DE3826226C2 - Use of dried, heavy metal-containing thick sludges for the sump phase hydrogenation of high-boiling hydrocarbon materials - Google Patents

Description

The invention relates to the use of dried, heavy tallhaltiger Dickschlämme as a catalyst in the swamp phases hydrogenation of high boiling hydrocarbon materials, such as z. As heavy oils and / or residual oils of petroleum processing and / or residual oils of petroleum processing and / or coal finishing and / or natural mineral oils to high quality Liquid products.

The hydrogenation of high-boiling hydrocarbon materials, such as B. of residual oils of petroleum distillation or Koh leveredlung or natural heavy mineral oils in counter The presence of catalysts is problematic because of these Materials contain substances that are the catalyst used Deactivate gate relatively quickly. Such deactivating sub punching are heavy metal compounds of nickel and vanadium, contained in concentrations of 10 to several hundred ppm asphaltenes with their high coking propensity and Heteroatom compounds, in particular nitrogen compounds. at the processing of such high-boiling materials according to Ver Driving the sump phase hydrogenation first became particular milled pure compounds of molybdenum and tungsten in part used mixed with zinc oxide and magnesium oxide (see W. Krö "The catalytic pressure hydrogenation of coals, tars and Mi Neralölen ", Springer-Verlag, 1950, p. 77) These mixtures were blie but not stable in suspended form as a mixture. It came for demixing the individual active components of the catalyst due to their different sinking speeds, what activi loss of life. By using pure, relative heavy molybdenum and tungsten compounds were high Costs for the catalyst supply and because of their settling phenomena were observed.

Furthermore, the molybdenum and tungsten compounds are only conditionally available. A recovery of the spent Kataly Although it is possible in principle, but usually with a high technical and financial effort. Therefore, these molybdenum catalysts were replaced by the  much lighter, well suspendable in oil cata replaced on the basis of activated lignite When Winklermultiklenstaub proved to be particularly suitable was impregnated with ammonium molybdate (W. Krönig 1950, p. 79).

Nevertheless, for cost and availability reasons also this catalyst by a much cheaper, ge as well suspendable but not so hydrogenating egg senhaltigen catalyst replaced, its production itself by soaking Winklermultiklonstaub with Eisensulfatlö solution and subsequent alkalization elaborately designed (see J. Zogala, Freiberger Forschungshefte, A 36, 1955, P. 31).

When using this catalyst, the asphaltenes are over predominantly not hydrogenated, but only adsorbed and with the Residue is discharged, which reduces the oil yield. Because of the lower activity of this contact he was in high concentrations up to 10 wt .-%, resulting in he considerable amounts of residue, to a costly residue processing and associated high oil losses, ultimately, the overall economics of the hydrogenation process negatively affected.

Furthermore, it is known that tin compounds for the conver of heavy oils have been used successfully. Thus, for the hydrogenation of heavy oils, tin oxalate was used in Combined with hydrogen fluoride and carbon tetrachloride (see Gordon Kenneth, J. Inst., Fuel 9 (1935) 69) 69).

But tin chloride was also used as a catalyst for the heavy oil hydrogenation used.

These tin-containing catalysts work because of their halo genidanteils on all thus coming into contact Rohrlei tions and plant components are strongly corrosive, so that they the uncontrollable corrosion problems on an industrial scale were used only for a short time. Another reason existed in the high price of tin compounds.

Recently, for the hydrogenation of heavy oils in particular relatively cheap catalysts proposed.  

After the in DE-OS-32 32 694, 32 38 689 and 35 34 552 described Processes are carbonaceous catalysts used. there these are coke-like dusts that are found in the hydrating Gasification of coal or coking coal in the stove incurred with metal compounds and in particular of the egg sens, in DE 35 34 552 of vanadium and nickel, elaborately doped and then alkalinized. It was because of that se cabbage materials are used because Winklermul Tiklon dust, the obsolete product of the Winkler gasification of Brown coal, no longer available.

However, these coal-based catalysts have the same Disadvantages on how the Winklermultiklonstaubkontakt. In the However, literature was referred to that a disturbance Free long-term operation without temperature inhomogeneity and coke deposits in the plant parts only below Addition of a lignite-based catalyst achieved who could. (U. Lenz, A. Gier, petroleum coal natural gas petrol Chemistry 38 (1985) 404).

