DE1050478B - Reforming process to increase the aromatic content of a completely or partially non-aromatic hydrocarbon mixture boiling in the gasoline boiling range - Google Patents

Description

GERMAN

The invention relates to catalytic reforming of petroleum hydrocarbons, especially for the production of motor gasoline,

In the known hydroforming process, gasoline fractions are produced at elevated temperatures and pressing in the presence of hydrogen treated with dehydrogenation catalysts, producing gasoline fractions with increased octane number. Catalysts are used here as commercially available catalysts made of molybdenum oxide on aluminum oxide and catalysts consisting predominantly of platinum an alumina carrier with or without bound halogen is used. One with catalysts out Platinum on aluminum oxide carried out hydroforming is called platforming and the resulting Product referred to as platformat.

It is also known that catalysts from the oxides of cobalt and molybdenum on an essentially made of aluminum oxide, which is used to a large extent for catalytic. Desulfurization of petroleum hydrocarbons are used, a noticeable reforming effect under suitable conditions to have.

The invention relates to a reforming process for a hydrocarbon starting material consisting wholly or partially of non-aromatic hydrocarbons and boiling in the gasoline boiling range at elevated temperatures and using catalysts which contain the oxides of cobalt and molybdenum as such or in bound form on a support consisting essentially of aluminum oxide, and is characterized in that the process is carried out at temperatures in the range from 450 to 580 ° C., pressures up to 4.55 kg / cm ² and without externally added or recirculated hydrogen.

In the case of the process according to the invention, there are also liquids under normal conditions Product with a significant content of aromatics and some olefins significant amounts of hydrogen-rich Gases as a valuable by-product.

The expression "at pressures up to 4.5 kg / cm ² " includes normal pressure and pressures below it. Normal pressure is preferred. The temperature should be in the already mentioned range from 450 to 580 ° C., but preferably in the vicinity of 525 ° C., and the space flow rate of the liquid starting material at 0.1 to 1.0 V / V / hour. lie.

The catalysts preferably contain between 1.5 and 5% cobalt oxide and between 5 and 25% Molybdenum oxide, based in each case on the weight of the total catalyst. These oxides can be used in in free form as cobalt molybdate or in both forms.

Reforming process
to increase the aromatic content

one in whole or in part

from non-aromatic existing

and boiling in the gasoline boiling range

Hydrocarbon mixture

Applicant:

The British Petroleum Company Limited,
London

Representative:
Dr.-Ing. A. v. Kreisler, Dr.-Ing. K. Schönwald,

Dipl.-Chem. Dr. phil. H. Siebeneicher

and Dr.-Ing. Th. Meyer, patent attorneys,

Cologne 1, Deichmannhaus

Claimed priority:
Great Britain 13 September 1956

John Arthur Edgar Moy,

Sunbury-on-Thames, Middlesex (Great Britain),
has been named as the inventor,

The catalysts can be used in the form of fixed bed, fluidized bed or fluidized bed catalysts will. Since the catalysts are made by burning carbonaceous precipitates in a stream of Allowing oxygen-containing gas to be easily regenerated is the process especially for fluidized bed or fluidized bed catalysts suitable.

As mentioned earlier, the process yields large amounts of hydrogen-rich gases as valuable By-product. The raw material used should boil in the light or gasoline sector. In particular, they consist essentially of a mixture of hydrocarbons having 5 to 7 carbon atoms existing fractions preferred.

According to one embodiment of the invention, a straight-run distillate, in particular a low-boiling fraction called primary flash distillate from a direct distillation used. The treatment according to the invention gives gasoline blending components with high Octane number and high volatility, especially with research octane numbers (without addition) of at least 90

809 74W352

3 4

and a volatility of at least 70% for cracked gasolines or alkylates

100 ° C.

According to another embodiment, 1 1

Starting material Products from a catalytic one by hydroforming a gasoline fraction

Reforming processes can be used. This is done over a catalyst made of platinum and aluminum oxide

The method according to the invention thus comprises a 2-stage reformate obtained in bound halogen

Reforming process, after the aromatics and separated into low and high boiling fractions and

Gasoline fractions with a high octane number, preferably the low-boiling fraction with a final boiling point

of about 100 (research octane number without addition), of 108 ° C. and a research octane number of 76.1

can be won. In the first stage, each (without addition) can continue under the following conditions

of the suitable reforming process for the user reformed:

dung come, a process in which platinum catalysis pressure 'normal pressure

Sators on a support made of aluminum oxide with room flow rate ". 0.2 V / V / hour.

