FI59118B - FOERFARANDE FOER KATALYTISK HYDROAVSVAVLING AV RESTKOLVAETEOLJOR - Google Patents

Description

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England-England (GB) 1 * 7299/72 (71) Shell Internationale Research Maatschappij BV, Carel van Bylandt-laan 30, The Hague, Netherlands-Nederländerna (NL) (72) Karel Maarten Adrianus Pronk, Amsterdam, Swan Tiong Sie, Amsterdam , Netherlands-Nederlanderna (NL) (7 * 0 Oy Kolster Ab (54) Process for the removal of sulfur from catalytic hydrogenation of residual hydrocarbon oils - Pörfarande för katalytisk hydroavsvavling av restkolväteoljor

The invention relates to a process for the removal of sulfur from catalytic hydrogenation without the addition of catalyst from residual hydrocarbon oils having a total vanadium and nickel content of more than 120 ppm by carrying out the process at 300-1 + 75 ° C at a hydrogen partial pressure of 50-200 bar at 0.1-10% by weight. a fresh feed of 1 part by weight of catalyst per hour and a hydrogen / ..... 3 feed rate of 0.15-2.0 mN Hg / kg of feedstock and using a catalyst consisting of one or more metals with hydrogenation activity on the surface of the support and having such an average specific pore diameter (p, nm) and an average specific particle diameter (d, mm) such that the quotient p / (d) ^ '9 satisfies the condition: 1 *, 5 x 10 "1 * (P) 2 ^ p / (d ) 0'9 ^ 9 x 10_1 * (P) 2, h2 h2 2 59118 where Pti is the partial pressure of hydrogen used (Pu, bar) and the pore volume of the catalyst is more than 0.1 + 5 ml / g, wherein at least 0.1+ ml / g of the pore volume is in pores with a diameter of 0 or more .7 x p and up to 1.7 x p and the pore-diameter distribution is sharp. Residual hydrocarbon oils generally contain significant amounts of sulfur compounds. When these oils are used as fuel, the sulfur in the sulfur compounds is converted to sulfur dioxide, which is released into the atmosphere. In order to prevent air pollution as effectively as possible when these oils are burned, it is desirable that their sulfur content could be reduced. This can be accomplished by removing sulfur by catalytic hydrogenation of the oils. For this purpose, methods may be used in which continuous or intermittent replenishment of the catalyst in the desulfurization reactor takes place during use, or methods in which such replenishment does not take place. For the sake of brevity, the latter processes, exemplified by the process of the invention, are referred to herein as "desulfurization by catalytic hydrogenation without catalyst addition".

The desulfurization of residual hydrocarbon oils by catalytic hydrogenation involves certain problems which do not arise when the process of the invention is used to desulfurize hydrocarbon oil distillates by hydrogenation. These problems are due to the fact that most hydrocarbon residual oils, such as those obtained from the distillation of crude oils under normal or reduced pressure, contain high molecular weight, non-distilled compounds such as asphaltenes and metal compounds, especially vanadium and nickel compounds, which are largely bound to asphalt. In hydrogen desulfurization, asphaltenes and vanadium and nickel compounds tend to precipitate on the surface of the catalyst particles. Some of the high molecular weight compounds precipitated on the catalyst particles are converted to carbon. As a result of the increasing concentration of vanadium, nickel and coke, a very rapid deactivation of the catalyst takes place on the surface of the catalyst. As the activity of the catalyst decreases, higher temperatures must be used to maintain the desired degree of desulfurization. However, at higher temperatures, hydrocracking reactions begin to play an increasingly important role and fuel oil of varying quality is obtained.

To prolong the life of the catalyst, it has been suggested that the asphaltenes should be removed from the feed mixture before the latter is desulfurized and that the separated asphaltenes should then be remixed with the purified product. However, this approach requires an additional step in the process, namely the removal of asphaltenes, and has other disadvantages. Thus, a desulfurization process by hydrogenation is preferred, according to which the feed mixture is treated as such, i.e. asphaltenes. However, this embodiment of the process requires catalysts which are not as easily deactivated as are currently generally recommended for this purpose.

