture of hydrogen, substrate, and product is in a near- critical or supercritical state.
  • Figure 6 describes how one can determine whether one has substantially homogeneous reaction conditions when one has process conditions corresponding to the conditions in
  • Figures 2 or 3. One observes the reaction rates as a function of substrate concentration. At lower substrate concentrations, the reaction rate increases linearly with substrate concentration. One has single-phase conditions until one reaches the maximal reaction rate. When one further increases the substrate concentration, one reaches a state where the reaction rate begins to decrease, and then falls very sharply. This is because parts of the catalyst surface begin to be covered by drops which comprise a substrate-rich and hydrogen-poor phase. The continuous phase is still rich in hydrogen. Finally, upon further increase in substrate concentration, one reaches a low reaction rate. Here, the catalyst has become completely covered by the substrate-rich and hydrogen-poor phase. The continuous phase around the catalyst has become hydrogen-poor. According to our definition, the reaction conditions are substantially homogeneous as long as the continuous phase is hydrogen-rich.
  • Figure 7 describes reaction pathways and upon hydrogenation of polyunsaturated fatty acids, ccc, to saturated fatty acids, "saturated”. The figure also describes some reaction pathways to trans-fatty acids, cct, ct and t.
  • c means a cis-bond t means a trans-bond
  • cct means a trans-bond
  • the position of the t is arbitrary. However, the bonds are not conjugated.
  • CLA means conjugated linoleic acid
  • CLnA means conjugated linolenic acid
  • Saturated means saturated fatty acids
  • Figure 8 describes to what extent different fatty acids react and how can affect the reaction with various process conditions.
  • the hydrogen concentration on the catalyst is crucial in determining the extent of formation of trans-bonds; the higher the amount of hydrogen on the catalyst, the lower the formation of trans-bonds. Lower temperatures reduce the reaction rate and it thereby becomes easier to transport hydrogen to the catalyst surface.
  • ccc fatty acids are the most reactive fatty acids, and are hydrogenated first.
  • the best selectivity is achieved when the reaction rate is not limited by the transport rate.
  • the transport requirements of ccc fatty acids to the catalyst are therefore very large if one is to obtain high selectivity regarding ccc fatty acids.
  • the transport rate is controlled by the product of diffusivity and concentration gradient.
  • the concentration should not be chosen to be so high that the product of the diffusivity and concentration gradient falls.
  • the substantially homogeneous area which we have defined above comprises a particularly suitable group of reaction mixtures to obtain these conditions
  • concentration of the oil should be high, so that the concentration gradient can be high.
  • Another condition is to have a solvent with good transport properties, high diffusivity and low viscosity. High concentrations of hydrogen on the catalyst are necessary to reduce formation of trans-fatty acids (WO9601304, US6265596, Harr ⁇ d, M ⁇ ller). Suitable solvents are the key to obtaining a good result.
  • a solvent which dissolves both oil and hydrogen in high concentrations. Good transport properties are another requirement of the solvent.
  • butane and dimethylether are technically most interesting solvents for triglycerides. They have good solvating ability for both oil and hydrogen. They further have good transport properties, low viscosity and high diffusivity. Butane is approved for use in food product processes within the EU. DME is not as yet considered as a solvent for food products within the EU.
  • NH 3 has earlier been shown to be good at reducing the activity of many catalysts, and thereby increasing the selectivity.
  • the use of NH 3 in food products is unclear. Therefore, reactions preferably take place in the absence of NH 3 (ammonia) and also in the absence of diamines.
  • Propane, ethane and CO 2 have a solvating ability for triglycerides which is too low.
  • these solvents e.g. FAME (fatty acid methyl esters), propane can work well.
  • solvents which could be considered due to their solvating abilities of the substrate are pentane, hexane, tetrahydrofuran (THF), dioxane, methanol, ethanol and acetone. These have a lower solubility of hydrogen, though, and a lower diffusivity and higher viscosity as compared to e.g. butane or DME. At the low reaction rates which are required for selective hydrogenation of triglycerides, the hydrogen transport requirements are reduced to such an extent that these solvents can be considered.
