DE1236701B - Process for lowering the pour point of gas oils - Google Patents

Description

FEDERAL REPUBLIC

GERMAN

PATENT OFFICE

EDITORIAL

German class: 23 b -1/05

Number: 1 236 701

File number: L 34054 IV d / 23 b

Filing date: August 25, 1959

Display day March 16, 1967

The method concerns the lowering of the pour point of gas oils which are suitable for their use have too high pour point, and allows more gas oil with lower gas oil to be produced from a given crude oil Pour point than gain without this treatment.

For the use of a gas oil, e.g. B. as fuel for diesel engines, there are quality standards, which, among other things, apart from a low sulfur content, a maximum viscosity, the boiling behavior and the cetane number also relate to the pour point. There are maximum values depending on the climatic zone called from -18 to -7 ° C.

The only known way to lower the pour point of a gas oil without fractionation and the resulting losses are the addition of small amounts of certain substances, such as polymethacrylates. However, the effect of such additives is quite small (see Ulimann, Encyklopädie der technical chemistry [1955], vol. 6, pp. 601/602).

According to the invention, another route is taken, which is based on known processes for hydro refining or hydrocracking of hydrocarbon oils. This will go for an immediate one at the same time Use of unusable portions of the crude oil in the usable gas oil fraction.

Accordingly, gas oils having a pour point above -18 ⁰ C or above -7 ⁰ C in the presence · of oxides of cobalt and molybdenum, which are applied to the modified silica with aluminum oxide, as catalysts at such a temperature between 400 and 450 ⁰ C and such a pressure between 5 and 100 at such a space velocity between 0.5 and 10 using less than 15 moles of partly added, partly recycled hydrogen per mole of gas oil used so that the pour point of the fraction of the treated gas oil with the same boiling range as the the gas oil used is reduced below -18 ° C or below -7 ° C.

Space velocity here is the number of volume units of the liquid material to be treated understood per apparent volume of the catalyst and per hour. The indication of the amount of to The hydrogen used refers in mol to 1 mol of average molecular weight of the used Gas oil.

The presence of considerable amounts of silicon dioxide in the catalyst is very essential for the success of the process according to the invention. This must be at least 5% silicon dioxide, based on the sum of the alumina and the Siliciumdioxyds, and a maximum of 40 ° / ₀ silica based method for lowering the pour point
of gas oils

Applicant:

Labofina Societe Anonyme, Brussels

Representative:

Dr. F. Zumstein, Dr. E. Assmann

and Dr. R. Koenigsberger, patent attorneys,

Munich 2, Bräuhausstr. 4th

Named as inventor:

Thierry Ghislain Marc de Menten de Hörne,

Crainhem;

Joseph Eugene Marcel Marechal, Watermael

(Belgium)

Claimed priority:

Great Britain of August 27, 1958 (27 538),
dated August 20, 1959

on the total amount of catalyst included. Preferably there is a maximum of 25 percent by weight of Aluminum oxide-silicon dioxide mass made from silicon dioxide.

A thermal pressure treatment of hydrocarbon oils of various types over catalysts made of cobalt molybdate applied to aluminum oxide modified with silicon dioxide as a carrier is, is carried out many times in technology. It is generally about refining, especially desulphurisation of oils, or the refinement of petrol through reforming. at these known processes, which occasionally also include the treatment of gas oils, come - considered individually and in certain combinations - the above for the method according to the invention specified individual features are also taken into account. The overall combination of features is in each known case is different from that according to the invention. Because you are at the hydro refining basically striving to comply with the mildest possible conditions, to get as little as possible into the Intervene in the molecular structure of the hydrocarbons to be treated. The same applies to that

709 519/509

3 4

Hydroforming where it is - limited to the value of the process according to the invention

Treatment of gasoline - not increased by any increase, not just that of course

downsizing, but about a conversion which an effective desulphurization is achieved when

Molecules through isomerization, aromatization, d. H. the treated gas oil contains sulfur, but rather

at most hydrogen splitting, and the like. Acts. In 5 also by the fact that the viscosity and the cetane number

In this context, suffice it to say that the gas oil is to be improved.

the known methods in the inventively in. .