3,5118

A study on the desulphurisation of residual hydrocarbon oils by catalytic hydrogenation without catalyst replenishment with a total vanadium and nickel content of more than 120 ppm has revealed that particle size and porosity requirements. For optimum catalysts, these requirements depend in part on the partial pressure of hydrogen at which the desulfurization hydrogenation is performed. For the purposes of this publication, a desulfurization hydrogenation of residual hydrocarbon oils without supplementation with a suitable optimum catalyst refers to a catalyst having a sufficiently long lifetime to desulfate a sufficient amount of residual hydrocarbon oil per kilogram of catalyst is obtained at an acceptable volume flow rate.

It has been found that in the catalytic desulfurization hydrogenation of residual hydrocarbon oils without catalyst replenishment having a total vanadium and nickel content of more than 120 ppm, the requirements for the optimum catalyst particle size and porosity of one or more metals with hydrogenation activity on a support. First, the mean specific pore diameter (p, nm) of the catalyst particles and its mean specific particle diameter (d, mm) must be such that the quotient p / (d) satisfies the condition U, 5 x 10_U (P) 2-rp / (d ) ° '9- 9 x 10-1 * (P) 2, H2 H2 where Pjj is the partial pressure of hydrogen used (Pj ^ »bar). Furthermore, the pore volume of the catalyst should be greater than 0.5 ml / g so that at least 0.1 ml / g of the pore volume is in pores with a diameter of at least 0.7 xp and at most 1.7 x p. Finally, the catalysts must have a sharp huokoshalkaisijajakautuma.

The process according to the invention is characterized in that the pore diameter distribution of the catalyst used is as follows: a) less than 20% of the pore volume is in pores with a diameter of less than 0.7 xp, b) less than 20% of the pore volume is in pores with a diameter of more than 1.7 xp, and (c) less than 10% of the pore volume is in pores with a diameter greater than 100 nm.

* 59118

The manner in which d is determined depends on the shape of the catalyst particles. If their shape is such that the particle diameter distribution of the catalyst can be determined by sieve analysis, d is determined as follows. After complete sieve analysis of a representative catalyst sample, d is read from the curve cumulatively plotting the percentage by weight of each successive sieve fraction as a function of the linear mean particle diameter of the relevant sieve fraction; d is the particle diameter corresponding to 50% of the total weight. This method can be used to determine d for spherical and granular materials with a similar shape, such as extrudates and spheres with a length / diameter ratio of 0.9 to 1.1. The determination of the value of d for extrudates and spheres with a length / diameter ratio of less than 0.9 or more than 1.1 and for similar cylindrical materials whose particle diameter distribution cannot be determined by sieve analysis is performed as follows. When a complete length distribution analysis (when the length / diameter ratio is less than 0,9) or a complete diameter distribution analysis (when the length / diameter ratio is more than 1,1) of a representative catalyst sample is performed, d is read from the curve cumulatively plotted for each for a successive length or diameter fraction, its percentage by weight of the total weight of the catalyst sample as a function of the linear average size of the relevant fraction: d is the value corresponding to 50% of the total weight.

Once the complete pore diameter distribution of the catalyst sample has been determined, p is read from a curve cumulatively plotted in the pore diameter range 0 to 100 nm for each successive portion of the pore volume less than or equal to 10% of the functional volume in the pore diameter range: p is the pore diameter corresponding to 50% of the total quotient at 100 nm.

