DE958234C - Process for stabilizing hydrocarbon distillates - Google Patents

Description

ISSUED FEBRUARY 14, 1957

U 2769IVc 123b

The invention relates to the stabilization of hydrocarbon distillates against discoloration and / or the formation of sediments.

The invention is intended for use with hydrocarbon distillates whose boiling range is substantially above that of gasoline, mainly in the range of about 150 to about 400 °. These oils are commercially available under various names such as burner oil, fuel oil, fuel oil, furnace oil, and diesel oil, and are preferably used in burner systems, diesel and internal combustion engines, and various other industrial and domestic appliances. This class also includes jet nozzle oils and other hydrocarbon distillates which, within the above-mentioned range, include constituents with a boiling point and also constituents with a lower boiling point. Jet nozzle oils can, for. B. have initial boiling points of only about 15 ° and an end boiling point in the range of about 230 to about 315 ⁰ or higher.

Most of these oils will sediment or discolor upon storage. The sedimentation is harmful because it easily clogs filters, burner tips or injectors. The im The precipitate contained in diesel oil tends to

application of varnish and sludge in the diesel engine. Discoloration of burner oil is z. B. disadvantageous for various reasons, in particular because consumers usually prefer light colored oils.

The discoloration and precipitation in storage containers vary considerably with the origin of the oil and with the treatment that the oil received in the refinery. Currently ίο the oils mainly come from two sources, namely from the non-destructive and the destructive, d. H. cracking distillation of petroleum. Products from the first source are referred to as direct distillates, while those from both non-catalytic and catalytic cracking in general as cycle oils are designated because they are separated from fractions that are recycled to the cracking process for the purpose of further conversion. Other sources of the oil can in the conversion of carbon monoxide with hydrogen in such processes as the Fischer-Tropsch synthesis and oxo processes exist. The scope of the invention also includes lubricating oils, transformer oils, turbine oils, which are subject to excessive decomposition during storage. The present shelf life issues get even more complicated when the Oil is blended from two or more different oils.

It has been found that oil decomposition of the type described through the use of an additive can be retarded as a salt of a carboxylic acid and an alkylalkylene polyamine can be designated.

According to the invention, hydrocarbon distillates are at least to a substantial extent Boil above the gasoline boiling range, stabilized by the fact that a salt is one of them Carboxylic acid and an alkyl substituted alkylene polyamine is added.

The carboxylic acids and to be used in each case for the preparation of the additive Amines can be very different depending on the particular oil to be stabilized. In general the carboxylic acid and the amine are selected so that the salt is easily in the oil in the too using salt concentrations is soluble. In general, it should be the total number of carbon atoms be at least 20 in the salt. As will be detailed below, there is a preferred additive of a fatty acid salt of an alkylpropyldiamine, its alkyl group comes from a fatty acid.

Suitable alkylene polyamines are the alkyl derivatives of ethylenediamine, propylenediamine, butylenediamine, amylenediamine, hexylenediamine and homologues as well as triamines, e.g. B. diethylenetriamine, dipropylenetriamine, dibutylenetriamine and Homologues, tetramines such as triethylenetetramine, tripropylenetetramine, tributylenetetramine and Homologues. Other polyamines can also be used, such as tetraethylene pentamine and tetrabutylene pentamine. As stated above, the additive contains a sufficient number of carbon atoms so that the additive is readily soluble in the burner oil. Appropriate can be an essential Part of the carbon atoms included in the alkyl substituent attached to the alkylene polyamine be. The preferred alkylalkylenepolyamines can be represented by the following general formula:

R-NH-R'-NHR ",

wherein R and R "are hydrogen or an alkyl group, at least in one case an alkyl group are, while R 'is an alkylene radical. R or R "are mainly alkyl groups with at least 6 carbon atoms, preferably 10 carbon atoms.

In the case of a particularly suitable alkylalkylenepolyamine, R 'denotes a propylene radical and R denotes Alkyl group derived from tallow and R ". Hydrogen. This alkylalkylene polyamine is commercially available and is hereinafter referred to as polyamine A. With others, appropriately substituted Propylenediatnines, R denotes an alkyl group derived from lauric acid, coconut oil or soya oil. The above-mentioned alkylpropylenediamines are currently commercially available and are mixed alkyl-substituted propylenediamines. In the case of polyamine A contains z. B. the alkyl radical 12 to about 20 carbon atoms per group and mostly 16 to 18 carbon atoms. If so desired however, the alkylalkylene polyamine can be represented as having any number of carbon atoms which are desired in the groups R and / or or R ". So either or both of these Groups from methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl or eicosyl. In general, one of the substituents R and R "is preferably hydrogen and the other is 105, an alkyl group having at least 6 and preferably more than 10 carbon atoms. To note is that a mixture of different amines can also be used.

