DD248138A1 - METHOD FOR THE SUMP PHASE HYDRATION OF HIGH-END HYDROCARBON MATERIALS - Google Patents

Abstract

The invention relates to a process for the bottom phase hydrogenation of high-boiling hydrocarbon materials of petroleum processing and / or coal refinement in the chemical industry. The object of the invention is to use a method that works with a cost-effective, available in any large quantities catalyst. The object is to use a method in which a well-suspendable catalyst with high catalytic activity is used. According to the invention, the object is achieved by adding a catalyst based on red mud, whose specific surface area is more than 50 m 2 / g, to high-boiling hydrocarbon materials. The process can be used continuously and discontinuously.

Description

Field of application of the invention

The invention relates to a process for the bottom phase hydrogenation of high-boiling hydrocarbon materials, such as heavy oils, petroleum refinery residues and / or coal refinement in the chemical industry.

Characteristic of the known technical solutions *

It is known that the high-boiling hydrocarbon materials, such as heavy oils or petroleum refining residues and coal refining, contain high levels of asphaltene, nitrogen compounds and heavy metal compounds. Especially these substances have a very adverse effect on the catalytic hydrogenation of high-boiling hydrocarbon materials in which they damage the catalyst, which ultimately has a negative effect on the service life of the catalysts and the operating costs.

For a long time, the hydrogenation treatment of tars and residues with molybdenum compounds, such as with molybdenum trioxide is known {see W.Krönig "The catalytic pressure hydrogenation of coals, tars and mineral oils", Springer-Verlag, 1950, Ss77).

Because of the availability of molybdenum, the high price, the high catalyst requirement and the resulting unsatisfactory economy of the overall process, later Winkler multiclonal dust based catalysts impregnated with molybdenum salt solutions were used.

These catalysts were also replaced by a much cheaper but not so active iron catalyst for cost reasons, which is known under the name Kontakt 10927 (see J.Zogala, Freiberger Forschungshefte A36, 1955,

This contact 10927 is an alkalized Winklermultiklonstaub soaked with iron sulfate. Furthermore, processes for the hydrogenation of heavy and residual oils in DE-OS 3238689 and DE-OS 3232694 are described, in particular with hydrogenation metal salt solutions impregnated dusts incurred in the hydrogenation coal gasification, or impregnated cokes, which arise during coking in the hearth furnace than Use catalysts.

However, these catalysts and also the contact 10927 have the disadvantage that their preparation is relatively expensive. This mainly concerns the preparation of the hydrogenation metal solution, the impregnation and the subsequent drying of the catalysts.

So far little is described the use of red mud, a by-product of alumina production, or iron ores as catalysts in the Sumpfphasenhydrierung of heavy oils, since they are less active compared to the contact 10927 and on the other hand have a much higher powder bulk density. The high density leads to inhomogeneity of the oil-catalyst suspension, Abs.etzerscheinungen and ultimately to malfunction. In addition, the low activity must be compensated by a higher catalyst addition.

Object of the invention

The object of the invention is to develop an improved process for the sump phase hydrogenation of high-boiling hydrocarbon materials, in which a high yield of target products is realized and which works with a cheap and available in large quantities catalyst.

Explanation of the essence of the invention

The object of the invention is to propose a process for the bottoms phase hydrogenation of high-boiling hydrocarbon materials, in which a readily suspendable catalyst having a high catalytic activity is used.

According to the invention the object is achieved in that high-boiling hydrocarbon materials, a catalyst based on red mud is added, wherein the specific surface of the catalyst is advantageously more than 50m ² / g. The preparation of the catalyst is carried out by dehydrated dried red mud at about 673 to 1 073 K in a tubular reactor in the gas stream for 0.1 to 1 second shock. It has proven to be beneficial that the surface-rich red mud catalyst having a particle size of 0 to 63, preferably O to 20μιη contacted immediately after its preparation without intermediate storage with the converting hydrocarbon material and the resulting oil-catalyst suspension is then heated and at 573 to 773 K and 7 to 30 MPa is hydrogenated, wherein the catalyst additive, based on the fresh heavy oil use 0.05 to 4Ma .-%, preferably 0.1 to 2Ma .-%, is.

embodiment

The invention will be explained in more detail below by means of an example:

Example:

250 g of residual sulfur oil residue (for analysis data see Table 1), representative of a heavy oil to be converted, were mixed homogeneously into a suspension with 25 g of thermally activated red mud catalyst (for properties and composition, see Table 2).

