DD266110A1 - METHOD FOR THE SUMP PHASE HYDROGENATION OF HIGH-ENDED HYDROCARBON MATERIALS - Google Patents

Abstract

The invention relates to a process for the bottom phase dehydrogenation of high-boiling hydrocarbon materials, such as. B. Schweroelen and / or residues soils of petroleum processing and / or coal refinement and / or natural mineral oils in the presence of catalysts to high quality Fluessigprodukten. The catalyst used is a very readily dispersible powdery material having a maximum powder shake density of 0.75 kg / l and consisting of a combination of dried heavy metal containing slurries and thermally unloaded compounds of magnesium and / or aluminum whose particles contain metal compounds as components do not separate and segregate by the action of gravity and are free of carbonaceous materials. The catalyst contains 15 to 60% by weight of heavy metal compounds, 10 to 60% by weight of aluminum and / or magnesium compounds and a maximum of 30% by weight of iron compounds and is used in a concentration of 0.01 to 3% by weight.

Description

Field of application of the invention

The invention relates to a method for Sumpfphasehyr '' iarung of high-boiling hydrocarbon materials, such. As heavy oils and / or residual oils of petroleum processing and / or coal refinement and / or natural mineral oils in the presence of catalysts to high-quality liquid products.

Characteristic of the known state of the art The hydrogenation of high-boiling hydrocarbon materials, such. B. of residual oils of petroleum distillation or the Coal upgrading or of natural heavy mineral oils in the presence of catalysts is problematic since

These materials contain substances that deactivate the catalyst used relatively quickly. Such deactivating

Substances are heavy metal compounds of nickel and vanadium, in concentrations of 10 to several hundred

ppm, asphaltenes with their high coking tendency and heteroatom compounds, in particular

Nitrogen compounds. In the processing of such high-boiling materials by the process of the bottom phase dehydrogenation were first

especially blended pure compounds of molybdenum and tungsten used in some cases mixed with zinc oxide and magnesium oxide (compare W. Krönig "The catalytic pressure hydrogenation of coals, tars and mineral oils", Springer-Verlag, 1960, p.77) These mixtures, however, remained in suspendie> 1er Form as a mixture not stable.There was a demixing of the individual

Active components of the catalyst due to their different sinking rates, which involves loss of activity

brought.

The use of pure, relatively heavy molybdenum and tungsten compounds resulted in high costs for the Catalyst sites and due to their high density Absetzerschei.iungen were observed. Furthermore, these are Molybdenum and tungsten compounds only conditionally available. A recovery of the spent catalysts is indeed

in principle possible, but usually associated with a high technical and financial effort. That's why these were

Molybdenum catalysts by the much lighter, easily suspended in oil catalysts based on activated Lignite replaced. Winklermultiklonstaub proved to be particularly suitable, soaked with ammonium molybdate

was. (KrOnIjI 950, p. 79)

Nevertheless, for reasons of cost and availability, this catalyst was also much cheaper, just as it was

replaced suspendable, but not as hydrogenation-active iron-containing catalyst, the production of which by impregnating

Winklermuhiklon dust with Eicensulfatlösung and subsequent alkalization elaborately gestultete (see J. Zogala, Freiberger Forschungshefte, A 36, 1955, p.31). In the case of a thawing catalyst, the asphaltenes are predominantly not hydrogenated, but rather are absorbed and mixed with the Residue discharged, whereby the oil yield goes back. Because of the lower activity of this sweetener he was in

high concentrations of bit to 10 wt .-%, resulting in significant amounts of residue, a costly

Residue processing and associated high oil losses resulted, which ultimately the overall economy of Hydrogenation negatively affected. Furthermore, it is known that tin compounds have been used for the conversion of heavy oils with good results. So

For the hydrogenation of heavy oils, tin oxalate was used in combination with hydrogen fluoride and telechloromethane (see Gordon Kenneth, J. Inst., Fuel 9 (1935) 69), but stannous chloride was also used as catalyst for heavy oil hydrogenation.