As new catalysts for the hydrogenation of heavy oil suspended in the oil, pure defined compounds of iron, Molybdenum, vanadium, chromium, manganese and titanium (See R. Bearden, C.L. Aldridge, Energy Pro Gress 1 (1981) 1-4, p. 44-88).

Because of the higher activity compared to kata kata The catalyst requirements are lower, but the Catalyst production costs for these pure transition metals tallverbindungen for a disposable catalyst not economically justifiable.

If the powdery sump phase catalyst consists of two or more metal compounds, is due to their different densities and sinking rates in the oil a separation of the catalyst components. This leads to lower the catalytic activities and ultimately for lowering the yield of target products.

Furthermore, the sedimentation tendency of the over transition metal compounds due to the relatively high bulk densities are generally much higher than kohlestämmi  conditions catalysts. It comes to deposits in the Anla parts which can lead to breakdowns.

So z. For example, pure iron sulfate has a density of about 5.25 to that of the generally desired bulk far below 0.75 g / l, so that it is can not be used in the heavy oil hydrogenation (See B. Strobel et al, petroleum coal natural gas petrochemical 34 (1981) 394; M. Höring in Lissner / Thau, "The Chemistry of Brown Coal ", Vol. II, VEB Wilhelm-Knapp-Verlag, Halle 1953, P. 276).

These disadvantages also apply to the DE-OS 33 45 815 before beaten gout dust catalyst.

It is well known that just when using egg Sodium-containing catalysts coking phenomena and Zu agglomerations occur (see B. Strobel et al, Erdöl Coal natural gas Petrochemie 34 (1981) 394; W. Krönig "The ka catalytic pressure hydrogenation of coals, tars and minerals oils ", Springer-Verlag, Berlin / Göttingen).

Furthermore, it was reported that in the mineral oil stämmi residues and heavy oils naturally contained Nickel and vanadium compounds as catalytically active Components are used. The content of these compounds however, generally enough for a maximum conversion not enough, so that depending on the desired degree of conversion and Coke formation tendency of the carbonaceous material Disposable catalyst or additive for stable operation a heavy oil hydrogenation plant with combined refining Part admixed by the Veba Combi-cracking method who must (see K. Kretschmar et al petroleum coal natural gas Pe Trochemie, 39 (1986) 418).

Despite these additive additions become coking observed that only about sufficient hydrogen partial to curb pressure.

The aim of the invention is an improved effective method ren for bottom phase dehydrogenation of high-boiling coal high-energy material, which is used for maximum conversion of  Residual oils to valuable liquid products under Ver Use of a cheap, highly active and well-suspendier Baren catalyst serves.

The technical problem solved by the invention consists of easily obtainable hydrogenation metal components in a catalytically particularly active form as very good suspen dierbare catalysts in an otherwise conventional method for the wet phase hydrogenation of high boiling hydrocarbons materials, such as B. heavy oils and / or residual oils of Petroleum processing and / or coal refinement and / or natural To use mineral oils.

According to the invention, this object is achieved in that the high-boiling hydrocarbon material z. B. residual oils of Petroleum processing and / or coal refinement and / or natural Mineral oils with a well-suspended catalyst, the powder bulk density is not more than 0.75 kg / l, treated, wherein the catalyst used a combination of ent watered heavy metal-containing Dickschlämmen and thermal unloaded compounds of aluminum and / or magnesium in the form of a finely divided material, its part are free of coal-based products and their existence divide by the action of gravity in the high-boiling Do not separate and separate hydrocarbon material. As Schwermetallhaltige Dickschlämme, the Hydriermetallkom components contained and free of coal-based materials are in particular in sufficient quantity ver available products, which in all industrialized countries as Abpro incurred and therefore very cost Ver to stand by.

These mentioned waste products are currently only in a few Cases and usually with larger expenses material  used economically. The largest share is on special dumped, represents an environmental problem and the heavy metals contained are therefore for the people economy lost.

