DE1470531A1 - Process for improving and / or stabilizing, in particular color stabilizing oils - Google Patents

Description

ESSO Research A Engineering

Company

Elizabeth. HJA, St, A. Hamburg, May 24, 1961

Process for improvement and / or stabilization, in particular color stabilization. of oils.

The present invention relates to a method for stabilizing, in particular dyeing tabulation, oils as well as for reducing the abdominal density during combustion. The present invention relates in particular to heaters and preferably to those which obtained by catalytic tracking; she lets but can also be used generally for hydrofined base oils and lubricating oils «

The catalytic cracking creates unstable substances, which are found in various oils and for example can be found in sohwerem heating oil «The effect of these unstable substances shows itself 'during storage or Warming up of the oil and is particularly noticeable if the oil has previously come into contact with oxygen is,. This is, for example, the tall if it is stored in the presence of extremely off-containing substances, such as air although decomposition occurs to some extent even in the absence of oxygen. The decomposition process is evidenced by darkening or discoloration

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of the oil and can proceed further to the point of precipitation of carbon, tar and gum, which leads to damage to machines or devices operated with such oils. These volatile substances are generally present in the cracked oil in small amounts, less than $ 1.

When fuel oils are burned, they are generally produced more or less smoke and soot. This smoke and soot build-up increases when the aromatic content of the oil increases according to its origin is greater · Understandably, one always strives to reduce the smoke density and soot formation as much as possible.

So far, methods have been used to overcome these disadvantages, which either aim to remove the unstable Substances or were based on the attempt to transform them into permanent colorless substances. Numerous Mineral clays, soils and artificial mineral absorbents were used to prevent the discoloration Removing contaminants from oils »There are numerous However, substances have been proposed with no noticeable success for converting these volatile substances into permanent or stable colorless substances; for example was proposed a treatment with quicklime, which, however, resulted in only an extremely small improvement, namely itself then when extremely violent and uneconomical methods

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were used · 'Also leads to hydrogen treatment to stabilize the substances, but only after the undesired color decomposition has occurred. tuck Methods as well as treatment with sulphurous acid, Iron-2-sulfate, tin-2chloride, acetic anhydride and other substances have so far proven to be satisfactory.

Surprisingly, it has now been found that certain substances belonging to the class of hydrazines and hydroxylamines, such as hydrazine, hydrazine · hydrate, fhenylhydrazine, dinitrophenylhydrazine, tetraphenylhydrazine, methylhydrazine, ethylhydrazine, hydrazobenzene, Hydrazone derivatives and hydroxylamine, even in extremely small amounts, have a remarkable stabilizing effect of troublesome substances and prevent their further implementation in the presence or absence of oxygen or delay, so that a discoloration, which may lead to further precipitation of the undesired substances can lead, avoid or delay; at the same time, the smoke density is also reduced during the combustion. It has also been found that, surprisingly, an even greater reduction in smoke density can be achieved if a metal sulfonate, such as for example calcium sulfonate, is added. The reaction can be carried out, for example, at room temperature a simple mixing process can be carried out, and it

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it was found that the addition of a weight part Hydrazine hydrate or an equivalent amount of above mentioned substances to 10 to 20,000 parts by weight of oil gives a substantial improvement, although the present Of course, the invention is not restricted to these quantities.

If a metal sulfonate is incorporated, it is preferably dissolved in a solvent such as benzene and is added in amounts of 0.001 to 1 weight percent »

In the following, the invention is intended to be based on examples to be discribed; in examples 1-7 the substance was added directly to the oil sample and shaken, to make either a solution or a fine dispersion obtain·

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■ * ■ · < X ··. '■' ■ ■ ■■■ "

example 1

A mixture of light and heavy rice was produced in a mixing ratio of 1: 2 parts by volume. The initial color values labeled "TR ¹ *" were read on a Tag-Robinson color measuring device. The test for color resistance was carried out after the robe had been stored for 16 hours at 100 ° C. and then cooled.

treatment treatment ΑγιΐΡ * νη £ ΤΡ— Sarcophagus
theness Treated Untreated color value 9 TR 1. 50 ppm hydrazine hydrate 100 ppm hydroxylamine 16.5 TR 9.75 2. as with 2 »after 3 washes
with water 0.1 i »Bydroxylamin 16.5 TR 10.5 3. 100 ppm hydrazine hydrate 1, O ^ hydroxylamine 16.5 TR 11.75 4th as with 4. after 3 washes
with water Example 3 16.5 11.75 5. Example 2 16.5 TR Barbeque
didceit 1. Outweighed *? -
color value 8 TR 2. 16.75 TR 11.5 TR 3. 16.75 TR 10 TR 4th 16.75 TR 9.7? TR 16.75 TR

The samples were shaken with oxygen and stored in contact with air at room temperature for 14 days before they were treated "

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ORIGWAL ΙΝβΡΒΟΤΒΟ

I ^ ftliftnfllwv At first
color value Taring stock
theness 13th 1.25 1ο Untreated 13th 9.25 2, 8.2 ppm hydroxylamine 14th . 9.25 3. as with 2. after washing
with water 13th 9 4, 50 ppm hydrazine hydrate 13th 9.25 5, as with 4ο after washing
with water

Example 4 Both samples were taken in the dark at room temperature

stored in the absence of air »

Treatment of the initial parboil

color value

1> Untreated 16.5 12.25

2, 10O ppm kortrazine hydrate 16.5 16.25

Example 5

In this experiment, a cracked fuel oil with a Throughput speed i # ce it of 10 VA per hour through a hot snake passed through · All samples were pre and under a nitrogen blanket during the experiment protected from air.