Considered temperature range only with e ι s ρ ι e

Working with catalysts of relatively low A gas oil that boils between 250 and 380 ° C

Reach into the effect. On the other hand, if you use io and have the following properties:

a catalyst modified with silicon dioxide, _o "

so this implies t>, / c in the point of initiation under consideration here

A reduction in the amounts of silica loading "f ^pul l ^ - Y '' ■ '■' ■ L '■ \ ΌΌ'Α λ

handling temperature. This must all the more space Redwood viscosity at 38 C 44

access how the silicon dioxide content of the catalyst 15 was with hydrogen in the presence of a catalyst

is increased so that then only treated at temperatures lysators, the following composition

down to 200 ⁰ C is worked. would have:

According to the new, different task MoO 14 ° / o

(Pour point reduction) the process according to CoO 2.4%

of the invention can be controlled differently. Coarse 20 g ^ Q 2i'o /

strives, it aims at the application of stricter conditions. AlO ... 72 6 ° / conditions of action, primarily through the

Use of catalysts with higher silicon working temperature 435 ⁰ C; Working pressure 50 kg / cm ² ; Dioxide content at relatively high temperatures. Without space velocity = 1; Hydrogen amount 15 moles that with high hydrogen consumption a widely 25 per mole of gas oil used. The product was added, unwanted cracking to gasoline and next by distillation in ^{gas boiling up to 200 0} C enters, thereby the gas oil boiling for the stagnation of the gasoline and from 200 ⁰ C boiling gas oil are broken down. Gas oil primarily responsible paraffins so the properties of these two fractions and modified so that they no longer interfere, and at the same of the separated from the gas oil Gas oil with the time, the highest boiling portions of the treatment 30 Initial boiling point 25O ⁰ C are good in the following Table I in advantageously only cracked so far that assembled in which the columns still remain in the gas oil boiling range as follows. In the end, the following are denoted: In this way, the badly used _{A Redwood} becomes effect. _Vi skosität at 38 ° C; raw gas oil em low-build gas oil in high τ. ο 1 · r> yield obtained. This yield ^{includes a 35% sulfur content} ; Top fraction with the start of boiling at 200 ^° C., C pour point;

which is known to be a normal component of a D volumetric yield, usable on use Represents gas oil. pulled.

Table I.

A. Al B. Bl C. Cl D. Dl mission 44
34
40 44
40 2.05
0.012
0.015 2.05
0.01
0.077 +1.7 ⁰ C
-9.4 ° C +1.7 ⁰ C
+1.7 ⁰ C 100
23
77
63 100
11
79 petrol Gas oil, start of boiling 200 ⁰ C
Gas oil, start of boiling 25O ⁰ C

If, in deviation from the invention, the same gas oil is treated under otherwise identical conditions, with the only difference that the catalyst is not silicon dioxide and instead more aluminum oxide contains, the results given in Table I under Al, B1, Cl and Dl are obtained. As can be seen, such a treatment has no effect on the pour point.

Example 2

A gas oil boiling from 250 to 39O ⁰ C with the following reproduced test results

lowing properties: draw on the reaction product, which after

Cloudy point 2 2 ⁰ C ^6o 12 hours running-in for a further 60 hours

Stocküunkt 1'7 ⁰ C was obtained. The fractions examined were

Redwood viscosity at 38 ° C ''.'.'"".'."41 ^{corresponding to a} ^ Example 1 described

Dieselindex g ^ewonnen 47 ^ways ·

Density at 15 ^o C / 4 ° C 0 876 In addition, the following properties were found

65 determined:

was under the conditions given in Example 1

treated with the amendment that the E Dieselindex;

The amount of hydrogen was 5 moles per mole. The im F density at 15 ° C / 4 ⁰ C.

