DD230872A1 - METHOD FOR HYDROGENATING HEAVY AND RESIDUE OILS AND CATALYSTS THEREOF - Google Patents

Abstract

The invention relates to a process for the catalytic treatment of heavy and backsoil soils with hydrogen using Staeuben as a catalyst, which are obtained in the hydrogenating gasification of coal (HKV dust: hydrogenating coal gasification), which dust itself can be used as a catalyst or as a catalyst carrier for a metal and / or its compounds.

Description

Rheinische Braunkohlenwerke AG.

Process for hydrogenating heavy and residual oils and catalysts used therefor

Application of the invention:

The invention relates to a method for the catalytic treatment of heavy and residual oils with hydrogen ν using dusts as a catalyst, which are obtained in the hydrogenation gasification of coal (HKV dust: Jiydrierede coal gasification), these dusts themselves are used as a catalyst can, or as a catalyst support for a metal and / or its compounds.

Catalysts for the hydrogenation of heavy oils, which include petroleum refining residues, but also oils from shale oil and tar sands processing, as well as other fossil raw materials and oils derived therefrom, are in particular subject to the following requirements: they should be materials that are not have to be recovered after hydrogenation, but can be discarded due to their low price, they should be tilted without causing 'environmental damage' and they should in particular have high catalytic activity.

Characteristic of the Known Technical Solutions: Catalysts have already been described for the so-called bottom phase dehydrogenation of heavy oils, which satisfy these requirements, albeit not yet satisfactory. 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: "A particularly suitable (catalyst) carrier proved to be activated lignite (in oil hydrogenation) ...".

On the same page, lines 25-29 it says: "The most favorable effect is a long-term activated with water vapor at 900 ° C activated Grude, but sufficient is already the activation, the lignite or brown coal mine in the dust-like gasification - eg. in Winkler generators (then low-pressure Winkler generator) - receives (Winkler dust) ... ", but a driving style of the Winkler generator on relatively low burnout (high remaining carbon content) is required, so in itself an uneconomical driving.

In the absence of Grude from Winkler generators, the catalyst support (Α-coal) had to be made especially, for which a so-called CIPA process is called after the activation of fine-grained, carbonaceous material as in the Winkler generator in the suspended state with air and Steam at temperatures around 900 ° C takes place. As a possible possible catalyst support finally normal lignite Schwelqrude is quoted (same page, lines 33-40), but worse results were obtained.

On the following page 80 of his book, Krönig then states (lines 6-8) that the metal (iron) sulfate 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, wherein the dry coarsely pre-milled catalyst in (as possible asphalt-free) oil to be finely ground to a catalyst slurry (line 15).

This prior art thus teaches that the lignite coke obtained in the gasification or charring must be activated with water vapor and (air) oxygen or, if lignite dust (Winkler dust) is used, must be driven on relatively small burnout in the Winkler generator. in order to gain in this way a useful catalyst for (heavy) oil hydrogenation catalyst or catalyst support.

Apart from the fact that from the Winkler gasification with a relatively low yield produced lignite (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 and catalyst support by sufficiently available and even more effective catalysts or catalyst support.

Explanation of the essence of the invention:

Surprisingly, it has been found that dust incurred in the hydrogenating coal gasification, to meet these requirements by those skilled in unpredictable extent. With these dusts are already without catalytically effective additives of metals or their compounds and in particular with the addition of such metals or their

Compounds obtain the desired low-boiling products in an amount and achieved sales, as they were previously unknown to the prior art.

The hydro-gasification of coal is the direct conversion of coal into gaseous hydrocarbons under normal conditions, in particular methane by treating the coal with hydrogen.

Hydrogenating gasification is a pressure gasification process in which coal is reacted with hydrogen at 80-100 bar and temperatures of 800-1000 ° C.

This technical new development is operated by the applicant in a harbtechnischen pilot plant, brown coal is used as a feedstock (see, for example H. Teggers, K.-A. Theis, L. Schrader, petroleum and coal-natural gas petrochemical combined with fuel chemistry, Bd. 35, Issue 4, April 1982, pp 181-184), but also when using other types of coal to obtain the catalysts of the invention.