Treatment of initial color value after

color value pass through to through the coil

cd 1 »untreated snake temp,

a> 260 ° C 16.25TH. 13th

K> 2 «Unb © acts snake nt · βρ. ^ 288-315 ° C

ο 3 '100 ppm ^ draainhydrat _f 260 ° C 2 4, 100 ppm 5 »1000 pp * fry ξβ | *

16 , 25 TR 10 TH 16 • 25 TR 15th TH; 16 • 25 SR. 12th TR 16 «25 TR 14th -7-

Example 6

Samples of light fuel oil (LHO) and heavy fuel oil (HHO) with the specified color values were after 16 hours of heat treatment at 100 ° C without additive (a), with 100 ppm hydrazine (b) and treated with 50 ppm hydrazine, with the following results:

Original color values after 16 hours of handling Color at 100 ° C

none 110 ppm 50 ppm hydrazine hydrazine hydrazine

LHO 22.75 TR 1 * 5 TR 9.0 TR 9.50 TR HHO 16.75 TR 0.25 TR 11.50 TR 10 TR LHO 23.25 TR 1.25 TR 9.25 TR 9.50 TR HHO 17th TR 0.25 TR 9.25 TR 8.50 TR LHO 24.50 TR 1 TR 9.25 TR 8.25 TR HHO 17th TR 0.25 TR 11.50 TK 8.75 TR LHO 22.75 TR 1.50 TR 9.0_ TR 9.50 TR HHO 16.75 TR 0.25 TR 11.50 TR 10 TR Example 7

A yambur qesöl, soaked in air for several months Storage decompose, was 1000 ppm (based on the Volume) hydrazine hydrate treated and hydrofined * Am comparison of the values of the treated and untreated Hydrogenated jambur gas oils showed a substantial Improving the turbidity of the oil used in accordance with the invention » namely:>

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Base oil: color value 12.75

Not treated with hydrazine "and hydrofined at 315 oil: color value 12.75

Hit hydrazine treated

and hydrofinishing at 315 °

tes oil color value '24, 5 IR

As already mentioned, the addition of hydrazine or the above-mentioned derivatives of hydrazine or of hydroxylamine not only improves the color fastness of the oils according to the invention, but also reduces the smoke density during their combustion, this effect being further increased by adding a metal sulfonate on the oils is strengthened. For example, the presence of phenylhydrazine in a concentration of 0.25% by weight results in a 27% reduction in smoke density. It was also found that adding hydrazine derivatives beyond a certain value does not result in any further reduction in smoke density, but that the additional incorporation of a metal sulfonate in the oils according to the invention achieves a further and surprising reduction in smoke density _e oil which contains 0.25% by weight of the above-mentioned phenylhydrazine, an amount of 0.15% by weight of calcium sulfonate was added

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there will be a decrease in smoke density from Ue to 46 #. This effect is illustrated by the following Examples explained which with a C.F.R. Motor F 5 were carried out under the conditions according to ASTM to determine the cetane number «

Example 8

10 g of phenylhydrazine were dissolved in 10 ml of benzene and to 5 1 one (Jasöle8 added, which at 15 ° C a Density of 0.840, a cetane index of 50 and a distillation characteristic according to ASTM of 185 ° C (starting point) and 355 ° C (end point). It became the following values obtained} whereby the comparison measurement was carried out with 5 l of gas oil which contained 10 ml of benzene:

Comparative measurement Measured value Reflectance 35 46 Smoke Diohte 45.6 33.7

Reduction in smoke consumption

₁₀ 0 χ , «26

Example 9

6.3 g of calcium sulfonate and 10 g of phenylhydrazine were in Dissolve 10 ml of benzene and add 5 l of gas oil according to Example 8 added »The following values were obtained!

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Verffleiohsmesaung measured value reflectance 35 57

Smoke density 45.6 24.4

Reduction in smoke density ¹⁰⁰ * 45.6

The smoke density was "determined by the proportion of the reflected light measured in percent with a suitable known device for determining the abdominal density and calculated according to the following formula

Smoke density - 100 χ log 10

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Claims (2)

Claims. 1. Process for improvement and / or stabilization of irritant and gas oils, characterized in that ( a hydrazine, a hydroxylamine or a derivative thereof is incorporated into the oils. 2. The method according to claim 1, characterized in that that a metal sulfonate is added to the oils » 3- The method according to claim 2, characterized in that that the hydrazine derivative is a phenylhydrazine and the sulfonate is a calcium sulfonate. 4. Process according to claims 1-3, characterized in that 50 to 1000 ppm based on the weight of hydrazine, hydroxylamine or a derivative are added to the oils same adds. 5. The method according to claim 2, characterized in that that one has about 2000 ppm phenylhydrazine and about 1250 ppm Adds calcium sulfonate. 909832/1050 -2- 6 «Improved and / or stabilized oil, manufactured according to the method according to claims 1-5 <> 909832/1050