DE1082597B - Organic metal deactivator compound for the stabilization of hydrocarbon oils or fatty acid glycerides - Google Patents

Description

Organic metal deactivator compound for the stabilization of hydrocarbon oils or fatty acid glycerides Refining in the copper sweetening process turns into gasoline treated with a copper-containing] reagent. As a result, it contains the sweetened Gasoline usually contains relatively small amounts of copper compounds, the oxidation reactions catalyze. In addition, gasoline comes with various metals in the course of refining, Storage and transport in contact, whereby there are small amounts of copper, Iron, cobalt, nickel, chromium or lead can absorb the oxidation reactions catalyze and also have a detrimental effect on the durability of the gasoline own. Also other animal or vegetable hydrocarbon oils or fatty glycerides Are of origin with metallic components in the course of refining, storage and the transport contaminated and accordingly by the metallic components attacked.

In order to avoid such harmful influences of metallic components on mineral, to switch off animal or vegetable oils as a result of catalyzed oxidative changes, Organic metal deactivator compositions are known, which consist of condensation products aromatic o-oxyaldehyde with alkylene polyamines and an organic solvent exist. A particular example of such a metal deactivator is disalicylalpropylenediamine, made by condensing 2 moles of salicylaldehyde with one mole of propylenediamine will. Disalicylal propylenediamine is used for easier handling and use usually prepared as a solution in an aromatic solvent. Although this Metal deactivator composition is very effective per se, it has the disadvantage that it is a has too high freezing point. For example, temperatures drop as they normally would Occurring in the winter months, disalizyialpropylenediamine out of solution. this interferes with the use of the deactivator compound and forces it to be heated to Dissolve the disalicylal-propylenediamine in the solvent if one is not at risk wants to run that the solution used at more or less low temperatures a different concentration and thus too little effectiveness. True is it is known that the solubility of such condensation products in the to be stabilized organic substances depends on their constitution, but there is none Way solved the problem that at lower temperatures the condensation product crystallized from oxyaldehyde and alkylenepolyamine and precipitated from the solution.

Furthermore, the use of somewhat different condensation products, namely those made from ammonia with an aromatic o-oxyaldehyde as metal deactivators known, and it was also provided that these metal deactivators along with certain To use gum inhibitors such as phenols in such a way that one can use the gum inhibitor in a suitable solvent, such as alcohol or ether, and dissolve the metal deactivator either as such or in the same solvent as the resin formation inhibitor dissolved added to the substance to be stabilized.

The invention is based on the surprising finding that a considerably greater stabilizing effect can be achieved if one for the dissolution of the condensation product is not a uniform solvent, but a solvent mixture is used, and that is the subject of the invention an organic metal deactivator composition comprised of 35 to 70 percent by weight of the aforesaid Condensation product of aromatic o-oxyaldehydes with alkylene polyamines and 65 bis 30 percent by weight of a solvent mixture of a benzene hydrocarbon and an alkanol having 1 to 4 carbon atoms per molecule, in which the Alkanol is present in a concentration of 5 to 35 percent by weight. When the crowd a disalicylal-alkylenepolyamine in which the alkyl group contains 3 or 4 carbon atoms according to the invention, the solvent mixture preferably consists of Toluene and methanol.

The invention has the essential advantage that the Metal deactivator compound remains in the form of a solution even in cold weather, although they contain a higher concentration of the active metal deactivator may be called any known mass of this type. As a result, permitted the metal deactivator composition according to the invention the exact addition and maintenance a suitable amount of active metal deactivator to a hydrocarbon oil or fatty oil under all blending conditions as they normally occur. One such a possibility was not given with the known metal deactivator solutions, because with them at least a partial separation of the active ingredient low temperature occurs. However, the separation of solids interferes with the dimensions and mixing the metal deactivator mass with the oil or gasoline to be stabilized.

As already mentioned, the condensation product was preferably made from Salicylaldehyde or obtained from o-vanillin or mixtures thereof. Others, for the formation of the condensation product are suitable aromatic o-oxyaldehydes 2-OXy-6-methyl-benzaldehyde, 2-oxy-3-methoxy benzaldehyde, 2-oxy-4-methoxy-benzaldehyde, 2,4-dioxy-benzaldehyde, 2,6-dioxy-benzaldehyde, 2-oxynaphthaldehyde-1, 1-oxy-naphthaldehyde-2, Anthracene-2-aldehyde-i and mixtures of various of these aldehydes.