The determination of the complete pore diameter distribution of the catalyst can very conveniently be performed by the nitrogen adsorption / desorption method (presented by EV Ballou and 0. K. Doolen, Analytical Chemistry 32, 532 (1960)) combined with the mercury penetration method (presented by HL Ritter and LC Drake, Industrial and Engineering Chemistry, Analytical Edition 787 (19 ** 5)) using mercury pressures of 1-2,000 bar. In this case, it is recommended to calculate the pore diameter distribution of the catalyst in the pore diameter range of 7.5 nm and less from the nitrogen desorption isotherm (assuming the pores are cylindrical) according to the method of J. C. P. Broekhoff 5 59118 and J. H. de Boer, Journal of Catalysis JO. 377 (1968) and the pore diameter and distribution of the catalyst in the pore diameter range above 7.5 nm is recommended to be calculated using the following formula:. . , ,, · - ·, ϊ 15 000 pore diameter (nm) - absolute mercury pressure (bar) o 9

The above catalysts in which the quotient p / (d) 'satisfies the requirement U, 0 ^ p / (d) ^' ^ i = 20.0 have already been described as new preparations in Applicant's GB Patent Publication No. Uo8,759. catalysts are characterized by a certain ratio between their average pore diameter and their average particle diameter at a given partial pressure of hydrogen and a certain pore diameter distribution within pore diameter ranges which depend on the average pore diameter of the catalysts. It is necessary that the average pore diameter and average particle diameter used to characterize the catalysts be determined according to the methods set forth above for the average specific pore diameter and average specific particle diameter, because if the average particle diameter or average particle diameter e.g., the average pore diameter calculated as a quadruple of the pore volume and area, or the average particle diameter calculated as a linear average), completely different results can be obtained.

The observed relationship between the quantities p, d and P «2 can serve three different purposes. First, this ratio makes it possible to determine the range from which Ph 1 must be selected in order to obtain good results with a catalyst having a defined p and d. Furthermore, the ratio can be used to determine the range from which the catalyst at a given p-value of material d must be selected in order to obtain good results at a given Pj ^ value. Finally, the ratio makes it possible to determine the range from which the catalyst p at a given d-value must be selected in order to obtain good results at a given Pj-value. The most suitable values for the quantities PH0 »d J * p in the observed areas are determined, among other things, by the composition of the hydrocarbon oil from which the sulfur is to be removed.

The surface area of the catalysts used in the process of this invention. The area is more than 50 m / g, preferably more than 100 m / g.

6 59118

The catalysts used according to the invention preferably contain 0.5 to 20 parts by weight and most preferably 0.5 to 10 parts by weight of nickel and / or cobalt and preferably 2.5 to 60 parts by weight and most preferably 2.5 to 30 parts by weight of molybdenum. and / or tungsten per 100 parts by weight of carrier. The atomic ratio between nickel and / or cobalt on the one hand and molybdenum and / or tungsten on the other can vary widely, but is preferably from 0.1 to 5. Examples of highly suitable metal combinations for the catalysts of this invention are nickel / tungsten, nickel / molybdenum, cobalt / molybdenum and cobalt / molybdenum. The metals may be present on the support in metal form or in the form of their oxides or sulfides. The most preferred catalysts of this invention are those in which the metals are on the surface of the supports as sulfides. The sulfidation of these catalysts can be performed by any catalyst sulfidation method well known in the art. The sulfidation can be carried out, for example, by contacting the catalysts with a sulfur-containing gas, such as a mixture of hydrogen and hydrogen sulfide, a mixture of hydrogen and carbon disulphide, or a mixture of hydrogen and mercaptan, such as butyl mercaptan. Sulfidation can also be performed by contacting the catalysts with hydrogen and a sulfur-containing hydrocarbon oil, such as sulfur-containing kerosene or gas oil. In addition to the catalytically active metals mentioned above, the catalysts may contain other catalytically active metals and catalyst accelerators such as phosphorus, boron and halogens such as fluorine and chlorine. Highly suitable supports for the catalysts of this invention include oxides of Group II, III and IV elements of the Periodic Table or mixtures of these oxides, such as silica, alumina, magnesium oxide, zirconia, thorium oxide, boron oxide, hafnium oxide, silicon alumina, silicon magnesium oxide, alumina -zirkoniumoksidi.

The preparation of the catalysts used according to the present invention can be carried out by mixing the metals on a support having a pore diameter distribution and an average specific pore diameter such that, after precipitation of the metals, a catalyst is obtained which meets the requirements of the invention either as such or after the average specific particle diameter of the catalyst has been increased or decreased.

