DE1470686B - Process for converting asphalt, sulfur, nitrogen and oxygen compounds as well as metallic impurities containing heavy hydrocarbon oil into lower boiling products - Google Patents

Description

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temperatures favor dehydrating activity, same as that in the first zone. Under the conditions used here to produce the poisoned hydrocracking or cracking catalyst, there is no nitrogen discharge: increasing excessive amounts of coke, water activation of the catalyst, and feedstock and hydrocarbon gases until the catalysts, which contain about 3000 ppm nitrogen, are regenerated or needs to be replaced. The opposing 5 are continuously converted into a lower-boiling product with excessive amounts of organometallic high yields and for a longer period of time complex compounds are also impaired in other durations. It is assumed that processes such as catalytic reforming, isome- that the pretreatment at low temperature ι risationen, hydrodealkylations. Vanadium itself mainly comprises hydrogenation reactions, while; is also harmful in low-viscosity heating oils and the subsequent treatment at higher temperatures: solid residues that are used as heating fuels mainly contain hydrocracking . because vanadium pentoxide is the tet at high temperature. Through the initial metal removal and remodeling; attacks refractory lines, pipes and other metal conversion of high molecular weight coke precursors under hy constituents of a heating device. The following hydro-It is known to use heavy liquid feed materials with minimal coke formation and materials with the above-mentioned impurities with minimal gas development and, accordingly, directly to gasoline, middle distillates and pure fuel, with the formation of a high yield of liquid heavy oils to crack catalytically or to hy- product.

drokracken, but with the conventional According to the invention, topped raw oils, Temperatures, e.g. B. above about 400 ° C, in strong 20 atmospheric distillates, heavy cycle oils.

! . Dimensions of hydrogen and "light hydrocarbon gases thermally or catalytically cracked material,

f '~) as well as large amounts of coke, and as a result light and heavy vacuum gas oils, but especially

V the coke deposit and accumulation of metallic feed materials, the oil-insoluble asphalts

The catalyst will quickly remove impurities, such as crude oil and impurities j activated. At lower temperatures the 25 residues are to be treated. Raw oil is preferred

Slight hydrocarbon conversions, also because the oil-insoluble asphalts are colloidally dispersed

like the release of nitrogen and sulfur. Are shown and thus more easily converted to oil-soluble hydrocarbons

In addition, the presence of some substances can be converted during the poisoning

1 ppm nitrogen in a distillate material of a ka- asphalt in topped crude oil already as a result of the

analytical hydrocracking in most cases 30 fractionation temperature to some extent agglomerated

the catalysts. are merged and therefore less easily converted

The object of the invention is a simple two-way. The procedure is also good for the

step process suitable for the conversion of a heavy-duty production of distillate materials that are oil-soluble

liquid hydrocarbon oils with non-metallic resins and asphalts, as well as the above

and metallic impurities in lower 35 metallic and non-metallic impurities

contain boiling products by means of hydrogen with increased gene.

Temperature and elevated pressure in the presence of one of the solid hydrogenation strengths used according to the invention Hydrogenation catalyst to purified co-catalyst consists of metallic components lenhydrogen as a product, the gasoline, means with hydrogenation activity and a carrier that consists of a distillate and pure, heavy-bodied materials around- 40 heat-resistant inorganic oxide synthetic grasps. or of natural origin, a large surface area and a well-developed pore structure characterized in that the heavy oil is partly owned.

evaporated and the resulting mixed-phase oil with Suitable carrier substances consist of aluminum hydrogen upward through a first fluidized bed- 45 nium oxide, silicon dioxide, zirconium oxide, magnesium zone in the presence of a hydrogenation catalyst made from oxide, titanium oxide, thorium oxide, boron oxide, strontium oxide Metal of group VI a of the periodic table oxide, hafnium oxide and complexes of two or and nickel on the refractory support for one of more oxides, such as silica-alumina, Temperature from 370 to 440 ° C under pressure. Silica-Zirconia, Silica-Mavon The low-boiling fractions of magnesium oxide, silicon dioxide — titanium oxide, aluminum ions of the oil stripped from the catalyst, then nium oxide - zirconium oxide, aluminum oxide - magnet Catalyst with unstriped higher sium oxide, aluminum oxide, titanium oxide, magnesium boiling ends Oil fractions from the first reaction zone oxide — zirconium oxide, titanium oxide — zirconium oxide, Magnein the second, the same catalyst as the first siumoxide-titania, silica-aluminum zone The reaction zone containing the reaction zone leads and with oxide — zirconium oxide, silicon dioxide — aluminum towards the direction flowing hydrogen, but the oxide-magnesium oxide, silicon dioxide-aluminum reaction temperature higher than in the first zone umoxide — titanium dioxide, silicon dioxide — magnesium im Holds range from 413 to 468 ° C in the di-oxide — zirconium oxide and silicon dioxide — magnets Reaction zone converted oil from the catalysis oxide-titanium dioxide. The carrier substance can gate particles and the stripped Ka- 60 is additionally used as an accelerator halogen, especially fluorine catalyst from the second zone back to the first or chlorine, boric acid, phosphoric acid and boron zone returns. contain phosphate.