Any suitable carboxylic acid can be used to form the additive be monobasic or polybasic. The particular carboxylic acid to be used is based on the The particular polyamine used is selected so that the resulting salt is readily soluble in the fuel oil is. It preferably contains at least 6 and in particular 10 carbon atoms per molecule. the Carboxylic acid can be made from formic, vinegar, propionic, butter, valerian, trimethylacetic, oxalic, Malonic, succinic, glutaric, itaconic, mesaconic, citraconic or glutaconic acid exist. Preferably However, it contains at least 6 carbon atoms and is therefore appropriate among the the following selected: Kapron-, Heptyl-, Capryl-, Adipin-, Pimelin-, Suberin-, Azelain-, Sebacin-, Phthalic acid, etc., capric, lauric, myristic,

Palmitin-, stearin-, arachin-, behen-, lignocerin-, cerotin-, decylene-, dodecylene-, palmitolein-, olein-, Ricinol, petroseline, vaccine, linseed oil, linolenic, Eleostearin-, Lican- ', Parinar-, Taurin-, Gadeloin-, Arachiodonic, cetoleic, erocin, selacholeic acid etc., aconitic, lemon, gluconic, hemimelittic, Trimellite, trimesic, prehnitic, mellophinic, pyromellitic and mellitic acids. It should be noted that a mixture of acids can be used.

«Ο A particularly preferred acid consists of one mixed by-product acid which is commercially available and hereinafter referred to as acid B. will. This acid is essentially a mixture of dibasic acids and is believed to have im

iS mean 35 to 50 carbon atoms per molecule.

Another particularly preferred acid consists of tall oil acid, which is a mixture of resin acids and is fatty acids and has an average of 16 carbon atoms contains per molecule.

In general, the neutral salt of the acid and the amine is preferred. The neutral salt will prepared by reacting stoichiometric amounts of acid and amine, in other words the concentration of carboxylic acid and amine is selected to be an equivalent number from carboxylic acid groups to amino groups is present. The respective concentrations depend So it depends on whether the acid is monobasic, dibasic, tribasic or higher basic and whether the amine is a diamine, triamine or higher polyamine. In another embodiment, the salt can be a basic salt, preferably by using a deficit of carboxylic acid groups in relation to the amino groups, ζ. Β.

by using 1 equivalent of carboxylic acid to 2 equivalents of amine. At a In another embodiment, an acid salt can be used which is obtained by using a Excess of acid (polybasic acid) in relation to the amine, e.g. B. 2 equivalents of acid to i equivalent "amine. It should be noted that these various salts are not necessarily are equivalent to each other in their effect.

The salt can be obtained in any suitable manner; in general it can be done easily by mixing the acid and the amine at room temperature, preferably with vigorous action Stir, represent. The salt is easily recovered at room temperature, although slightly increased Temperature, which in general should not exceed 93 °, can be used. Excessive Temperature should be avoided because amides and other undesirable reaction products can be formed. Depending on the particular amine and acid used, it may be appropriate be to use a solvent to get a better mixture of the acid and / or the To achieve amines before or during their mixing. In some cases it may be desirable mixing the salt with a solvent to form a more fluid end product. Each suitable solvents can be used; a hydrocarbon distillate is expediently chosen.

The amount of additive to be used depends on the particular salt and oil in which which one to use. In general, the additive will be in a concentration of less than about 5 percent by weight, ranging from 0.0001 percent to 5 percent by weight, preferably within the range from 0.0001 to ι percent by weight of the distillate. This additive can be used together with the other additives required for special. Purposes to be added to a distillate.

The following examples serve to further illustrate the invention.

example 1

The alkyl polyamine used in this example is polyamine A. As noted, polyamine A is commercially available and has a theoretical molecular weight of 320 and a composite molecular weight (based on 80% active ingredients) of about 400. It is a soft paste and has a melting range of 44 to 48 ⁰ . The acid B used in this example is, as already mentioned, commercially available and liquid at 25 °. It has an acid number of about 150 and an iodine number of about 36. It can be assumed that this acid contains about 35 to 50 carbon atoms in the molecule. As mentioned above, this acid is a by-product and is therefore available at a relatively low cost. Since, as will be shown in the following examples, it provides a very effective additive, the use of this acid is particularly attractive because of its low cost. 374 parts by weight of polyamine A are moderate, that is at about 52 ^0, heated, and 726 parts of the acid B are mixed. Mixing is carried out at room temperature and then vigorously stirred. A hydrocarbon solvent is added to increase the flow activity.

The resulting salt is a neutral salt and was used to stabilize common fuel oils used. The fuel oil samples were subjected to accelerated aging for 2 hours at 100 ° subjected, and the colors of the various pro-im ben were in a spectrophotometer, which is particularly suitable for such color determinations is determined. Distilled water was given as a comparative value of 100 and a very dark oil with O specified in this analysis.

A # 2 commercial catalytic fuel oil had an original color of 93.7. After accelerated aging, the color of the oil fell to 3. That prepared in the above-mentioned manner Salt was added to another sample of this fuel oil in an amount equal to 0.005 percent by weight of the oil was added, and after accelerated aging the sample had a color of 71.