In order to demonstrate the high catalytic activity of the surface-rich red mud catalyst used in comparison to known suspended hydrogenation catalysts in heavy oil hydrogenation, comparative experiments with normal red mud (properties and composition see Table 2) obtained in the production of alumina as a waste product, and with the commercial sump phase contact for Heavy oil 10927 performed. All contacts used had a grain spectrum up to 45μΓη. The composition and method of preparation of Kontakt 10927 are given in an article by Zogala, Freiberger Forschungshefte A36, 1995, p.

The heavy oil catalyst suspension was hydrotreated in a shaking autoclave at 623 K and a hydrogen hot pressure of 22 MPa for 60 minutes. The hydrogenation product thus obtained was centrifuged in a laboratory centrifuge at about 3500 rpm to separate the solid phase-phase catalyst. From the solids-free hydrogenation product, the density was determined (for analytical data, see Table 3).

In addition, this hydrogenation product was analyzed by IR spectroscopy and determined the proportion of aromatics and paraffins.

The ratios paraffins to aromatics are given in Table 3.

From the experimental results shown in Table 3, it is clear that the surface-rich red mud catalyst is superior to the contact 10927 and the conventional red mud in catalytic activity, molecular weight degradation (density) and hydrogenation strength (paraffin-aromatic ratio).

The use of the surface-rich catalyst gives rise to further advantages for the process for the sump phase hydrogenation of high-boiling hydrocarbon materials:

- high distillate oil yield

- The catalyst can be homogeneously suspended in the hydrocarbon material to be converted

- The suspension is maintained over a long period

- There are no settling phenomena of the catalyst and consequently no malfunction

- The raw material for the catalyst is available cheaply in large quantities

- The catalyst price is low and this results

- Low operating costs of the process

- The catalyst does not corrosive

Table 1

Analytical values of the Schwelereimittelolruckstandes

Density (at 323 K) 0.983

Pour point 305 K

Flashpoint 388 K

Asphalt content 3,1 Ma .-%

Viscosity (at 313 K) 39.4mPa-s

(at 330K) 11, OmPa-S

Water content -

Initial boiling point 417 K

5 vol .-% at 526 K.

50 vols I. -% at 668K

Table 2

Properties and composition of red mud catalysts

conventional surface rich

Red Mud Catalyst Red Mud Catalyst

60 0.62 31.2 26.1 18.6 2.6 2.6 4.5 14.0 0.4

Table 3

Experimental result of the hydrogenation of sulfur oil residue with various slurry phase catalysts

Surface area (m ² / g) 29 Powder bulk density (g / ml) 0.98 Fe ₂ O ₃ Ma .-% 31.2 Al ₂ O ₃ Ma .-% 26.1 SiO ₂ % by mass 18.6 CaO Ma .-% 2.6 MgO Ma .-% 2.6 TiO ₂ Ma .-% 4.5 Na ₂ O Ma .-% 14.0 other ingredients Ma .-% 0.4

Contact 10927 conventional high surface area Rotschlammkatalysator Rotschlammkatalysator Temperature K 623 623 623 H ₂ -DrUCkMPa 22.0 22.0 22.0 Reaction time min 60 60 60 Density at 323 K g / ml 0.960 0.984 0.950 Paraffins / aromatics 4.40 4.35 5.21

Claims (5)

A process for the sump phase hydrogenation of high-boiling hydrocarbon materials, such as heavy oils, residues of petroleum processing and / or coal upgrading, using a suspendable catalyst, characterized in that a shock-heated dehydrated, surface-rich red mud catalyst is used, which has a specific surface area of at least 50 m ² / g owns. 2. The method according to claim 1, characterized in that the surface-rich red mud catalyst is supplied after its preparation without intermediate storage to be hydrogenated high-boiling hydrocarbon material and mixed and the oil-catalyst suspension is then treated by hydrogenation. 3. The method according to claim 1, characterized in that the maximum particle size of the surface-rich red mud catalyst is 63μιη. 4. The method according to claim 1 and 3, characterized in that the surface-rich red mud catalyst in an amount of 0.05 to 4 wt .-%, based on the fresh heavy oil, is added. 5. The method according to claim 1, characterized in that the surface-rich red mud catalyst has a powder bulk density of less than 0.8 g / ml.