Because of their halide content, these tin-containing catalysts have an effect on all incoming pipes

and plant parts strongly corrosive, so that they were used industrially only for a short time because of the uncontrollable corrosion problems. Another reason was the high price of tin compounds.

More recently, relatively cheap catalysts have been proposed for the hydrogenation of heavy oils. Carbons are used according to the processes described in DE-OS-3232694 and 3238689. These are coke-like dusts, which in the hydrogenating gasification before coal or in the coking coal fm Hearth furnace incurred and doped with metal compounds in particular of iron consuming and then be alkalized. It was therefore resorted to these charcoal-based materials because Winklermultiklonstaub, the Obtained product of the Winkler gasification of lignite, is no longer available. However, these kohleatämmigen catalysts have the same disadvantages as the Winklermultiklonstaubkontakt. In the literature, however, it was pointed out that a trouble-free long-term operating behavior without Temperature inhomogeneities and coke deposits in the system parts only with the addition of a lignite-based Catalyst, could be educated. (U. Lenz, A. Gier, petroleum coal natural gas petrochemical 38 (1985) 404) As new catalysts for the hydrogenation of heavy oil, in the oil suspendiorte, pure defined compounds of iron, Molyb'Jans, vanadium, chromium, manganese and titanium (see R. Bearden, C.L. Aldridge, Energy Progress 1 [1981J

1-4, p.44-e8).

Because of the higher activity compared to the kohlestämmigen catalysts, the catalyst requirement gerir.ger, but the Catalyst production kotten for these pure transition metal compounds for a disposable catalyst not economically

justifiable.

If the pulverulent sump phase catalyst consists of two or more metal compounds, it is due to their

different densities and sinking rates in the oil segregation of the catalyst components This leads to

Lowering the catalytic activity) and ultimately lowering the yield of target products. Furthermore, the tendency to saddle the transition metal compounds due to the relatively high bulk densities

generally much higher than with kohlestämmigen catalysts. Deposits occur in the system components, which can lead to malfunctions.

Thus, e.g. pure Eisensulfdt a density of about 5.25, from the generally desired bulk density, in smaller

0.76 g / l is far away, so that it can not be used in the heavy oil hydrogenation (see B. Strobel et u, petroleum coal

Natural Gas Petrochemistry 34 (1981) 394; M. Höring in Lissner / Thau, .The Chemistry of Brown Coal, Vol. II, UEB Wilhelm-Knapp-Verlag,

Hall 1953, p. 276).

ηΐβκβ disadvantages also apply to the proposed in DE-OS 3345815 Gichtstaubkatalysator.

It is well known that when iron-containing catalysts are used, coking phenomena and Clumps occur (see B.Strobel et al, petroleum coal natural gas Petrociiemiö 34! 1981] 3 ^ t; W. Krönig .The catalytic Pressure hydrogenation of coals, esters and mineral oils *, Springer-Verlag, Berlin / Göttingen). It has also been reported that the naturally occurring nickel in the mineral oil-based residues and heavy oils

and vanadium compounds are used as catalytically active components. However, the content of these compounds is generally insufficient for a maximum conversion, so that depending on the desired degree of conversion and

Carbonaceous tendency of the carbonaceous material incorporates a disposable catalyst or additive for stable operation Schwerölhydrieranlage with combined refining part according to the Veba Combi-Cracking process must be mixed.

(See K.Kretschmaret al petroleum coal natural gas petrochemical, 3911986] 418).

Despite these additive additives coking phenomena are bo observed, which only have sufficient Wassersteffpartialdruck

are to be contained.

Object of the invention

The aim of the invention is an improved effective method of Sumpfphasehydrierung of high boiling hydrocarbon material, which is used to maximum conversion of, in particular residual oils iu valuable liquid products using an inexpensive, highly active and well-suspendable catalyst.