The hydrogen used may be pure hydrogen; but also technical hydrogen, which still contains CO and CO-, can be used successfully.

Embodiment:

The figure shows that the raw gas flowing from the reactor 1 overhead passes into eiii-en cyclone 2, where entrained dusts or dust-like residual coke separated from the raw gas

become.

The dust passes through the dust lock 3 in the Restkoksbunker 4 together with discharged via the Restkoksschleuse 5 residual coke. However, the cyclone dust can also be deducted directly via 6.

It has surprisingly been found that both the dust and the coke usually present in less fine distribution alone and in mixtures due to their properties caused by the hydrogenating gasification properties, in particular under high temperature and pressures under hydrogenation under this formation have excellent catalyst properties. Although there is no exact knowledge of the catalytically active centers of this catalyst, it must be assumed that particularly active centers are present for the addition and transfer of hydrogen, as is important for the hydrogenation of heavy oils. Of course, the catalytic efficiency of the residual coke can be improved by fine grinding. '

Although pore volume and pore radii of the catalyst do not sufficiently explain the particularly favorable properties, the suitability of the catalysts according to the invention for the hydrogenation of heavy oils is also evident from these data, as shown in Table 1.

Table 1

Specific surface area> 200 m / g

Pore volume 67% (example)

50% of the pore volume have pore radii 1900.10 m

Water content _: ^. λ wt.% Ash content 2-70 wt.% (anhydrous)

C content 20-90% by weight (anhydrous)

Oxygen content 1-5% by weight (anhydrous)

The increase of the catalytic. Activity of the prior art catalysts by treating them with metals or their compounds, as explained above, known. It has been shown that the catalysts according to the invention have unprecedented carrier properties. In particular, by applying iron or its salts, iron sulfate being preferred, excellent catalysts are obtained. But also } other catalytically active metals, eg. B. Mo, W, Ni, Co lead to very active catalysts, although the economy is affected by the cost of these metals and also the tilting is not safe.

A catalyst prepared according to the invention contains z. B. 9 5 parts by weight of HKV dust or HKV dust / residual coke mixture and 5 parts by weight of iron sulfate or equivalent amounts of other compounds of iron or equivalent amounts of compounds of other metals such as Mo, W, Co, Ni, further 100 parts by weight of heavy oil and enough sodium hydroxide solution that an aqueous extract of this mixture has a basicity of pH 5 - pH 13.

However, the ratios of Katalysatortraqer, metal compound and heavy oil can be varied within wide limits.

The preparation of the mixture is advantageously carried out so that HKV dust or HKV dust / residual coke mixtures 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 caustic soda can 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. If the above mixture is milled for about one hour in a ball mill at a temperature of 95 ⁰ 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.

Instead of aqueous sodium hydroxide, other bases can be used.

Usually, however, the dust or the dust / residual coke mixture are ground as such to a particle size smaller than 0.1 mm. After the metal salt doping can then be carried out wet grinding to a particle size of 50% less than 30. 10 ~ ⁶ m.

The effectiveness of the new catalysts is shown in Table 2. Dust from the former low-pressure Winkler gasification reactor serves as comparative catalysts.

The results are based on hydrogenations at 450 ° C of heavy or residual oils consisting of 50 wt.% Of a vacuum distillate with boiling range 350-500 ° C and 50 wt.% Of a residual oil with boiling range> 500 ° C.

Hydrogenations with the catalysts of the invention can be carried out within wide limits of 380-500 ° C, with the range of 420-480 ° C is preferred.

The comparative experiments were carried out at a pressure of 300 bar. However, it is known to those skilled in the art that the hydrogenations, as they. also z. B. in the swamp phase carried out

be led, can be varied in wide pressure limits. The type of reactor used for the hydrogenation can also be chosen according to the requirements.

The treatment of the catalysts with FeSO. took place as indicated on page 9.