The treatment in the lower temperature A hydrogenation catalyst with porous, heat-resistant

first zone with hydrogen makes the use of a digem, inorganic oxide carrier has the ability

a nitrogen-insensitive catalyst and the 65 speed, in its pores a substantial amount, z. B.

Use of several separate systems for charging up to 50 percent by weight, high-boiling coal

No need to manufacture the product. The hydrogenation catalyst adsorbs hydrogen while it is still dry

in the second or higher tempered zone is and appears to flow freely. It was also found

that converted asphalts, d. H. Asphalts which under the conditions of a mild hydrating Cracking gave high boiling hydrocarbons, an excellent solvent for untreated Represent asphalts which are insoluble even in pentane and are colloidally dispersed in a crude oil material or agglomerated dispersed in a topped crude oil material. The untreated Asphalts are much more easily converted to oil-soluble products when initially in one Solvents are dissolved as if they are treated suspended in a flowing vehicle. The asphalt solvent is held in the particles of the hydrogenation catalyst preferentially over lower-boiling fractions of the hydrogen treated feed material if these particles are exposed to a gaseous stripping agent such as hot hydrogen. As a result, the high-boiling fraction becomes in the hydrogenation catalyst adsorbed - and the oil-bearing particles are then in the high temperature stripping conversion zone treated with hot hydrogen to convert adsorbed preheated oil into lower boiling point To convert hydrocarbons and this lower-boiling product from the catalyst ponds stripped, which are then returned to the first zone, although they still have some asphalt solvent contain.

The concentration of the metal component in the catalyst with the carrier substance is primarily determined by the depend on the respective metal. For example, the Group VIa metals are preferably in one Amount between 1 and 20 weight percent and Nikkei between 2 and 10 weight percent present.

The heat-resistant inorganic carrier can be formed by acid treatment of a natural clay, mixed precipitation or stepwise precipitation from hydrosols, optionally combined with activation steps which include evaporation, drying, oxidation, reduction, calcination. The active metal components can be formed on the carrier by impregnation with a solution or by mixed precipitation of the metal with the carrier from an aqueous solution. Supported catalysts suitable for use in the invention preferably have a surface area of 50 to 700 m ² / g, a pore diameter of 20 to 600 Å, a pore volume of 0.10 to 0.80 ml / g and a Bulk density from 0.20 to 0.80 g / cm ³ . Since the catalyst is used in the fluidized bed process, the catalyst particles should be between 20 and 100 microns in diameter. A very satisfactory hydrogenation catalyst consists of 2% nickel and 16% molybdenum on an aluminum oxide-silicon dioxide carrier (63% Al ₂ O ₃ , 37% SiO ₂ ). Another good catalyst consists of 1% nickel and 8% molybdenum on an alumina-silicon dioxide-boron phosphate support with 68% Al ₂ O ₃ , 10% SiO ₂ and 22% BPO ₄ .

The advantages of the two-step process of the invention over conventional one-step treatments are illustrated by the following preliminary tests, with test A in a single Stage at high temperature and test B was carried out in two stages, with only lower and then worked at a high temperature.

Experiment A: 100 g of a Wyoming sour crude oil with a specific gravity of 0.9180 / 15 ° C. with 2700 ppm nitrogen were placed in a 850 cm ³ shaking autoclave. Then 20 g of catalyst, which consisted of 2% nickel and 16% molybdenum on an alumina-silicon dioxide carrier with 25% silicon dioxide, were added to the autoclave filling and the catalyst was thoroughly mixed with the crude oil. The autoclave was sealed, pressurized with hydrogen and quickly brought to a temperature of 440 ° C, at which the hydrogen pressure was about 130 atmospheres. The treatment was continued at 440 ° C. for 3 hours, after which time the reaction gas was analyzed, the pressure was released from the autoclave and the liquid product was recovered.

Trial B: Trial A was performed using the same crude oil and catalyst repeated, but with the exception that the reaction mixture is first heated to 402 ° C and Was held for 2½ hours. Then you increased it Reaction temperature to 440 ° C and held there for 30 minutes; it was gradually left to during the next 30 minutes the temperature will drop to 427 ° C.