Presentation of the essence of the invention

The technical problem that is solved by the invention is to develop a process for the bottom phase dehydrogenation of high-boiling hydrocarbon materials, such as heavy oils and / or residual oils of petroleum processing and / or coal refinement and / or natural mineral oils, after which easily obtainable hydrogenation metal components in a catalytic particularly active form can be used as very good stspendierbare catalysts. According to the invention, this object is achieved by a process for the bottom phase dehydrogenation of high-boiling hydrocarbon material, after which a high-boiling hydrocarbon material z. B. Residual oils of petroleum processing and / or coal refining and / or natural mineral oils with a ddrin well-suspended catalyst whose powder bulk density is not more than 0.75 kg / l treated, the catalyst used a combination of dehydrated heavy metal-containing thick sludge and thermally unloaded compounds of Aluminum and / or magnesium in the form of a finely divided material whose particles are free of coal-based products and whose constituents do not separate and segregate due to the action of gravity in the high-boiling carbon wax material.

As Schwermetallhahigü Dkksrhllmme containing Hydriermatallkomponenten and are free of kohlestämmigen materials are particularly suitable in sufficient quantities available products that are produced in all industrialized countries as waste products and therefore are very inexpensive available.

These abovementioned waste products are currently used only in a few cases and thereby usually with greater expenses in terms of material economy. The largest share is stored on special landfills, represents an environmental problem and the heavy metals contained are therefore lost to the national economy.

The waste products used contain one or more hydrogenation metal compounds, in particular of Zn, Ni, Cr, Cu, Fe. Besides corrosion and toxicological reasons, mainly chlorides, free cyanides, As, Pb and Cd compounds are interfering. To such heavy metals »?! Dickschlämmen include u.a .:

Ni, Zn, Cr (III) and Cu-containing electroplated sludges

- Cf (lll) -signable sludges produced in wastewater treatment in the leather processing industry

- Zn-hahlge waste products of the Llth jponeheretellung

- Zn-containing residue "from the Zn-Photphati tion brw. -beizerei

- Cr (VI) -free, Cr (III) blends containing waste products from the chromation of aluminum

- Chloride- and cyanide-free precipitated sludges from the etching and etching treatment of metallic surfaces

- Dickschlimme of electrochemical metalworking

These heavy metal-containing thick sludges are admixed with low-alkali, thermally unloaded compounds of Al and / or Mg, which may also be constituents in waste product slurries. This suspension is z. B. processed by spray drying, bubble drying or Rotatlonsdünnlschichtverdampfunq. This contains a powdered free-flowing product having a residual water content of about 1 to 8 wt .-% and a particle size of about 20 to 350 m. Through targeted addition of magnesium and / or aluminum compounds, the bulk density of the catalyst is adjusted to about 0.4 to 0.75 kg / l. This ensures that the catalyst can very well be suspended in heavy oil and that no sedimentation of the catalyst takes place in the pipelines and apparatus. It has been found to be beneficial if the catalyst used contains from 15 to 60% by weight of one or more heavy metal compounds, such as, for example. As the nickel, zinc, copper and chromium, 10 to 60 wt .-% aluminum and / or magnesium compounds and a maximum of 30Ma .-% iron compounds. The particles of the catalyst contain a combination of intimately mixed heavy metal and light metal compounds, wherein the individual compounds are held together by special binding forces such that separation or separation of the individual compounds due to their different ~ .i densities during pneumatic transport and in suspended Form takes place. This also applies to the fragments of the catalyst particles, if appropriate, if the catalyst is suspended in the oil via machine mills and the spray-dried catalyst particle is split into several smaller pieces.

The catalyst is in heavy oil in special stirred tanks or in Mlschorn, such as. B. in Malschemühlan einuspended. The catalyst mixture prepared in this way is then intimately obtained with further high-boiling hydrocarbon materials to be hydrogenated, the concentration of the catalyst being 0.01 to 3% by weight, based on the total amount of high-boiling carbon material to be converted , This heavy oil catalyst suspension is then pressurized, further heated and passed through a sump phase reaction zone at temperatures of 573 to 773K and a pressure of 7 to 30 MPa in the presence of hydrogen. The reaction is then passed through a separator system in which the separation into different fractions takes place. The valuable distillate oils obtained, in particular the light and medium oils, can either be refined directly after the combined process or after cooling and optionally further fractionation in a separate Hydrordffinationsanlage to high-quality fuel components and Chemiepr be processed products.