Experiment no.

catalyst

1 2

5 6

Low-pressure Winkler dust (60% by weight C,% by weight of Fe)

Low-pressure Winkler dust as under 2, additionally treated with 5 wt.% FeSO ₄ )

HVK dust (20% by weight C, 2% by weight Fe)

* HKV dust (30% by weight C, 2% by weight Fe)

HKV dust as under 4, additionally treated as 5 wt.% FeSO ₄

50% by weight HKV dust / 50% by weight residual biscuit , ground (40% by weight C, 3.5% by weight Fe)

as under 1, additionally treated with 5 wt.% FeSO ₄

Residual coke (60% by weight C, 5% by weight Fe)

Products in% by weight

Distillate residue> 500 ° C

relative throughput

70

82 78

25

21.5

73 19 80 11 80 11

13

11 12

1.0

1.5

1.5 2.7 2.7

3.3

2.6

2.8 2.5

H (D

Experiment No., catalyst products in wt.% Relative throughput

Gas distillate residue > 500 ° C

HKV dust, as under 4, doped with 2.5% by weight of molybdenum and 2.5% by weight of nickel 8 83 9 3.4

* Higher coalification rate of coal used in gasification than in No. 4 (or 6, 7, 8 and 9)

The table shows the unexpectedly good properties of the catalysts according to the invention.

Compared to the previously used low-pressure Winkler dust, in which a relatively high carbon content was a prerequisite for good catalyst properties, which was possible only by low burnout of the coal used in the Winkler generator with correspondingly uneconomical driving, plays in the erfindngsgemäßen Catalysts of carbon content no significant role, as is apparent from the experiments 4, 5, 7 and 9.

Particularly striking is the unexpected result for the expert that even mixtures with ground coke, which is withdrawn from the bottom of the hydrogenation reactor, almost equally good results as HKV dust alone deliver.

Of particular importance is the result that the iron sulfate treated HKV dust (Run 6) provides distillate at the high relative flow rate of 3.3, which has not previously been achieved. These excellent properties of the catalyst are of great economic importance in the increasing use of heavy oils for the recovery of distillates in the boiling range below 500 ° C.

Also, a mixture of HKV dust and ground residual coke yields excellent results after treatment with ferrous sulfate according to Experiment 8.

An HKV dust treated with (NH ₄ J _{3 MoO 2) and nickel sulfate was used} in Experiment 10. Excellent results were also obtained with this catalyst, especially with regard to the relative throughput achieved.

Claims (5)

Invention claim: 1. A process for the catalytic treatment of heavy and residual oils with hydrogen in the presence of dusts and dust / residual coke mixtures, in particular as carriers for one or more catalytically active metals and / or compounds thereof, characterized in that dusts and dust / residual coke Mixtures in mixture ratios of 0-100 wt.% Dust can be used as a catalyst and / or catalyst support incurred in the hydrogenating gasification of coal (HKV dust:, hydrogenating coal gasification). 2. The method according to item 1, characterized in that the HKV dust and / or the HKV dust / residual coke mixture is treated with a solution of metal compounds. 3. The method according to points 1 and 2, characterized in that the catalyst in concentrations of 0.1 to 10 wt.% Based on the heavy or residual oil to be hydrogenated is added. 4. The method according to points 1 to 3, characterized in that HKV dust and / or HKV dust / residual coke mixture with sulfates, oxides, sulfides and other compounds or • mixtures thereof, of catalytically active metals, aqueous sodium hydroxide solution and heavy oil or residual oil are mixed and ground to be added to the heavy oil or residual oil to be hydrogenated. 5. Catalyst for treating heavy and residual oils with hydrogen in the presence of dusts and dust / residual coke mixtures, in particular as carriers for one or more catalytically active metals and / or compounds thereof, characterized in that dusts and dust / residual coke Mixtures in mixing ratios of 0-100 wt.% Dust as Catalyst and / or catalyst support used in the hydrogenating gasification of coal used (HKV dust: .Hydrierende coal gasification). " ^ Cm9 drawings