A comparison of the results from experiment A and B is given in the table:

Reaction conditions

Time in hours

Temperature ⁰ C Liquid product

specific
Weight
at 15 ° C

nitrogen
ppm

Reaction gas

H ₂

Weight percent

C ₁ -C ₅

Weight percent

Attempt a
Attempt B

2.5 1

440

402 440 to 0.8227
J 0.8193

166
164

72.0
88.4

25.6
5.8

While nitrogen removal exceeded 90% in both cases, the preheat stage decreased the Crude oil with hydrogen at 402 ° C (experiment B) results in the formation of light gaseous hydrocarbons by more than 75%. Nonetheless, the liquid product consisted of a large proportion of gasoline boiling material, as can be seen from the low specific weight.

65 The two step process of the invention can easily be carried out continuously by a heavy oil stream with or without admixture of hydrogen to a temperature in the range of 370 heated to 440 ° C, the oil in a first reaction zone with a stream of hydrogen in the presence of a Treated hydrogenation catalyst, which adsorbs the heavy components of the pretreated oil

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and thus acts as a means of transporting oil. The pretreated oil, which contained a fluidized bed catalyst, is then heated with or without admixture (2% nickel and 16% molybdenum on a porous hydrogen) to a higher temperature than the heat-resistant carrier made of 63% aluminum oxide pretreatment temperature, namely to and 37%> silica from a particle size of 413 to 468 ° C and then in the main reaction 5 from 10 to 150 microns). Introduced as a stripping and opening zone, which contains the same hydrogenation catalyst fluid serving hydrogen at the bottom as the first reaction zone, and into which one of the first reaction zones is introduced in an amount of hydrogen stream. A 4450 Nl / 1 feed is obtained. The temperature of hydrorefined product of improved purity in the first reaction zone was raised to 421 ° C and and lower average molecular weight. The io the pressure was kept at 136 atmospheres. The hydrogen used is recovered outside the hydro space velocity in the first reactor zone and returned to the recycle zone was 0.85 kg of oil per kilogram of catalyst. In an economic processor and hour. A vaporous product stream can this recovered hydrogen until it was withdrawn from the first reaction zone at the top, 50 mole percent of other gases, such as light carbons, which was essentially catalyst-free and comprised of hydrogen gases, hydrogen sulfide, nitrogen, am- hydrogen, light hydrocarbon gases and monia and water vapor, contain. The water and oil vapor as well as some entrained material can contain 890 to 53 400 Nl / 1 of feed oil with its liquid droplets. However, the fraction of the treated oil which boils out to the highest and preferably between 1780 and 37,600 Nl / 1 remained the same. The hydrogen to oil ratio is 20 adsorbed on the catalyst particles. A flow in the first zone and second zone was not necessary from the lower part of the first redigerweise the same, since only a part of the water action section has to be withdrawn, added with heated waste to the first zone and grazing and upstream hydrogen mixed and in the remainder is then introduced into the second zone, the second (high temperature) reaction zone transports the entire outflow from the first zone also 25 benefits, namely in an amount of 6230 Nl / 1 Begelangt. In general, one becomes a general consignment. The temperature here was kept at 452 ° C. from 37.6 to 376 Nl / 1 charge and the pressure was kept at 136 atmospheres. Expend the kungmaterial, depending on the nature of this circulating amount of the catalyst between the loading. The process in connection with the zones was 855 kg / m ^{3 of} feed. The amount of hydrogen generation or purification systems 30 including hydrogen consumption was 190 Nl / 1 loading, which resulted in an impure stream. Liquid product, which was continuously separated from the total outflow of hydrogen from a circulation system of the second reaction zone, had to be withdrawn in order to keep the hydrogen purity at a constant level of 0.824 at 15 ° C. From the outside, the system is supplied with sulfur content of 0.3 percent by weight and a stem of fresh hydrogen to reduce the nitrogen content of 300 ppm. This product is a depleted hydrogen supplement. held only 0.03 percent by weight insoluble in pentane

. . ₁ substances, 0.06 ppm vanadium and 0.03 ppm nickel.

Example j-jj _e yield of liquid substance in weight per

A topped Wyoming sour crude (90% of the cent was 87% of the total feedstock oil, portions boiling below 204 ° C were removed) with 40 If in the above example the first reaction

a specific gravity of 0.9367 at 15 ° C zone and the topped crude oil feed

and a content of 8.5 percent by weight in pen- ping material directly at a temperature of

Tan-insoluble asphalt, 3 percent by weight sulfur 452 ° C treated under otherwise identical conditions

fei, 2850 ppm nitrogen, 84 ppm vanadium and would would be due to the yield of liquid

21 ppm nickel was combined with hydrogen in an amount of 45 more extensive cracking processes and increasing

of 890 Nl / 1 charge mixed. The mixture draws on light hydrocarbon gases

was preheated and about 65 weight percent dropped into a first reaction zone.