It should be noted that after the accelerated aging, the sample without additives is very dark

and had a color of 3, while the sample with additive was still after the accelerated Aging had a color of 71.

Example 2

As mentioned above, the burner oil may be used in the system in which it is used, do not clog. This is being accelerated

Circulation test determined in which a sample of 7.57 l of oil was passed by means of a gear pump at constant flow rate in the circuit first through a nozzle of the so-called gun burner with the usual screen filter and then through an edge filter with openings of 0.005 ^cm . A clogging of the filter at the nozzle is indicated by an increase in pressure on the outlet pump, while a clogging of the edge filter is indicated by the development of a

ao suction is displayed on the pump inlet side. The suction on the pump inlet side holds at zero for a time and then shows a rapid one Increase, simulating an induction period. The one required for this climb

»5 Time is called the» inflection point «. This The experiment is easily reproducible and shows the clogging properties of the oil.

The oil used in this example was a # 2 commercial fuel oil. This oil had one original inflection point of 33 hours. After adding 0.005 percent by weight (based on on the oil) of the additive described in Example 1 the inflection point rose to 61. After adding 0.01 percent by weight of this additive the inflection point increased to 84 hours for another oil sample.

From the above values it can be seen that the additive according to the invention to one serves to delay the inflection point of the oil considerably, and thus the clogging properties delayed.

Example 3

The oil used in this example was West Texas Thermal No. 2 fuel oil, which is a original inflection point of 7 hours. After adding 0.005 percent by weight (based on on the oil) of the additive described in Example 1, the inflection point rose 14 hours. The time before constipation occurs is thus doubled.

Example 4

The additive used in this example was a basic salt of polyamine A and acid B. and was prepared by mixing 2 equivalents of amine to 1 equivalent of acid. 0.01 percent by weight (based on the oil) of the additive increased the inflection point of another Sample of fuel oil No. 2 as described in Example 1 from 33 hours to 84 hours.

Example 5

The additive used in this example is polyamine A dioleate made from polyamine A. and oleic acid.

0.005 percent by weight (based on the oil) of this additive increased the inflection point of a Another sample of fuel oil No. 2, as described in Example ι, of 33 hours 76 hours.

Example 6 Example 7 Example 8 Example 9

In order to confirm the results that can be achieved with the cycle test according to Example 2, Samples of the oil described in Example 2 analyzed according to the oil circulation method, as reported by Rescorla, Cromwell and Milson in "Analytical Chemistry", Vol: 24, lines 1959 bis 1964 (December 1952). The original oil had an inflection point of 40 hours. The addition of 0.01 percent by weight (based on the oil) of the additive, as it is in Example 2 described increased the inflection point of the oil to 72 hours.

An additive was prepared by mixing 186 parts by weight of polyamine A and 292 parts by weight of tall oil acid.

The additive prepared in this way can be used in a concentration of 0.02 percent by weight (based on the oil) are incorporated into a blended fuel oil that consists of a mixture a directly obtained distillate and a catalytic cycle mass. This will a delay in the oil and a reduction in sedimentation achieved.

The polyamine used in this example is N-lauryl-1,4-butylenediamine. The lauryl radical represents an alkyl group derived from lauric acid. The lauryl-butylenediamine is combined with stearic acid mixed to form the corresponding salt.

The additive prepared in the above manner becomes a commercially available light color catalytic cycle oil in a concentration of 0.008% (based on the cycle oil) added and serves to delay the discoloration and the formation of a sediment therein.

A jet fuel consisting of a mixture of cracked recycle feed and directly obtained distillate can be prevented from decomposition by adding 0.01 percent by weight (based on the mixture) of lauryl butylene

diamine, as described in Example 8, can be stabilized.

Example io

Lubricating oil can prevent spoilage by adding 0.5 percent by weight (based on the oil) of the additive prepared according to Example ι be stabilized.

Claims (4)

Patent claims: i. Process for stabilizing hydrocarbon distillates, which boil mainly above the gasoline boiling range, characterized in that they have a soluble and at least Salt of a carboxylic acid and a salt containing 2O carbon atoms in the molecule alkyl-substituted alkylenepolyamine in an amount of stabilization effecting 0.0001% to 5% by weight of the distillate is added. ao 2. The method according to claim r, characterized in that the distillate is a salt of a Carboxylic acid and an alkyl substituted propylenediamine in which the alkyl substituent at least 6 and preferably 12 to as Contains 20 carbon atoms, is added. 3. The method according to claim 1 or 2, characterized in that the distillate is a Salt of a polybasic, in particular dibasic, carboxylic acid with 35 to 50 carbon atoms is added in the molecule. 4. The method according to claim 3, characterized in that the distillate is a neutral salt from the acid and the amine is added. © 609579/466 8.56 (609 797 2.57)