  • the processes can be further improved with specially designed catalysts.
  • Stable activity is necessary.
  • the catalysts should have a small, specific area, and the particles should be small.
  • the catalytic activity should be low, preferably a low concentration of the active catalyst component. Different types of deliberate inactivation of the catalyst may be interesting.
  • the pressure drop across the reactor determines the size of the particles.
  • a guide value is 20-50 ⁇ m, yet the proportion and distribution of the smallest particles is very important.
  • the solvent lowers the viscosity of the mixture and this makes it possible to use particles which are significantly smaller than in traditional continuous processes without solvent. Small particles shorten the transport distance in the particle and thereby increase the gradient and mass transport.
  • the temperature should therefore be low, preferably room temperature or even lower. The requirement for solubility sets the lower boundary for usable temperatures.
  • Each catalyst has its own optimal temperature.
  • a more active catalyst requires a lower inlet temperature so that the surface of the catalytic site does not become so high that the next most active bond begins to react and the selectivity is thereby reduced.
  • the relationship between temperature and selectivity is unique for each reaction system.
  • One usually ranks the common metals which hydrogenate C C bonds according to: Cu ⁇ Ni ⁇ Pt ⁇ Pd.
  • the required selectivity is obtained at a higher temperature for copper than nickel, and so on.
  • the basic principle still applies: the more active a catalyst is, the lower the optimal temperature will be.
  • Hydrogenation can occur in many different steps in successive reactors. For example, one might selectively hydrogenate bond 1 in a first reactor, bond 2 in a second reactor, and so on.
  • reaction time is fixed.
  • reaction rate is minimised, so that mass transport is not the limiting factor.
  • Solvent concentration weight% 99 - 5 95 - 20 90 - 50
  • the principle can also be used on other substrates in which one has at least two bonds of similar type which can be hydrogenated, but which are of slightly different reaction rates and absorption coefficients and which can be catalysed by the same catalyst.
  • the principles for the choice of process parameters for other substrates are the same as discussed above for fatty acids and fatty acid derivatives.
  • table 2 we have summarised suitable limits for the various process parameters so that one may obtain selective hydrogenations. It is important that one has substantially homogeneous conditions, a lot of hydrogen on the catalyst, a high mass-transport of the substrate to the catalyst and a low catalytic activity chosen in such a way that the mass transport is not the limiting factor.
  • water and ammonia may be usable for polar substrates.
  • Solvent concentration weight% 99 - 5 95 - 20 90 - 50
  • Hydrogenation is initiated by adding a known amount of hydrogen to a continuous flow of solvent, dimethylether (DME) or butane, and then adding a flow of substrate (rapeseed oil from the local store).
  • DME dimethylether
  • substrate rapeseed oil from the local store.
  • the total system pressure was usually 200bar.
  • the entire reaction mixture is warmed to the desired temperature and passes through a solid catalyst bed which is warmed to the same temperature.
  • Samples are taken at regular intervals from the reactor outlet for triglyceride analysis by HPLC. Under certain chosen periods, a large amount of produce is collected for methylation and analysis of fatty acid composition by HPLC. Both HPLC methods are based on silver ion chromatography.
  • the triglyceride method is described in Macher, 2001 and Macher Holmqvist 2001 and the methyl ester method is described in van den Hark 2000, and Elfman et al 1997. The method does not analyse chain length. This means that we regard 18:0 as being completely saturated and that this is calibrated against 18:0; 18:t represents all methyl fatty acids with a trans calibrated against 18:t, etc.
  • a high resolution GC method is used in Tables 8 and 9 to determine the composition of the fatty aicds (column: WCOT fused silica 0.25mm * 100m; gradient [+80°C -> 130°C, +45°C/min (Omin) -> +220°C, +1°C/min (10min)]; Injector: 240°C, detector +280°C, carried gas: helium)
  • the reaction time is based upon the calculated total volume flow of the reaction mixture (at the current temperature and pressure), divided by the volume of the catalyst bed.