or without bound halogen, recirculated gas volume -

however, it is preferred that the treatment lasts 5 hours

With such a two-step process, that can

total reformate from the first stage to the second under the above conditions become three

Stage to be reformed. However, since his higher boiling point attempts to use various catalysts and

The final fraction is rich in aromatics, the temperatures are not further different, carried out as follows:

can be refined, the reformate is preferred 20 1. Catalyst made of 2.9% cobalt oxide and 14.1%

wise fractionated and here a lower-boiling molybdenum oxide on a carrier made of aluminum oxide;

relatively aromatic-free fraction obtained, which then process temperature: 530 ° C.

is further treated. Optionally, the reformate can be 2. Catalyst of experiment no. 1; Process tem-

also subjected to solvent extraction and temperature: 475 ° C.

the "raffinate or part of it is treated further 25 3. Catalyst of experiment no. 1 with an additional

the. If necessary, the product can then have an additional content of 3.4% fluorine; Process temperature

with the higher boiling fraction or the solution temperature 530 ° C.

medium extract or with other components The comparison values for the three experiments are in

with high octane number, e.g. B ₁ high-boiling catalytic table 1 listed.

:: ■ Table 1

Attempt no.

Butane-free liquid product

Yield percent by weight

Research octane number (without addition)

Exit gases flow rate

H ₂ content percent by volume

1 2 3

.48

'68

58

106.3 * 93.6 93.7

386 238 350

70 72 79

_ * Calculated according to the following equation: Octane number = 100+

PN-100

in the PN means the Army and Navy performance numbers.

As can be seen from the table, the fluorine-containing ones are the low-boiling ones used as the starting material term catalysts less effective than the same Ka- platformat and for the products of experiments 1 and 2 catalysts without fluorine. The observed values for 45 are shown in Table 2 below.

Table 2
. Observed values for raw material and products

Low boiling
Platform format
Source material Reformate
from experiment 1 Reformate
from experiment 2 ASTM distillation ( ⁰ C)
Initial boiling point
10% recovered at
50% recovered at
90% recovered at
Final boiling point
% evaporated 100 ° C
Composition ;;:
Aromatics (volume percentage)
Olefins (volume percentage) ;.
Saturated hydrocarbons
(Percent by volume) .... .5 ^; . .......... 34
49
72
100
108
90
16
1
83 46
62
95
115
159
61.5
81.5
2.5
16 43
58
90
119
166
65.5
44
5
51

Example 2

A straight-run, low-boiling gasoline with an ASTM boiling range of 43-107 ° C and a research octane number of 60.5 (without addition) is treated under the following process conditions.

Pressure 'normal pressure

Space flow velocity. . 0.2 V / V / hour

Recirculated gas volume · - ■

Travel for about 5 hours

Experiments are carried out with the catalyst of Example 1 at different temperatures. The results are shown in Table 3 below.

Tabel

temperature
⁰ C

Butane-free product

yield
Weight percent

Research octane number (without additive) outlet gases
Flow rate

H ₂ content
Volume percentage

474
525

71.4
45.9

82.6 97.2 294
550

84
72.5

Claims (5)

Patent claims: 1. Reforming process to increase the aromatic content of a hydrocarbon mixture consisting entirely or partially of non-aromatic hydrocarbons and boiling in the gasoline boiling range at elevated temperatures and using catalysts that convert the oxides of cobalt and molybdenum as such or in bound form on a support consisting essentially of aluminum oxide , characterized in that the process is carried out at temperatures in the range from 450 to 580 ° C, pressures up to 4.55 kg / cm ² and without externally added or recycled hydrogen. 2. The method according to claim 1, characterized in that that catalysts with 1.5 to 5% cobalt oxide and 5 to 25% molybdenum oxide are used will. 3. The method according to claims 1 and 2, characterized in that the space flow velocity of the liquid starting material 0.1 to 1.0 V / V / hr. amounts to. 4. Process according to Claims 1 to 3, characterized in that an im as the starting material A mixture consisting essentially of hydrocarbons with 5 to 7 carbon atoms is used will. 5. The method according to claims 1 to 4, characterized in that a starting material Straight-run distillate fraction or part of a catalytic reformate, in particular a platform, be used. Considered publications: British Patent Nos. 653 320, 682 317;
U.S. Patent No. 2,510,189. 809 749/352 2.