The porosity of the finished catalyst depends to some extent on the amount of metal used. In general, it can be said that starting from a support having a certain porosity, a catalyst with a lower porosity is obtained according to the higher amount of metal used. This phenomenon has only a minor significance τ 59118 when using relatively low amounts of metal, i. about 20 parts by weight or less of metal per 100 parts by weight of support. In this case, with relatively low amounts of metal, the porosity of the final catalyst is determined mainly by the porosity of the support used, and in the preparation of catalysts of the invention with relatively low metal contents, supports whose porosity differs only slightly from the desired final porosity. At higher metal contents, the effect of the amount of metal on the porosity becomes more important, and the use of a large amount of metal can provide a means of preparing the catalysts of the invention from supports with too high a porosity. The porosity of the carrier can also be influenced by high temperature treatment, either in the presence or absence of steam.

The porosity of the carrier is mainly determined by the way in which the carrier is prepared. Metal oxide type catalyst supports are usually prepared by adding to one or more of the above. an aqueous solution of a metal salt with one or more gelling agents, as a result of which the metals precipitate in the form of metal hydroxide gels, which are then shaped and calcined. Usually, metal hydroxide gels are allowed to age for some time before being formed. During the preparation of the carrier, there are many possibilities to influence the porosity of the carrier. The porosity of the final carrier depends, among other factors, on the rate of addition of the gelling agents and the temperature and pH used during gel formation. The porosity of the final carrier can also be affected by the addition of certain chemicals to the gel, such as phosphorus and / or halogen compounds. If aging is used, the porosity of the final carrier also depends on the aging time and the temperature and pH used during aging. One aspect of the preparation of metal oxide alloy carriers that is important in view of the porosity of the final carriers is the manner in which the metal hydroxide gels are precipitated: simultaneously or separately, e.g., one on top of the other. The porosity of the final carrier further depends on the manner in which the carrier particles are formed, the conditions used during shaping, and the temperature used during calcination.

During shaping, the porosity of the carrier particles is affected by, for example, the type and amount of peptizing and binders usually added at this stage of carrier preparation, the addition of certain chemicals, and the addition of small amounts of inert substances such as silica and / or zirconia. If the carrier particles are formed by extrusion, the porosity of the final carrier is affected by the extrusion pressure used. If a spray-drying technique is used, the porosity of the carrier is affected by the spray temperature and pressure used.

The catalysts used in accordance with this invention can be prepared by any of the multi-component catalyst valraic techniques well known in the art. It is not necessary that the catalytically active metals be precipitated on the finished support; they may also be incorporated into the carrier material during their manufacture, e.g. before shaping. The incorporation of catalytically active metals into the support at an early stage in the preparation of the catalyst can also have a strong effect on the porosity of the finished catalyst. The catalysts used according to the invention are preferably prepared by single or multi-stage co-impregnation of the support using an aqueous solution containing one or more nickel and / or cobalt compounds and one or more molybdenum and / or tungsten compounds, followed by drying and calcination. If the impregnation is carried out in several stages, the material can be dried and calcined, if desired, between successive impregnation steps. The drying is preferably carried out at a temperature of 50 to 150 ° C and the calcination at a temperature of 150 to 550 ° C, respectively. Examples of suitable water-soluble compounds of nickel, cobalt, molybdenum and tungsten that can be used in the preparation of these catalysts include nitrates, chlorides, carbonates, formats and acetates of nickel and cobalt, ammonium molybdate and ammonium tungstate. To increase the solubility of these compounds and to stabilize the solutions, certain compounds such as ammonium hydroxide, monoethanolamine, and sorbitol may be added to the solutions.