The waste products used contain one or more Hy metal compounds in particular of Zn, Ni, Cr, Cu, Fe.

For corrosion and toxicological reasons disturb in particular chlorides, free cyanides, As, Pb and Cd verbin fertilize. To such heavy metal-containing Dickschlämmen tough len u. a .:

• Ni, Zn, Cr (III) and Cu-containing galvanic sludges,
• Cr (III) -containing thick sludges used in wastewater treatment development in the leather processing industry,
• Zn-containing waste products of lithopone production,
• - Zn-containing residues from the Zn phosphating or -bei zerei)
• Cr (VI) -free, Cr (III) compounds containing waste products from the chromating of aluminum,
• - Chloride- and cyanide-free precipitated sludges from the and corrosive treatment of metallic surfaces,
• - Thick muds of electrochemical metalworking.

These heavy metal-containing thick sludges become alkaliarme, thermally unloaded compounds of Al and / or Mg, the also constitute components in Abproduktschlämmen can, mixed in.

This suspension is z. B. by sputtering method drying, bubble drying or rotational thin layer evaporation processed. This gives a powdery free-flowing product with a residual water content of about 1 to 8 wt .-% and a particle size of 20 to 350 microns.

By targeted addition of magnesium and / or aluminum ver bonds, the bulk density of the catalyst on 0.4 to 0.75 kg / l set.  

This ensures that the catalyst is very good suspended in heavy oil and that no sedimentation the catalyst takes place in the piping and apparatus.

It has proved to be favorable if the kata used lysator 15 to 60% by weight of one or more heavy metal ver compounds of nickel, zinc, copper and chromium, 10 to 60% by weight of aluminum and / or magnesium compounds and contains a maximum of 30 wt .-% iron compounds.

The particles of the catalyst contain a combination in nig mixed heavy metal and light metal connections, whereby the individual connections over special le binding forces are held together so that no Separation or separation of the individual compounds Reason of their different densities during the pneumati transport and in suspended form. The also applies to the fragments of catalyst particles, though optionally the catalyst via mills in the oil is suspended while the spray-dried catalyst is broken into several smaller pieces.

The catalyst is in heavy oil in special stirred tanks or in mixers, such as. B. einhespendiert in mash grinders. These catalyst mashes prepared in this way is then treated with white higher-boiling hydrocarbon material to be hydrogenated intimately mixed, the concentration of the catalyst 0.01 to 3% by mass, based on the total amount to convert high-boiling hydrocarbon material. These Heavy oil catalyst suspension is then ge to pressure brought, further heated and at temperatures of 573 to 773 K and a pressure of 7 to 30 MPa in the presence of water passed through a swamp phase reaction zone. The Reak tion product is then passed through a separator system, in the separation into different fractions takes place. The ge won valuable distillate oils, especially the light and Middle oils, can either raf directly after the combined method  Finished or after cooling and optionally further Frak tion in a separate hydrofinishing plant high quality fuel components and chemical products ver to be worked.

The catalyst falls after the reaction zone in the first hot Separator in the bottom product with high or non-boiling Hydrocarbon materials as hydrogenation residue on. He remains in this residue as its recovery tech nologically too expensive and because of the low catalyst price is too uneconomical.

The residue is fed to a vacuum distillation, at which won the precious distillate oils still contained become. Since by the inventive use of Kataly his concentration is very low, falls a little Arrears. There are few distillate oils adsorptive at the Ka tied to the catalyst and the entire costly return Stand processing is simplified. The at the vacuum de still obtained residue is usually energetic used.

Surprisingly, it has been found that the catalytic Ak tivity of the catalyst with its novel properties in terms of molecular weight degradation of large heavy oil molecules and the formation of distillate oils, especially in the boiling range the light and medium oils are extraordinarily high and even the activity of pure and expensive heavy metal compounds exceeds. Much of the asphaltenes are not just ad sorptively bound as in the coal-based catalysts, but transferred to valuable distillate oils. This will the catalyst deactivates less quickly, the oil yield increases, there is less residue, it comes to no results Agglomerationserscheinungen and there were no Verko observed. Only the formation of a very tough and sticky residue could be observed so that a stable, trouble-free Langzeitbetriebsverhal th of the hydrogenation complex is guaranteed. At the invent Sumpfphasehydrierung according to the invention run in addition to hydrocracking Reactions leading to a decrease in the average molecular mass , Hydroraffinationreaktionen from, so that after the  Sumpfphasehydrierung already pre-refined light and co incurred oil oils that are known to weiterver better let work. The method according to the invention is suitable Excellent for maximum conversion of residues Petroleum processing, such as. B. for the processing of Vis breaker residue and very heavy natural mineral oils, as well as for the much more reactive tar residues de the coal refinement. This high boiling hydrocarbon Fabric materials are also successfully processed in a mixture tet.