Table II

A. B. C. D. E. F. mission 41
34.9
35.4
37.9 1.98
0.01
0.038 + 1.7 ⁰ C
-6.7 ° C
-6.7 ⁰ C
-3.9 ⁰ C 100
21
79
76.3
60.4 47
53
53
56 0.876 petrol 0.852
0.853
0.854 Gas oil over 180 ° C Gas oil over 200 ° C Gas oil over 25O ⁰ C

The hydrogen consumption was 471, that at O ⁰ C Heren noticeably decreased, while the diesel index increased.

and 760 mm were measured, based on 11 takes,

of the treated gas oil. The distillation curve of the fraction of the treated

As can be seen, the pour points of the gas oil take a boiling point at 250 ° C

Fractions, which in the same interval distil- 15 little below that of the use:

Start of boiling 10% 30% 50% 70% 90% mission 250 ° C
250 ⁰ C 270
262 300
290 322
310 349
. 332 382
368 Fraction of the treated gas oil

If, in deviation from the invention, one works under the same pressure and throughput as well as with the same amount of hydrogen over a catalyst, in which the silicon dioxide again passes through Aluminum oxide is replaced, significant reductions in the pour point are only achieved with Temperatures above the according to the invention in

The area under consideration, with an extraordinarily large proportion of the gas oil being split into gasoline will. This is shown in Table III below. The hydrogen consumption is below these Conditions 70 to 801 per liter of treated gas oil, that is more than under the conditions according to the invention of example 2.

Table III

A. B. C. D. E. F. mission 41
32.6
34.9
31.8
34.3 1.98
I.
0.01
0.01
0.01
I.
0.01
0.01
0.01 + 1.7 ⁰ C
operating recom
- 9.4 ^° C
-1.1 ^° C
operating temp
-15 ° C
-9.4 ⁰ C 100
temperature 465 ⁰ C
47
53
37
: temperature 480 ° C
76.5
23.5
7.5 47
45.5
48.5
35
37 0.876
0.856
0.860
0.871
0.883 Gasoline (0 to 200 ° C)
Gas oil over 200 ° C
Gas oil over 250 ⁰ C
Gasoline (0 to 200 ° C)
Gas oil over 200 ° C
Gas oil over 250 ° C

One tried to work in another way of the invention, in which the amount of silicon dioxide deviating, under the rest of Example 2 increased to 71% at the expense of aluminum oxide speaking conditions with a catalyst was 50, the following values were obtained:

Table IV

A. B. C. D. E. F. mission 41
32.8
35.4 1.98
0.01
0.03
0.03 + 1.7 ⁰ C
-6.7 ⁰ C
-6.7 ° C 100
42.5
57.5
47.5 47
50
59.4 0.876
0.851
0.852 Gasoline (0 to 200 ° C)
Gas oil over 200 ° C
Gas oil over 250 ° C

The hydrogen consumption in this experiment reached 155 1 H ₂ per liter of treated gas oil.

So here you can see a very pronounced increase in hydrogen consumption and, on the other hand, a notice considerable change in the yields of the various fractions. The light gasoline fractions have increased noticeably.

Claims (1)

Claim: Process for the catalytic treatment of gas oils in the presence of oxides of cobalt and molybdenum, which is modified with up to 40% of the total amount of catalyst silica Aluminum oxide are applied at I 236 elevated pressures and elevated temperatures with the addition and recycling of hydrogen, characterized in that gas oils with a pour point above -18 ° C or above -7 ° C in the presence of a catalyst which at least. 5% silicon dioxide, based on the sum of the aluminum oxide and silicon dioxide, and at most 40% silicon dioxide, based on the total amount of catalyst, at such a temperature between 400 and 450 ⁰ C and such a pressure between 5 and 100 at at a such a space velocity between 0.5 and 10 using employed under 15 moles of hydrogen per mole of gas oil treated such that the pour point of the fraction reduced the treated gas oil having the same boiling range as the used gas oil below -18 ⁰ C or below -7 ⁰ C will. Considered publications: German Auslegeschriften Nos. 1014692, 1019786; Patent No. 12392 of the Office for Invention and patent systems in the Soviet zone of occupation in Germany; British Patent Nos. 785 158, 793 812; French Patent No. 1 108 294; U.S. Patent Nos. 2,689,821, 2,760,907. 709 519/509 3.67 © Bundesdruckerei Berlin