During the formation of the condensation product, in a known manner the aromatic orthoxyaldehyde with an alkylene polyamine, e.g. B. Ethylenediamine, Propylenediamine, 1,3-diamino-propane, 1,2-diaminobutane, 2,3-diaminobutane, diethylenetriamine, Dipropylenetriamine or triethylenetetramine or a mixture of these Amines condensed.

The aromatic hydrocarbon in the solvent mixture used consists. preferably from a benzene hydrocarbon such as benzene, toluene, xylene or cumene or a mixture of such hydrocarbons. It is generally used as a Alcohol methanol preferred.

The metal deactivator acts in an entirely different way than a resin formation inhibitor; for such a thing does not suppress the catalytic Effect of the metal to a considerable extent, and on the other hand suppresses the Metal deactivator does not inhibit resin formation in and of itself to a considerable extent.

Any suitable resin inhibitor can be used in conjunction with the metal activator composition of the invention. These gum inhibitors are well known and generally include various phenols, amines, aminophenols and fractions of wood tar oil. The resin-formation preventer may be prepared as a mixture with the metal deactivator in the known manner and the mixed solution as the sole - be applied additive.

Example 1 Disalicylal propylenediamine was prepared as a solution of the active ingredient in toluene and methanol. The following table shows the solubility of disalicylalpropylenediamine in various mixtures of these solvents at 2'C. Solubility of Solvent disalicylal propylenediamine Weight percent ° / o toluene I / o methanol of the solution 100 0 54.5 95 5 61 91 9 66.7 88 12 67.5 76 24 70 56 44 30.6 0 100 5.7 The use of methanol in a concentration above about 350 /, therefore leads to a lower solubility of the disalicylal propylene diene. On the other hand, the use of the mixture with methanol at a concentration of 5 to 35 percent by weight results in a considerable increase in the solubility of the disalicylal propylenediamine, which was particularly pronounced at a methanol concentration of about 8 to about 32 percent by weight.

Example 2 Another series of solvent tests was carried out using the disalizylal-propylenediamine and the toluene-methanol solvent as in Example 1 at -15 ° C. Their results are compiled in the following table. Solubility of Solvent disalicylal propylenediamine Weight percent 0 / a toluene I 0 / a methanol of the solution 100 0 29.6 95 5 34.6 91 9 41.5 88 12 41.0 84 16 37.3 74 26 33.3 69 31 33.1 58 42 25.6 52 48 22.5 It is. it can be seen that the same general results were also obtained at -15 ° C. when the solvent mixture contained 95 to 65 percent by weight of toluene and 5 to 35 percent by weight of methanol, in particular 92 to 68 percent by weight of toluene and 8 to 32 percent by weight of methanol.

Example 3 The metal deactivator of this example consisted of disalicylal-1,3-diaminobutane, obtained by condensation of 2 moles of salicylaldehyde with 1 mole of 1,3-diaminobutane. A mass of 44 weight percent disalicylal-1,3-dianinobutane in toluene has one Freezing point of about 81 ° C. However, the freezing point is lowered considerably, if you use a mixed solvent consisting of 90% toluene and 10% methanol, used instead of toluene. - Example 4 A metal deactivator composition was prepared by having salicylal propylenediamine as the active compound in a mixed solvent dissolved from 85 percent by weight benzene and 15 percent by weight secondary butyl alcohol, wherein the active compound in an amount of 55% by weight of the total composition was introduced.

Example 5 The metal deactivator active ingredient of this example was made by condensation of 2 moles of salicylaldehyde with 1 mole of propylenediamine (1,2-diaminopropane) manufactured. A solution consisting of 50 percent by weight of the active metal deactivator, 45 weight percent toluene and 5 weight percent methanol were prepared.

A thermally split gasoline that unstabilizes for an induction period of 36 minutes when it was tested by ASTM D525-55 for resistance to oxidation of gasoline was tested, showed when added of 0.01 percent by weight of an antioxidant consisting of N, N'-di-sec-butyl p-phenylenediamine, an induction period of 802 minutes. With the addition of 1 part every million (1 mg every liter) of copper in the form from copper oleate to a sample of the gasoline contained in the antioxidant Induction period of gasoline to 36 minutes. With the addition of 7 parts per million the deactivator solution according to the above information on a gasoline sample, which is both antioxidant as well as copper (in the above-mentioned concentrations), the increased Induction period to 745 minutes. The metal deactivator solution according to the invention served to offset the harmful influence of copper and a gasoline of to deliver high resistance.

Example 6 The metal deactivator solution described in Example 5 was used to stabilize lard, the lard had a normal shelf life of 4 hours when determined by the active oxygen method, a standard test to determine the shelf life of lard, which consists in letting air through blows a sample of the lard and periodically determines the peroxide number. The results are reported as the number of hours required to obtain a peroxide number of 20 to reach.

