DE1122653B - Process for improving the color and color fastness of petroleum hydrocarbons - Google Patents

Description

INTERNAT. KL. C 10 g

GERMAN

PATENT OFFICE

B 58281 IVc / 23 b

REGISTRATION DATE: JUNE 21, 1960

KNOWLEDGE OF THE REGISTRATION AND ISSUE OF THE
EDITORIAL: JANUARY 25, 1962

The invention relates to a process for the catalytic hydrogenation of petroleum hydrocarbons, in particular color-unstable fractions boiling in the range of 150 to 300 ⁰ C, z. B. kerosene and vaporising tractor oils.

It is known to subject petroleum fractions boiling in the range from 150 to 300 ^° C. to catalytic hydrogenation in order to lower the sulfur content and improve the odor. However, straight-run fractions consist of certain crude oils, ζ. Β. ίο certain crude oils from Iran or Iraq, such as Agha Jari and Jambur crude oils, have an additional problem, namely poor color and poor color stability. Color instability can also result in an inherently color-stable material through previous treatment, e.g. B. by catalytic cleavage, are brought in. This color instability is of course undesirable. It has now been found that when catalytic hydrogenation is used to improve color and color stability, there is an optimal temperature for this treatment. The improvement is less at lower temperatures, but too high a temperature is also unsuitable. This optimum temperature has no relation to the temperature for maximum desulfurization, since the sulfur removal increases with the increase in temperature to at least 427 ^° C. This optimal temperature will also vary depending on whether the product is subsequently distilled to remove a small percentage of the bottoms.

According to the invention, a color-unstable ^{fraction boiling in the range from 150 to 300 0} C is treated in the presence of hydrogen with a hydrogenation catalyst at a temperature of 354 to 399 ° C, with any hydrogen sulfide formed being separated from the product and the product is redistilled to a remove low percentage of bottom product.

Process for improvement

of color and color fastness

of petroleum hydrocarbons

Applicant:

The British Petroleum Company Limited,
London

Representative: Dr.-Ing. A. ν. Kreisler, patent attorney,
Cologne, Deichmannhaus

Claimed priority:
Great Britain June 24, 1959 (No. 21 626)

Dennis George Adlington and Kenneth Tupman,

Sunbury-on-Thames, Middlesex (Great Britain), have been named as inventors

In addition to improving the color stability the process also reduces the sulfur content of the insert if it contains sulfur. The procedure is particularly suitable for the treatment of straight-run fractions and their extracts.

Any suitable hydrogenation catalyst can be used, which must also be sulfur-resistant if the Use contains sulfur. A catalyst that is preferably used consists of cobalt oxide and molybdenum oxide (as such or in bound form or in both forms) on a heat-resistant oxide, for example aluminum oxide, as a carrier. The following proportions can be selected:

Cobalt oxide (expressed as Co O) 1 to 8 percent by weight

Molybdenum oxide (expressed as MoO ₃ ) 5 to 40 percent by weight

Alumina remainder

A temperature of 360 to 388 ^° C. is particularly preferred. The pressure can be between 4.5 and 71 kg / cm ² . In general, higher pressures result in higher color stability, so pressures of 36 to 71 kg / cm ^{2 are} preferred, although they are not essential. The room flow velocity can be between 0.1 and 20 V / V / hour. lie. The use of higher pressures usually enables higher space flow rates to be used. The process is carried out in the presence of hydrogen, which can be recycled or used in straight pass with a net hydrogen consumption. It can be pure hydrogen or a larger part of hydrogen

109 787/368

3 4

Gas, ζ. B. the residual gases from a catalytic refor- Example 1

mieranlage, can be used. The amount of hydrogen A obtained from Iranian crude oil (Agha-Jari)

can be up to 360 m ³ / m ³ . The lower limit straight-run kerosene of a specific gravity of

corresponds at least to the gross hydrogen 0.8050 at 15 ° / 15 ° C, its initial boiling point at 176 ° C

Consumption, which for most of the feedstocks 5 and whose end boiling point was 257 ° C., was below

and processing conditions at least 1.8 m ^s / m ³ Use of a catalyst made of 2.4 weight

amounts to. percent cobalt oxide (expressed as CoO) and

The hydrogen sulfide can be expressed in part by the 14.3 percent by weight molybdenum oxide (

usual high pressure and low pressure gas separator as Mo O ₃ ) hydrogenated on aluminum oxide. The sulfur

and also by washing soda and / or stabilization ίο hydrogen was stabilized by the product

removed. removed, which was then redistilled, with 1 to 2

During the redistillation, percent by weight of the bottom product is preferably removed,

no more than 10 percent by weight of the soil product

removed. Usually, 0.5 to c and that at various temperatures are sufficient

5 percent by weight. 15 products obtained are listed in Table 1.

