DD210295A1 - METHOD FOR HYDROGENATING HEAVY AND RESIDUE OILS AND CATALYSTS THEREOF - Google Patents

Abstract

Method for hydrogenating heavy oils and residual oils in a residual phase, and catalysts used in such method. Such catalysts are obtained by coking lignite, particularly in a hearth furnace, as well as by gasifying lignite in a high temperature Winkler generator; the catalytic properties of such catalysts are further improved by addition of metal compounds, particularly iron compounds.

Description

The invention relates to a process for the hydrogenation of heavy and residual oils in the context of a commonly known as sump phase dehydrogenation process using lignite coke and / or brown coal foundations from a high-temperature Winkler generator (HTW dust) as a catalyst, in particular as a carrier for can serve a heavy metal catalyst. The lignite coke and / or the brown coal foundations either serve themselves as catalyst or as support for a heavy metal catalyst.

Characteristic of the known technical solutions: Processes for working up heavy and residual oils in the bottoms phase hydrogenation using lignite coke and brown coal foundations as catalyst or catalyst carriers are known per se. So describes z. B. Krönig in his book "The catalytic pressure hydrogenation of coals, tars and mineral oils", Springer Verlag Berlin, Göttingen, Heidelberg, 1950, page 79, lines 13 and 14; "Activated lignite foundations (in oil hydrogenation) have proven to be particularly suitable (catalyst) carriers ...".

On the same page, lines 25-29 it says: "The most favorable effect is an activated in longer exposure time at 900 ° C with water vapor Grude, but sufficient is already the activation, the brown coal or Braunko.hlengrude in the dusty gasification -. In Winkler generators' (formerly bodice pressure Winkler

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Gen.era.tQj :) - receives (W / inklerstaub) ... ", but a Fahrrad of the Winkler generator on relatively low burnout (high remaining carbon content) is required, so in itself an uneconomical driving style.

In the absence of Grude from Winkler generators, the catalyst support (Α-carbon) had to be made especially, for example, what is called a CIPA process, after the activation of fine-grained, carbonaceous material as in the Winkler generator in the suspended state with air and Water vapor · takes place at temperatures around 900 ° C. As a further possible catalyst support is finally normal "lignite Schwelgrude quoted (same page, lines 33-40)., But. However, worse results were obtained.

On the following page 80 of his book, Krönig then states (lines 6-8) that the metal (iron) sulphate impregnated on the green should be reacted with sodium hydroxide solution. Finally, it is stated that for the effectiveness of the "catalyst" whose fine grinding is important, the dry coarsely pre-milled catalyst in (as possible asphalt-free) oil should be .feingemahlen- to a catalyst slurry (line 15).

This prior art teaches that the. in the gasification or charring obtained lignite coke must be activated with water vapor and (air) oxygen or, if lignite (Winkler dust) is used, must be driven to relatively low burnout in the Winkler generator in order in this way one for the ¹ (Heavy -) Ö! Hydrogenation useful catalyst or catalyst to win.

Apart from the fact that from the Winkler gasification with relatively little burnout produced lignite dust (Winkler dust) is not available in sufficient quantities, since for economic reasons, the gasification processes are directed by the Winkler method to complete as possible gasification of lignite used, it has It has also been shown that the activation of the lignite coke with steam is very complicated and expensive, not least because of the relatively long exposure time and high temperatures.

Object of the invention:

The invention is therefore based on the object to replace the known catalysts or catalyst support on lignite enbasi's possible by sufficiently available and even more effective catalysts or catalyst support based on lignite.

DISCLOSURE OF THE NATURE OF THE INVENTION Surprisingly, it has now been found that lignite fine coke, which is produced by the coking of lignite in a furnace, and that Winkler dust from a high-temperature Winkler generator (HTW dust), regardless of the burnout on a beneficial Catalyst or catalyst support fully meet expectations and that, moreover, the lignite coal coke still allows a higher throughput in the treatment of heavy and residual oils with hydrogen.

When coking in the hearth furnace finely ground and pre-dried lignite is placed on downpipes on the outer edge of the hearth furnace plate and moves under their constant rotation and the action of the fixed paddles slowly to .Mitte, from where

the finished coke is discharged. During the passage, the volatiles escape from the lignite / coke bed and are partly burned while supplying air from outside above the coke bed. The coking process is conducted via this combustion of some of the volatiles, i. it is operated under air deficiency, so that each burns only such an amount of volatile components, as is needed to maintain the coking temperature. The browning of lignite in the hearth furnace generally takes place without supply of water vapor or water from the outside, since the water content of the pre-dried lignite can be adjusted so that coke with the desired properties is obtained.