The catalyst falls after the Reaktio.iszono in the first He'ßabscheider in the bottom product with high or non-boiling hydrocarbon materials as the hydrogenation residue. He remains in this backlog, as his recovery technologist too expensive and because of the low Kutalysatorpreises too uneconomical.

The residue is fed to a vacuum distillation, in which the still contained valuable distillate oils are recovered. Since the ertindungsgemäße use of the catalyst, its concentration is very low, falls little residue. Little distillate oils are adsorptively bound to the catalyst and all the costly residue processing is simplified. The residue obtained in the vacuum distillation is usually used energetically. Surprisingly wurdo found that the catalytic activity of the catalyst with its novel properties in terms of Molmassenabuaus the large heavy oil molecules and the formation of distillate especially in the boiling range of the light and medium oils is extremely high and even exceeds the activity of pure and expensive heavy metal compounds. A large part of the Asphartene are bound not only adsorptively as with the kohlestämmigen catalysts, but transferred into valuable distillate oils. As a result, the catalyst is deactivated less rapidly, the yield increases, there is less residue ai, there are no agglomeration phenomena and no coking phenomena were observed. Only the formation of a very viscous and sticky residue could be observed, so that a stable, trouble-free long-term operation behavior of the hydrogenation complex is ensured. Hydrogenation reactions take place in addition to hydrocracking reactions which lead to a reduction in the average molecular weight, so that after the bottom phase dehydrogenation already pre-refined light and medium oils are produced, which, as is known, can be further processed better. The erfindungsgomäße method is ideal for the maximum conversion of residues of petroleum processing, such. As for the processing of Visbreakerrückständen and very heavy natural mineral oils, as well as for the much more reactive tar residues of coal refinement. These high boiling hydrocarbon materials are also successfully blended.

Auzfuhrungibeitpiel · The invention will be explained in detail with reference to the following examples.

BetsptoM

The testing of the catalysts was carried out in a 21-Schtel autoclave under f nendon standard conditions:

Hj-Anfangekaltdruck 9MPA reaction pressure 22.0 to 27.6 MPa heating Bgrd / min Holding time at 703 K 16min Einutzproduktmenge about 700 g (Heavy oil)

700g lignite heavy oil (2utammensetzuno and properties sieha Table 1) were each with 1 Ma. %

Catalyst mixed at 353K. A photograph was made of the contact 10927, in an amount of 5% by mass, based on the Heavy oil amount was used. The composition and properties of the eingedetzten catalysts are shown in Table 2. The heavy oil catalyst mixture was charged to the autoclave and charged to the o. Hydrogenated standard conditions. After cooling the autoclave, the reaction product was subjected to distillation. The amount of up to 623K

distilled off light and middle oils diunte to assess the effectiveness of the catalysts used and can be seen from the table.

The results clearly show that the catalysts prepared on the basis of heavy metal-containing slurries a

expand significantly higher activity than the catalyst known under the name Kontakt 10927.

In addition, it was found that the catalysts according to the invention, in their preparation before drying aluminum and / or

or magnesium oxide was admixed, clearly has higher activities with respect to the formation of light and medium oils than the known catalyst A.

The highest efficiency was surprisingly found in the catalysts containing aluminum and magnesium oxide

contained.

Example 2 The Kr.Xa -;% A \ oton A, E, H and contact 10927 were used in various concentrations. The experimental conditions were similar to those in Example Table 4 shows the results of the results. It follows that the catalysts of the invention already in

relatively low concentrations compared to the known catalysts have significantly higher activities with respect to the formation of light and Mlttjlölen.