Alumina and silicon alumina are recommended as supports for the catalysts used in accordance with this invention. Highly suitable carriers are alumina particles prepared by spray-drying alumina gel and then forming larger particles from the spray-dried microparticles, e.g. by extrusion, and spherical alumina particles obtained by a well-known oil sputtering method. In the latter method, an alumina hydrosol is formed, a suitable coagulant is combined with the hydrosol, and the mixture is dispersed in drops in an oil maintained at an elevated temperature; the drops are allowed to remain in the oil until they have solidified into spherical hydrogel particles, which are then separated, washed, dried and calcined. Highly suitable silica-alumina supports for these catalysts are the combined gels of aluminum hydroxide gel and silica hydrogel. These co-gels are preferably prepared by first precipitating a silica hydrogel from an aqueous solution containing silicate ions by adding mineral acid, then adding a water-soluble aluminum salt to the mixture, and then precipitating the aluraine hydroxy gel by adding an alkali-reactive compound. It is recommended that the formed silica hydrogel be allowed to age for some time at an elevated temperature before the co-gel preparation is continued. Aging conditions, especially aging time and aging temperature, have a strong effect on the porosity of the final co-gel. The preparation of the catalysts based on the above co-gels used according to the present invention can be carried out, e.g., as follows: First, the co-gel is formed, e.g., by extrusion, followed by drying and calcination of the hydrogel particles. The xerogel particles thus obtained are then neutralized with nitrogen base and dried. Finally, the catalytically active metals are precipitated on the support by impregnation of the latter with one or more aqueous solutions containing said. metal salts, followed by drying and calcination of the mixture. The preparation of the catalysts based on the above co-gels used according to the present invention can also be carried out by the following simplified method. The catalytically active metals are incorporated into the co-gel by mixing with the latter one or more aqueous solutions containing said. metal salts, after which the mixture is formed, e.g., by extrusion, dried and calcined.

The catalytic desulfurization hydrogenation of residual hydrocarbon oils without catalyst replenishment is preferably carried out by passing the hydrocarbon oil upwards, downwards or radially in the presence of hydrogen at elevated temperature and pressure and in the presence of hydrogen through one or more vertically arranged reactors containing one or more solid catalyst layers. The desulfurized hydrocarbon oil may be completely or partially saturated with hydrogen and, in addition to the hydrocarbon phase and the catalyst phase, there may be a hydrogen-containing gas phase in the reactor. Further, a portion of the liquid product, with or without dissolved hydrogen, hydrogen sulfide and / or hydrocarbon gases, can be recycled to the catalyst bed.

Desulfurization hydrogenation can be performed either in one reactor or in two or more reactors. Generally, desulfurization hydrogenation reactors contain more than one catalyst bed. The catalysts used in the separate catalyst layers and / or in the separate reactors may differ in terms of their p- and / or d-values and / or chemical composition. If several reactors are used, it is possible to use all these reactors simultaneously to carry out the desulfurization reaction. It is also possible to use the reactors alternately for desulfurization, in which case the desulfurization is carried out in one or more reactors while the catalyst is regenerated in the other reactors.

, 0 591 1 8 The desulfurization hydrogenation of residual hydrocarbon oils without catalyst replenishment can very conveniently be carried out by passing the hydrocarbon oil together with hydrogen through a vertically arranged solid catalyst bed at an upward rate of liquid and / or gas such that the catalyst bed expands. Another suitable embodiment of the desulfurization hydrogenation of residual hydrocarbon oils without catalyst replenishment is one in which the hydrocarbon oil is passed with hydrogen through an upwardly positioned solid bed and the adiabatic temperature rise due to the desulfurization hydrogenation reaction is kept below 20 ° C by recycling hydrogen at various points in the catalyst bed.

Catalytic desulfurization hydrogenation of residual hydrocarbon oils without catalyst replenishment generally utilizes catalyst particles having an average specific particle diameter of 0.5 to 2.5 mm. If the desulfurization is carried out by passing the hydrocarbon oil to be purified together with hydrogen through a vertically arranged solid catalyst bed upwards or downwards, catalyst particles with an average specific particle diameter of 0.6-2.0 mm are preferably used.