Embodiment:.

The figure shows the recovery of the HTW dust. The high-temperature Winklergenerator 1 is followed by a cyclone 2, are returned to the generator over the non-gasified components. The HTW dust is recovered in a cyclone 3. Since the gas velocity in the HTW Winkler generator is much higher than in the previous low pressure generator, the cyclone cyclone 2 is required, while the low pressure generator had only one cyclone in the raw gas stream.

The: High-temperature Winklergenerator is a new technical development of the applicant.

A technical unit is under construction (see eg H. Teggers, K.-A. Theis, L. Schrader, Erdöl und Kohle - Erdgas-Petrochemie united with Brennstoffchemie, Bd. '35, Issue 4, April 1982, p 178-131). '

Therefore, "Sta, ub, and HTW ~ Sta.ub differ in essential properties, as shown by a typical analysis (Table 1):

Table 1 1- HTW % By weight low pressure 15 (Jl % By weight 0.6% by weight water content 22- 65 % By weight 38.0% by weight ash content 0.1 80 % By weight 60-65% by weight C-content - 2 5-7% by weight Iron content

It has also been found according to the present invention that the efficacy of the lignite hearth coke and the HTW dust as a catalyst can be further enhanced by treating them with a solution of a metal compound.

By lignite coke usually considered as a catalyst or catalyst carrier has a grain size which is smaller than 6 mm. His pore volume is dangerously 50%.

lumen is less than 10 angstroms at pore radii

An average sieve analysis of HTW dust gives the following grain size distribution:

diameter in um Percentage ownership %   2000 0.02 1000 - 2000 0.04 500 - 1000 0.5 .315 - 500 2.0 315 - 200 6.0 200 - 125 10 125 -   90 7 90 - 63 5 63 - 50 5

Diameter m μπι proportion of in % 50 - 40 3 40 - 32 10 <32 51 5.

When using the HTW dust as a catalyst (carrier), it is recommended to sieve the coarse fraction y- 90 μΐη or grind to a diameter of <l90 μm.

50% of the pore volume of the HTW dust have pore radii -C 2000 S. The surface area is> 300 m ² / g.

As already taught by Krönig, the effectiveness of the novel catalysts can be increased by treatment with sulfates of catalytically active metals. A catalyst prepared according to the invention based on lignite coal coke contains z. B. 98 parts by weight of brown coal fine coke with 2 parts by weight of sulfates or other compounds in an equivalent amount of Fe, Mo, Co, Wo, ^f ie catalytically active heavy metals and 100 parts by weight of heavy oil and so much aqueous sodium hydroxide solution (NaOH) that an aqueous extract of this mixture Basicity of about pHc to pHo. However, the ratio of catalyst support to metal salt can be varied within wide limits.

The preparation of the mixture is conveniently carried out so that Herdofenkoks and / or HTW dust are presented in the mixer and after start-up of the mixer, the addition of the metal salt solution is carried out through nozzles to obtain a uniform mixing. Subsequently, the sodium hydroxide solution can then be injected, followed by the heavy oil additive.

Instead of the sulfates of the metals mentioned, it is also possible to use other salts or oxides or sulfides. When the above mixture is milled for about one hour in a ball mill at a temperature of C, the catalyst is present as a powdery solid having a particle size of less than 0.1 mm,

Equivalent catalysts can also be obtained when milling in other mills.

The effectiveness of the new catalysts in comparison with previously known activated lignite-based catalysts is shown in Table 2.

The results are based on hydrogenations at 450 ° C of Schwer bz-w. Residue oil consisting of 50% by weight of a vacuum distillate having a boiling range of 350 ° to 500 ° C. and 50% of a residual oil having a boiling range of 500 ° C. Hydrogenations with the catalysts according to the invention can be carried out within wide limits of 380 ° to 500 ° C., the range of 4 20 - 480 ° C is preferred. The comparative experiments were carried out at a pressure of 300 bar. However, it is known to the person skilled in the art that the hydrogenations, as carried out in the bottom phase, can be varied within wide pressure limits. Also, the type of reactor used for hydrogenation can be chosen arbitrarily depending on the requirements.

The treatment of the catalysts with FeSO. took place as indicated on page 6.

Table 2

Experiment no.

catalyst

Low pressure Winkler dust (60% by weight C; 5% by weight Fe)

Low-pressure Winkler dust as under 2, in addition to FeSO ₄ . treated

furnace coke

HTW dust (25% by weight C, 1% by weight Fe)

HTW dust (25% by weight C), treated with FeSO ₄ (5% FeSO ₄ based on the support)

as 6, but 10% FeSO ₄ , based on the carrier

HTW dust (70% by weight C), treated with FeSO ₄ (5% FeSO ₄ based on the support)

HTW dust (25% by weight C) doped with Mo.