Tabeii ·

Composition and properties of heavy oil

Density at 293 K (G / ml) 1.0190 pour point (K) 309.6 Flash point (K) 418 Conradsontert (%) 9.8 Asphattgeha'.t (%) 8.4 Vakuumsiedekurve SB (K) 565 5Vol .-% (K) 591 10 vol .-% (K) 604 20vol .-% (K) 623 30Vol .-% (K) 647 40 vol .-% (K) 672 50 vol .-% (K) 698 60Vol .-% (K) 713 70Vol .-% • (K) 766 SE (K / vol .-%) 791/74

table Composition of the catalysts used (in% by mass) catalysts

A B C D e F G H Contact 10927 36.0 23.0 22.0 32.4 17.8 1.8 18.0 18.0 - 10.8 8.9 6.6 9.7 5.3 0.54 5.4 5.4 - 7fi 4.9 4.6 8.8 3.7 0.38 3.8 3.8 - 9.6 8.1 5.8 8.8 4, V 0.48 4.7 4.7 - 7.1 4.5 4.3 8.4 3.5 0.35 3.6 3.8 4.3 4.6 2.9 2.7 4.0 2.2 0.23 2.2 2.2 2.5 3.5 2.2 2.1 3.1 1.7 0.17 1.8 1.8 - 0.8 0.5 0.5 0.7 0.4 0, (V, 0.4 0.4 - 10.0 8.4 8.1 XO 4.9 0.60 5.0 5.0 3.6

PO ₄ ¹ '9.2 5.9 5.6 8.3 4.5 0.46 4.6 4.6 -

CC 0.5 0.3 0.3 0.5 0.2 0.03 0.2 0.2 -

AI ₁ O, - 38.0 - 5.0 27.0 44.0 17 35 -

MgO - - 39.0 5.0 24.0 41.0 33 15 -

Catalyst A was prepared by spray-drying a phosphate-containing slurry. This solids-containing slurry contained the following waste products in the form of DicfcscHamm:

- Abprodukt aus der Lithoponeherst, tion

- residue from ZinK phosphating

- Cu, Ni, Cr and Zn-capable Galvanikechlamm.

The catalysts B to H compared with the catalyst A additionally contain AljO ₃ and / or MgO, the or before the Spray drying were suspended in the slurry. Contact 10927 was obtained by impregnation of fine-grained multiclon dust (C-Gahalt

65% by mass, ash content 35% by mass) with iron-end-sulfate solution and 35% sodium hydroxide solution, followed by drying and

Grinding (see J. Zogala, Freiberger Forschungshefte A36, 1955, p.31). All catalysts used had a particle size s 150 pm.

Table 3 Hydrogenation result

catalyst Catalyst concentration Light and middle oils boiling up to 623 K Catalyst concentration Light and middle oils boiling to S23 K A B C D E F G H Contact 10927 1 1 1 1 1 1 1 1 5 49.5 51.0 50.6 51.5 53.3 5V2 52.6 53.8 48.6 0.1 1.0 2.5 43.1 49.5 52.6 TtbsHs 4 Hydrogenation Results Dependent on the KaMlysator Concentration 0.1 1.0 2.5 50.2 53.3 56.7 catalyst 0.1 1.0 2.5 51.0 53.8 57.4 A 5 48.0 e H Contact 10927

Claims (2)

1. A process for the bottom phase dehydrogenation of high-boiling hydrocarbon materials, such as. As heavy oils and / or residues of petroleum processing and / or coal refining and / or natural mineral oils, which works with a suspendable catalyst whose powder bulk density is not more than 0.75 kg / l, characterized in that a powdery material of a combination of dried heavy slurry and thermally unloaded compounds of magnesium and / or aluminum, the particles of which contain metal compounds as constituents which do not separate and segregate by the action of gravity and are free of charcoal materials. 2. The method according to claim 1, characterized in that the Kstalysatorkonzentration 0.01 to 3Ma .-%, based on the amount of high-boiling hydrocarbon material is. 9 ·