The observed dependence between the quantities p, d and Pjj makes it possible to prepare catalysts for the desulfurization hydration of residual hydrocarbon oils with a certain Py ^ value, which gives the optimum efficiency. If a catalyst or catalyst support is available whose d is not optimal with respect to the p-value of P1, it is possible to prepare an optimal catalyst or catalyst support by fitting d to p. This can be accomplished in a simple manner by increasing or decreasing the particle size of the catalyst or catalyst support. size (e.g., by combining the particles with or without a binder or by grinding the particles).

The following problem may arise when preparing the optimum catalysts of this invention from a given catalyst or catalyst support material from desulfurization. The optimum for a large d at a given Pp? Value corresponding to the magnitude p of the material from which the catalyst is to be made can be so small that the use of these small catalyst particles for desulfurization hydration can result in difficulties. In this case, it is recommended that these small particles, whose d is optimal with respect to the values of p and Pw, be formed. 2 agglomerates having more than 10% of the pore volume in the pores with a diameter greater than 100 nm. It is recommended that the small particles be formed into agglomerates having more than 25% of the pore volume in pores with a diameter of more than 100 nm. The use of these porous catalyst agglomerates in the desulfurization hydrogenation of residual hydrocarbon oils offers the same advantages as the use of small optical catalyst catalyst particles without the disadvantages inherent in the use of these small catalyst particles. in the presence of material which is incorporated into the agglomerates and then removed by evaporation, incineration, dissolution, rinsing or other means so as to leave sufficient pores with a diameter of more than 100 nm in the agglomerates. Suitable compounds for this purpose include cellulose-containing substances, polymers and compounds which are soluble in organic or inorganic solvents.

In the desulfurization hydrogenation process of the invention, the reaction conditions used can vary widely. The desulphurisation hydrogenation is preferably carried out at a temperature of 300-1 + 75 ° C with a partial hydrogen pressure of 50-200 bar at a volume flow rate of 0.1-10 parts by weight of fresh feed per 1 part by weight of catalyst per hour and a hydrogen / feed ratio of 0.15-2.0 m ^ H ^ / kg feed. The most preferred reaction conditions are at temperatures of 350 to 55 ° C, a partial pressure of hydrogen of 80 to 180 bar, a volume flow rate of 0.5 to 5 parts by weight of fresh feed per 1 part by weight of catalyst per hour and a hydrogen / feed ratio of 0.25 to 1, 0 m ^ H ^ / kg feed.

This publication restricts the use of catalysts that meet certain requirements in terms of quotient p / (d) ^ '^ and pore diameter distribution to the desulfurization hydrogenation of residual hydrocarbon oils without catalyst replenishment with a total vanadium and nickel content greater than 120 ppm. The use of these catalysts for the desulfurization hydrogenation of residual hydrocarbon oils without catalyst replenishment with a total vanadium and nickel content of up to 120 ppm is described in Applicant's GB Patent Publication 1 1 * 08 759.

The desulfurization hydrogenation process of this invention may very suitably be preceded by a metal removal process. As a result of the metal removal, the deactivation of the desulfurization-hydrogenation catalyst is considerably reduced. In any case, the residual hydrocarbon oils used as feed for this combined process must contain a total of more than 120 ppm of vanadium and nickel. The dewatering of these residual hydrocarbon oils should be carried out in such a way as to obtain a product with a total vanadium and nickel content reduced above 120 ppm.

12 591 1 8 The metal removal of residual hydrocarbon oils is preferably carried out by passing the hydrocarbon oil upwards, downwards or radially in the presence of hydrogen at elevated temperature and pressure and in the presence of hydrogen through one or more vertically arranged reactors containing suitable solid or mobile bed catalyst particles. A very suitable embodiment of the dewatering process is one in which the hydrocarbon oil is passed through a vertically arranged catalyst bed and in which fresh catalyst is periodically fed onto the catalyst bed during use and the spent catalyst is removed from it (dewatering by silo-flow operation). Another very suitable embodiment of the demetallization process is one having a plurality of reactors containing a solid catalyst bed which are used alternately for demetallization; while dewatering is performed in one or more of these reactors, the catalyst is replenished in other reactors (dewatering by solid bed exchange operation). If desired, metal removal can also be performed by suspending the catalyst in a hydrocarbon oil from which the metals must be removed (metal removal with a slurry phase operation). Excellent catalysts for the removal of metals from residual hydrocarbon oils are catalysts containing one or more metals with hydrogenation activity on the surface of the support, which catalysts meet the following requirements 1} pore volume greater than 0.1+ ml / g 2) percentage by volume of pores consisting of pores the diagonal is more than 100 nm (v) is less than 50 and 3) the quotients of the quantities p and d are more than 10-0.15 v.