Herdofenkoks treated with FeSO ₄ (5% FeSO ₄ based on the carrier)

Products in wt. % 500 ° C relative throughput gas Distillate residue 25 21.5 5 70 19 1.0 6 5 72 13 1.5 8th 73 1.5 12 75 2.5

75

14

13 79 8th 13 80 7 13 79 8th 12 81 7 10 '83 7

2.5

2.5 2.6

2.5 2.7 3.0

The table shows that the catalysts according to the invention have unexpectedly good properties for the person skilled in the art, which represent a substantial improvement over the prior art.

As stated on page 1, paragraph 3, it has been assumed that suitable Winkler dust must be produced with low burnout, so that a relatively high C content is present in the dust. In addition, in the case of low-pressure Winkler dust (ND dust) was known that with increasing iron content in the dust itself was accompanied by an increasing activity of the catalyst. Attempt. 2 gives the product distribution using a N'D dust having a carbon content of 60% by weight and an iron content of 5.5% by weight. The additional treatment with FeSO, and NaOH shows, as experiment 3 shows, no significant improvement.

Surprisingly, it has been found, as experiment 5 shows that when using HTW dust with only 25 wt.% C, ie at high and therefore very economical burnout in the generator , results are obtained, despite low Fe content in the dust those of the experiments 2 and 3 significantly exceed. From this it is clear that the different driving style of HTW-Generato.r - An.lage. compared to the LP generator plant to a dust that has unpredictable improved catalytic properties by those skilled in the art.

The superior properties of large-scale plants with annual throughputs of 1.9 million t of lignite per year represent a significant technological advance, which represents an important contribution to the improved use of heavy oils.

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It is also clear from the experiments β and, 8 that the burnout is of no importance for the catalytic properties of the HTW stub. However, they show that the Fe doping causes a further improvement of the catalytic properties.

In experiment 9, HTW dust was treated with (NH ₄ I ₂ MoO ₄ , the molar amount of Mo corresponding to the Fe amounts used in experiment 6 and 8. Although the doping with Mo gives an improvement over the Fe doping, it does For economic reasons, the Fe doping preferred.

In experiment .9 the ratio FeSO./catalyst carrier was doubled compared to experiment 6. As a result, as the numbers show, the result is improved.

As experiment 4 shows, also hearth furnace coke leads to significantly better results than the known ND dust catalysts. The best results, however, were obtained with a hearth furnace coke doped with Fe. Particularly noteworthy here is the unexpected increase in the relative throughput.

Further comparative tests not included in Table -2 have shown that lignite coker produced in another way also gives better results than the known ND Winkler dusts.

Good catalysts can also be prepared by treating lignite dusts, such as those used in Winkler generators, with active metal salts and NaOH before gasification or coking.

Claims (2)

Invention claim: 1. A process for the catalytic treatment of heavy and residual oils with hydrogen in the presence of particular serving as a carrier for a heavy metal lignite coke, characterized in that by coking in a hearth furnace obtained lignite coal coke is used as the catalyst and / or catalyst support. 2, Process for the catalytic treatment of heavy d residues oils with hydrogen in the presence of lignite, in particular as a carrier 'for a heavy metal, characterized in that in a H.och tempera tur.-Winkler gasification reactor dust (HTW- Dust) is used as a catalyst and / or catalyst support. J, method according to item 1 or 2, characterized in that the brown coal fine coke and the HTW dust are treated with a solution of metal compounds. 4. Method according to one of the points 1 -. 3, characterized in that brown coal fine coke and / or HTW dust with sulfates, other salts, oxides or sulfides or mixtures thereof, of catalytically active metals, aqueous sodium hydroxide solution and heavy oil are mixed and finely ground be added to the heavy oil to be hydrogenated. 5, Method according to one of the items 1-4, characterized in that the catalyst is added in concentrations of 0.1 to 10 weight percent, based on the heavy oil to be hydrogenated. 6 _f catalyst for treating heavy and Rücksta.nd.solen 'with hydrogen in the presence of particular serving as a support for a heavy metal lignite coke and / or lignite, characterized in that by coking, especially in a hearth furnace obtained lignite coke and / or in a High-temperature Winkler gasification generator dust (HTW dust) used as catalysts and / or catalyst carrier werden.werden. For this 1 page drawings