Claims (1)

Claim: Process for converting an asphalt, sulfur, nitrogen and oxygen compounds as well as heavy hydrocarbon oils containing metallic impurities in lower-boiling products by reaction with hydrogen in two reaction zones under excess pressure and in the presence of a solid hydrogenation catalyst which is an adsorptive heat-resistant Contains carrier and at least one metal, with a higher in the second reaction zone Temperature than is maintained in the first reaction zone, characterized in that that the heavy oil is partially evaporated and the mixed-phase oil obtained with hydrogen upwards through a first fluidized bed zone in the presence of a metal from group VIa des hydrogenation catalyst Periodic table and nickel on the heat-resistant support at a temperature of 370 to 440 ° C under a pressure of over '34 atü passes the low-boiling fractions of the Strips oil from the catalyst, then the catalyst with the higher-boiling ones that are not stripped Oil fractions from the first reaction zone into the second, the same catalyst as the reaction zone containing the first zone passes and reacts with hydrogen flowing upwards, however, the reaction temperature is higher than in the first zone in the range from 413 to Holds 468 ° C, the converted oil in the second reaction zone strips from the catalyst particles and moving the stripped catalyst from the second zone back to the first zone returns. 40 The invention relates to a method for converting an asphalt, sulfur, nitrogen and oxygen compounds as well as heavy hydrocarbon oils containing metallic impurities into lower-boiling products by reaction with hydrogen in two reaction zones under excess pressure and in the presence of a solid hydrogenation catalyst which is an adsorptive refractory carrier and contains at least one metal, wherein in the second reaction zone a higher temperature than is maintained in the first reaction zone. Such a two-stage hydrogenation process is in U.S. Patent 2,915,452, but its aim and purpose is the manufacture of anti-oxidant petroleum lubricants that are more responsive to anti-oxidant additives. What is essential is this known process converts the aromatic rings of some lubricating oil components into Naphthenic rings. This results in a reduction in undesirable reaction products in the following sharper treatment level. In the first hydrogenation stage is in the range from about 230 to 400 ° C at a pressure of about 10.5 to 211 atmospheres and in the second hydrogenation stage in a temperature range worked from about 343 to 454 ° C under a pressure of about 7 to 176 atü. The catalysts contain Cobalt, molybdenum, platinum, nickel, iron etc. or their oxides or sulfides on carriers such as Bauxite, alumina, silica gel, silica-alumina masses, etc. A refined one is used as the feed and dewaxed lubricating oil distillate from paraffinic naphthenic crude oil is used. The German Auslegeschrift 1115 393 describes a catalytic processing of vapors or Gases from coking, gasification or smoldering, namely in the first pressure refining stage a high mechanical strength catalyst used as an active filter while in the a different catalyst is used in the second stage. It is considered a particular advantage that it is possible to work in the second zone at a lower temperature than in the first zone. The two known processes start from relatively pure feeds. In particular, it is missing the various impurities that act as catalyst poisons. It is also in In both cases it is not about the production of a gasoline-like, liquid product. Heavy hydrocarbon oils such as are used as feed in the process of the invention, that is z. B. contaminated crude oil, residue from the first distillation and other heavy hydrocarbon fractions and distillates separated therefrom, contain various non-metallic and metallic impurities such as nitrogen, sulfur and oxygen. Nitrogen poisons various catalysts involved in the conversion of petroleum fractions can be used. But nitrogen and sulfur are also unpleasant because they release nitrogen oxides and sulfur oxides when the hydrocarbons are burned. sulfur also leads to the formation of resinous components and reduced lead sensitivity. Another group of crude oil contaminants is asphalt, which is non-distillable and insoluble in oil and represents high molecular weight coke precursor and contains sulfur, nitrogen, oxygen and metals. When heated, for example during vacuum distillation, asphalt coagulates and / or polymerizes and are extremely difficult to convert into more valuable oil-soluble products. Therefore, they are in the heavy-bodied Residues from a vacuum distillation column remove the polymerized asphalt at normal Temperature fixed. Such a product is only to be used as road asphalt or in dilution with middle distillates as inferior fuel. The most common metallic impurities are nickel and vanadium, although other metals are often also so iron, copper, and zinc, are present. They lie mainly as thermally stable organometallic complexes, such as poryphyrins and their derivatives, and are mostly with the Asphaltenes are combined and are concentrated in the residual fraction. Although their concentration in oil distillates can be relatively low (often below 10 ppm), it does subsequent work processes are often impaired. If z. B. a hydrocarbon material with 3.0 ppm organometallic compounds such as metal porphyrins, hydrocracking or catalytic If cracking is subjected to lower boiling hydrocarbons, the metal precipitate increases and its concentration on the catalyst over time. Because vanadium and the ferrous group metals at the usual cracking temperatures