If the desulfurization according to the invention is preceded by metal removal, it is preferably carried out as a silo flow operation or a fixed bed exchange operation, and the desulfurization is a conventional solid bed operation.

Examples of feed mixtures to which the desulfurization hydrogenation process according to the invention (with or without a metal removal process) can be used are crude oils and residues obtained by distilling crude oils under normal and reduced pressure. It is recommended that the desulfurized feed mixture contain less than 50 ppm, preferably less than 25 ppm of alkali metal and / or alkaline earth metal. If the alkali metal and / or alkaline earth metal content of the feed mixture is too high, it can be reduced, for example, by removing salts from the feed mixture.

The invention will now be illustrated by the following examples.

Example I

Catalyst preparation

Catalyst A

A catalyst was prepared containing U, 7 parts by weight of cobalt and 13,591 1 8 11, U parts by weight of molybdenum per 100 parts by weight of alumina, as follows:

An aqueous solution of 1,163 g of cobalt nitrate (6 water of crystallization) was mixed with an aqueous solution of 1,051 g of ammonium molybdate (the ammonium molybdate used in the examples of this publication contained molybdenum in 5, 3% by weight).

After adding 350 ml of 25 Game ammonia, the mixture was diluted to 3,800 ml with water. This mixture was used to impregnate 5,000 g of 1.5 mm alumina extrudates. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst B

A catalyst containing U, 7 parts by weight of cobalt and 11.1% by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

An aqueous solution of 38.9 g of cobalt nitrate (6 water of crystallization) was mixed with an aqueous solution of 35.1 g of ammonium molybdate. After 10 ml of 25 # ammonia was added to the mixture, it was diluted with water to 125 ml. This mixture was used to impregnate 166.9 g of 1.5 mm alumina extrudates. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst C

A catalyst containing U, 7 parts by weight of cobalt and 11. U parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

An aqueous solution of 33.1 g of cobalt nitrate (6 crystalline water) was mixed with an aqueous solution of 29.9 g of ammonium molybdate. After 10 ml of 25 # ammonia was added to the mixture, the mixture was diluted with water to 108 ml. This mixture was used to impregnate 1 to 2.3 g of 1.5 mm alumina extrudates. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalysts D and E

Two catalysts containing 3.8 parts by weight of cobalt and 9.5 parts by weight of molybdenum per 100 parts by weight of alumina were prepared as follows:

An aqueous solution of 9 ** 0 g of cobalt nitrate (6 water of crystallization) was mixed with an aqueous solution of 876 g of ammonium molybdate and 1,000 ml of 30% H 2 O 2. After diluting with water to 3 L * 50 ml, the mixture was used to impregnate 5,000 g of 0.8 mm alumina extrudates, after 30 minutes the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for j hours. A part of the catalyst D thus obtained was crushed to prepare catalyst E, where d is 0.2 mm.

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Catalysts F, and G

23.2 kg of an aqueous solution containing 5.256 kg of sodium silicate (SiO 2 content: 26.5 wt.%) Was heated to + 0 ° C. The pH of the solution was lowered from 11.1 to 6 by adding 2,200 ml of 6N HNO 2 over 30 minutes with stirring. The resulting silica gel was aged for 2b hours at 140 ° C. 2 J + U8 g of an aqueous solution containing 1,528 g of Al (NO 2) 3 .9HgO and a temperature of U0 ° C was added to this mixture over 5 minutes with stirring. After stirring for an additional 10 minutes, the pH of the mixture was raised to U.8 by the addition of 25 # ammonia. After 10 minutes, the pH of the mixture was further raised to 5.5 (total ammonia consumption about 900 ml). The silica-alumina joint gel was filtered off and washed with water until it contained no sodium. The gel was extruded into 1.5 mm extrudates. The extrudates were dried at 120 ° C and calcined at 500 ° C.