example 1

The catalysts were tested in a 2 l shaker autoclave under the following standard conditions:

- H₂ initial cold pressure | 9 MPa - reaction pressure 22.0 to 27 5 MPa - Heating rate 5 grd / min - Test temperature 703 K - Holding time at 703 K 15 minutes - input product quantity (heavy oil) about 700 g

700 g lignite-based heavy oil (composition and egg see Table 1) were each with 1 Ma .-% Ka talysator mixed at 353. An exception was the Kon 10 927, in an amount of 5% by mass, based on the Heavy oil amount was used.

The composition and properties of the Ka used catalysts are shown in Table 2.

The heavy oil catalyst mixture was ge in the autoclave ge fills and at the o. g. Hydrogenated standard conditions.  

After cooling the autoclave became the reaction product subjected to distillation. The amount of down to 623 K Distilled light and medium oils served for evaluation the effectiveness of the catalysts used and is made Table 3 can be seen.

The results clearly show that the base is heavy Metal-containing Abschlämme produced catalysts have much higher activity than that under the Be drawing contact 10927 known catalyst.

In addition, it was found that the catalyst according to the invention in the production of which, prior to drying, aluminum and / or Magnesium oxide was added, clearly higher Akti with regard to the formation of light and medium oils have as the known catalyst A.

The highest effectiveness was surprisingly in the Catalysts found that contain aluminum and magnesium oxide contained.

Example 2

The catalysts A, E, H and contact 10 927 in used in different concentrations.

The experimental conditions corresponded to those of Example 1.

Table 4 shows the test results. from that shows that the catalysts of the invention already in relatively low concentrations compared to the known Catalysts significantly higher activities in terms of Formation of light and medium oils.  

Table 1

Composition and properties of heavy oil

Table 2

Composition of the catalysts used (in% by mass)

The catalyst A was by spray drying a solid produced slurry. This solids-containing slurry contained the following waste products in the form of thick sludge:

• Waste product from lithopone production,
• - residue from zinc phosphating,
• - Cu, Ni, Cr and Zn-containing galvanic sludge.

The catalysts B to H contain compared to the cata- Gate A still additionally Al₂O₃ and / or MgO, the or before the spray-drying were suspended in the slurry.  

The contact 10 927 was by impregnation of the Winkler Ver gassing accumulating, fine-grained Multiklonstaub (C content 65% by mass, ash content 35% by mass) with iron (III) sulphate solution and 35% sodium hydroxide solution and subsequent drying and grinding (see J. Zogala, Freiberger Forschungshefte A 36, 1955, p. 31).

All catalysts used had a particle size of 150 μm on.  

Table 3

Hydrogenation

Table 4

Hydrogenation results as a function of the catalyst concentration

Claims (2)

Use of dried, heavy metal-containing Dickschlämmen in an otherwise customary process for Sumpfphasenhydrierung high-boiling hydrocarbon materials, characterized in that

• a) the heavy metal-containing thick sludges are mixed with alkali-poor, ther mically unloaded compounds of Al and / or Mg to form a catalyst suspension,
• b) this suspension is dried in the usual manner, brought to a particle size of 20-300 microns and the bulk density of the catalyst is adjusted to 0.4 to 0.75 kg / l,
• c) the catalyst contains 15 to 60% by weight of nickel, zinc, copper and / or chromium compound, 10 to 60% by weight of Al and / or Mg compound and a maximum of 30% by weight of iron compound

and the catalyst concentration 0.01 to 3% by weight based on the amount of high boiling hydrocarbon material is.