  • the productivity (LHSV) is given as the number of millilitres of substrate which pass through the reaction volume per unit time, i.e. ml sub str a .e/rnl rea ctor * hour.
  • the activity describes the mass transport in the reactor by mmol H 2 /litre reactor and second.
  • a catalyst containing 2 weight % Pd on alumina-silica zeolite (Engelhard) is used as a Pd catalyst.
  • This catalyst is used as delivered, and is warmed to 150°C in a nitrogen gas-hydrogen gas mixture.
  • the density of the catalyst is 0.5kg/l
  • Table 4 describes hydrogenation trials with rapeseed oil, DME and copper catalyst. There are also some selected reference trials which represent the best trials which we found in the literature.
  • the amount of cc-fatty acids does not begin to decrease until ccc-fatty acids fall below 1 weight%.
  • the S n is above 9, see exp 18! Saturated fatty acids do not begin to be produced until the amount of cc-fatty acids is less than 5 weight%.
  • S Lo is greater than 100 in the majority of our experiments! It is only when we do not succeed in supplying the catalyst sufficiently with cc-fatty acids that c- fatty acids begin to be hydrogenated to saturated fatty acids.
  • trans-fatty acids t and ct are produced at approximately the same rate, while IV decreases (see exp 19-16).
  • the reaction rate for production of trans- also falls (see 18:2 and 18:ct in exp 16-14 and in exp 12-10). This reaction rate is low, as there is a lot of hydrogen on the catalyst.
  • ⁇ means thai the content is so low that we have given it to the lowest amoun we have calibrated respective peak in the chromatogram 1 Gritz G ⁇ bel DE4103490 Henkel 1992 14,2 - 23,4 55,8 6,6 133 SBO from Kuiper Ex 1 Cu/Zn 240 20 100 7200 0,3 13,0 - 86,0 1,0 0,0 76 99 100 info on trans missing Ex V1 Cu/Mn 240 20 100 21600 0,1 18,0 36,0 44,0 2,0 0,0 72 59 1 ,8 62 97 100

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Abstract

L'invention porte sur un procédé d'hydrogénation de groupes fonctionnels dans des substrats hydrogénables, le gaz hydrogène étant mélangé au substrat et à un solvant, et le mélange mis en contact avec un catalyseur. L'hydrogénation est effectuée dans des conditions qui sont adaptées à l'activité du catalyseur utilisé, la température étant suffisamment basse et la concentration du substrat suffisamment élevée de même que la diffusivité de façon à obtenir une hydrogénation sélective du groupe fonctionnel ayant une réactivité supérieure à celle d'un autre groupe. Les groupes fonctionnels peuvent comprendre, par exemple, différents groupes C=C dans des substrats se présentant sous la forme de lipides, des acides gras primaires et des dérivés d'acides gras tels que des triglycérides et des acides gras de méthyle. Les acides gras partiellement hydrogénés et les dérivés d'acides gras obtenus présentent une faible teneur en acides gras trans ainsi qu'une haute sélectivité sous la forme du nombre SLn et du nombre SLo.
EP05722305A 2004-03-31 2005-03-31 Hydrogenation selective de groupes fonctionnels dans des substrats et acides gras partiellement hydrogenes et derives d'acides gras Withdrawn EP1737806A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US55770704P 2004-03-31 2004-03-31
SE0400868A SE527229C2 (sv) 2004-03-31 2004-03-31 Selektiv hydrering av C=C bindningar i triglycerider och fettsyror
PCT/SE2005/000481 WO2005095306A1 (fr) 2004-03-31 2005-03-31 Hydrogenation selective de groupes fonctionnels dans des substrats et acides gras partiellement hydrogenes et derives d'acides gras

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PL3237369T3 (pl) 2014-12-22 2021-01-25 Novamont S.P.A. Ulepszony sposób selektywnego uwodorniania olejów roślinnych

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GB642012A (en) * 1947-05-02 1950-08-23 Procter & Gamble Partial hydrogenation of unsaturated glyceride oils in solvents
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