In order to determine the influence of metal, one was made about 72 mm wider Strips of copper wire 1 mm in diameter were added to a sample of the lard. The shelf life of the lard was reduced from 4 hours to 1 hour. at Addition of the metal deactivator solution described above to that containing the copper However, Schmalz has increased its shelf life to 4 hours. Here again it can be stated that that the metal deactivator solution according to the invention the harmful influence of copper picked up.

Example 7 Comparative Experiment Pure disalicylal propylenediamine which by condensation of 2 moles of salicylaldehyde with 1 mole of propylenediamine (1,2-diaminopropane) was used to prepare the following solutions A and B: Solution A 40 percent by weight disalicylal propylenediamine 60 percent by weight pure toluene Solution B 40 percent by weight disalicylal propylenediamine 54 percent by weight pure Toluene 6 percent by weight pure methanol The glass flasks containing these solutions were cooled to -17.8 ° C, then with crystals of disalicylal-propylendia.min. vaccinated and in a cold box at a temperature of -15 to -20.6 ° C for 48 hours kept for a long time with occasional shaking. In the glass flask with the solution A copious crystal deposition occurred during this 48 hour period on the other hand, there was very little crystal growth in the flask with the solution B on. The supernatant solution from each flask was removed and used for the copper deactivation test, as described above, used in a gasoline blend made by Mixing of fractions of catalytically cracked gasoline, reformed gasoline and directly extracted light petrol was produced. They were from this mixture Mercaptans removed by treatment with @ a solution of caustic soda in methanol been. The gasoline mixture thus obtained for these tests had an induction period of 95 minutes when tested according to ASTM method D 525-55 for resistance to oxidation of gasoline as indicated in Example 5. After adding 0.01 percent by weight of the Antioxidant N, N'-di-sec-butyl-p-phenylenediamine to another sample of the same Gasoline, the gasoline induction period was increased to 560 minutes.

Part of the gasoline mixture with 0.01 percent by weight of the N, N'-di-secondary-butyl-p-phenylenediamine Enough copper naphthenate was added to achieve a copper content of 1.0 mg per liter to surrender. Part of this solution with the added copper naphthenate was such an amount of the supernatant liquid from solution A was added that the metal deactivator content the resulting gasoline mixture C would be 20 ° / a higher than the stoichiometric Amount that is required to bind all the copper, if the supernatant solution nor the 40 percent by weight of the disalicylal-propylene-dianzin originally containing solution A would have had. In general, at least this excess amount is disalicylal propylenediamine required for significant copper deactivation, and usually becomes a An excess of 50 to 100% is used to completely deactivate the copper. One Induction period of only 75 minutes was observed on gasoline mixture C, the the antioxidant, the added copper naphthenate and the deactivator of the supernatant liquid of the cooled solution A.

Another gasoline blend D was prepared, which is also 0.01 Percentage by weight of the antioxidant N, N'-di-secondary-butyl-p-phenylenediamine, Copper naphthenate in an amount corresponding to 1.0 mg copper per liter of gasoline. and such an amount of the supernatant portion of solution B contained that the metal deactivator content the resulting gasoline mixture would also be 20% greater than the stoichiometric one Amount required to bind all of the copper if the protruding Solution still the 40 percent by weight of what was originally in solution B. Disalicylal-propylenediamine. An induction period of -405 minutes was observed on this gasoline mixture D. It should therefore be noted that the Metal deactivator solution according to the invention does not cause any loss of active ingredient suffered during the extended cooling even at -15 to -20.6 ° C and was able to to counteract the harmful influence of copper, so that a gasoline of high Persistence was obtained.

Claims (2)

PATENT CLAIMS: 1. Organic metal deactivator composition for the stabilization of hydrocarbon oils or fatty acid glycerides of animal or vegetable origin against the oxidative change catalyzed by metals, consisting of condensation products of aromatic o-oxyaldehydes with alkylene polyanines and an organic solvent, characterized in that the metal deactivator composition consists of 35 to 70 percent by weight of said condensation product and 65 to 30 percent by weight of a solvent mixture of a benzene hydrocarbon and an alcohol having 1 to 4 carbon atoms per molecule, in which the alkanol is present in a concentration of 5 to 35 percent by weight. 2. Composition according to claim 1, containing a disalicylal-alkylenepolyamine in which the alkylene group has 3 or 4 carbon atoms, characterized in that the solvent mixture consists of toluene and methanol. Pamphlets considered; U.S. Patent Nos. 2181121, 2181122, 2533205.