Table 1

working conditions
Pressure, kg / cm ² 15

Space flow velocity,

V / V / hr 4.0

Gas cycle volume, m ³ / m ³ 180

Product treatment H ₂ S and bottoms removal

Results mission 327 ° C temperature
388 ° C 416 ° C Sulfur content, percent by weight ..
Saybolt color
at the start
after storage at 71 ⁰ C for
1 day
4 days
12 days 0.237
23 0.020
> +30
+25
+21
+21 0.004
> +30
> +30
> +30
+23 0.002
+ 30
+30
+26
+ 17

The results show that although the desulfurization increased with increasing temperature and the color of the Products was good at all three temperatures but obtained maximum color stability at 388 ° C became.

Example 2

An evaporating tractor oil with the following key figures was treated: Specific weight at 15 ° / 15 ° C = 0.8170, initial boiling point 148 ° C, final boiling point 251 ° C. It consisted of 53 percent by volume of straight run naphtha and 30 percent by volume of with SO ₂

obtained kerosene extract and 17 percent by volume straight-run kerosene. All components originated from Iranian crude oil (Agha-Jari). This oil was

4 ° using that mentioned in Example 1 Catalytically hydrogenated catalyst. The hydrogen sulfide was removed from the product by stabilization removed. The products were then redistilled to remove 1 to 2 percent by weight of bottoms.

45 distant. The working conditions and indicators of use and at different temperatures The products obtained are shown in Table 2.

Table 2
working conditions

Pressure, kg / cm ² 15

Space flow velocity,
V / V / hr 4.0

Gas cycle volume, m ³ / m ³ 180

Product treatment Removal of H ₂ S and bottoms

Results mission temperature
327 ° CI 388 ° C 0.006
> +30
> +30
+30
+ 17 416 ° C Sulfur content, percent by weight ..
Saybolt color
at the start
after storage at 71 ° C for
1 day
4 days
12 days 0.450
<16 0.053
> +30
+22
+ 18
+ 17 0.003
> +30
> +30
+24
+ 13

The table shows that hydrogenated with respect to sulfur deaerator. The removal of hydrogen sulfide

Distance, color and color stability values similar to those obtained in Example 1 were obtained.

Example 3

The use mentioned in Example 2 was carried out using the catalog described in Example 1 and redistillation were also carried out as in Example 2.

The working conditions and indicators of use and those obtained at different temperatures Products are listed in Table 3.

Table of working conditions

Pressure, kg / cm ² 10.5

Space flow velocity,

V / V / hr 3.0

Gas circulation volume, m ³ / m ³ 180

Product treatment Removal of H _{2 and} bottom product

Results

mission

327 ° C 343 ⁰ C

temperature
36O ⁰ C

388 ° C

416 ° C

Sulfur content, percent by weight

Sayboldt color
at the start

after storage at 71 ° C for

1 day

4 days

12 days

0.450

0.055 +30

+

+ +> +30

+ 19
+ 11
+ 9

0.010
> +30

> +30
+ 30

+22

0.009> +30

> +30 +26

+ 17

0.005> +30

+ 29

+21

+ 4

The results show that the desulfurization increased with increasing temperature and the initial color of the products was good at all five temperatures but the maximum color stability was achieved at 360 ° C.

The results obtained in the three examples are shown graphically in the attached diagram. It can be seen that the optimum temperature for color stability is in the range from 360 to 388 ^° C. This optimal temperature is not related to the temperature for maximum desulfurization.

Claims (2)

PATENT CLAIMS: 1. A process for improving the color and color stability of color-unstable hydrocarbon reactions (boiling point 150 to 300 ° C) by hydrogenation in the presence of sulfur- resistant catalysts, characterized in that the starting material is at 354 to 399 ° C, preferably at 360 to 388 ° C , treated and the product redistilled. 2. The method according to claim 1, characterized in that at pressures between 4.5 and 71 kg / cm ² , preferably between 36 and 71 kg / cm ² , room flow rates between 0.1 and 20 V / V / hour. and a hydrogen velocity up to 360 m ³ / m ³ works. Documents considered: German Patent No. 927 593;
French patents nos. 1 147 441, 958 951, 1,134,183; U.S. Patents Nos. 2,761,815, 2,794,766, 2,061,845; British Patent Nos. 721 302, 769 510; Austrian Patent No. 173,684; Chem. Zentralblatt, 1956, p. 13895, work by W. W. Scheumann; Kalichevsky and Stagner, Chemical Refining of Petroleum, New York, 1942, pp. 237 and 198. 1 sheet of drawings © 109 787/368 1.62