620 g of this silica-alumina co-gel were neutralized with 6.2 l of 0.1 M NH 4 NO 2 solution and 15 ml of 25 # ammonia. The silica-alumina was filtered off, washed with water and dried at 120 ° C.

The above-mentioned silicon alumina (95 wt.% Solids) was used as a support for two catalysts containing 2 parts by weight of nickel and 16 parts by weight of molybdenum per 100 parts by weight of silicon alumina. The catalysts were prepared as follows:

An aqueous solution of 176 μg of ammonium molybdate was mixed with an aqueous solution of 37.7 g of nickel formate (2 water of crystallization). After adding 110 ml of monoethanolamine, the mixture was diluted with water to 700 ml. This mixture was used to impregnate 630 g of the above silicon alumina (598.5 g of dry matter). After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours. A portion of the catalyst F thus obtained was crushed to prepare catalyst G, where d is 0.5 mm.

Catalyst H

116.25 kg of an aqueous solution containing 26.25 kg of sodium silicate (SiO 2 content 26.5 wt.%) Was heated to 0 ° C. The pH of the solution was lowered to 6 by the addition of 6N HNO 2 over 30 minutes with stirring. The resulting silica gel was aged for 1U0 hours at 100 ° C with stirring. 30 L of an aqueous solution containing 7.66 kg of Al (NO 2) 3 .9HgO and a temperature of U0 ° C was added to the mixture over 5 minutes with stirring. After stirring for an additional 10 minutes, the pH of the mixture was raised to b, 8 by the addition of 25 # ammonia. After 10 minutes, the pH of the mixture was further raised to 5.5 · The silica-alumina co-gel was isolated by centrifugation and washed until it contained no sodium. This co-gel (12, U% dry matter) was used as a support for a catalyst containing 2 parts by weight of nickel and 16 parts by weight of molyMene per 100 parts by weight of silicon alumina. The catalyst was prepared as follows:

1,008 g of a silica-alumina co-gel (= 125 g of dry matter) was beaten for 10 minutes. Then 7.87 g of nickel formate (2 water of crystallization) was added and the material was beaten again for 5 min. A solution of 36.83 g of ammonium molybdate in a small amount of water and HgO 2 (molar ratio H 2 O 2 / Mo = 0.25) was added and the mixture was beaten for 1 hour. The product was extruded into 1.2 mm extrudates. The extrudates were dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours. Catalyst I

A catalyst containing H, 3 parts by weight of nickel and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

An aqueous solution containing 11.9 g of molybdenum as ammonium molybdate and 7.1 g of HgOg (molar ratio H 2 O 2 / Mo = 0.5) was mixed with an aqueous solution containing **> 73 g of nickel as nickel nitrate. After diluting the mixture with water to 110 ml,

it was used to impregnate 110 g of alumina. After 15 minutes, saturate •. .. Is , . .... O

The material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours. The alumina used as the support was obtained by extruding spray-dried alumina. The alumina extrudates had the following properties: pore volume: 0.68 ml / g pore volume in pores with a diameter of -0.7 xp and -1.7 xp: 0.56 ml / g 2 surface area: 250 m / g,% of the pore volume in the pores, with diameter c0,7 xp: 9% ·,% of pore volume in pores with diameter> 1,7 xp: 7, **% of pore volume in pores with diameter> 100 nm: 2,0%, average specific pore diameter (p): 13, 0 nm, average specific particle diameter (d): 1.5 mm.

Catalyst J

Catalyst containing U, 3 parts by weight. cobalt and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina were prepared as follows: An aqueous solution of 30.3 g of ammonium molybdate and 28 .mu.l of 30 .mu.l of HgO2 was mixed with an aqueous solution of 30.3 g. cobalt nitrate (6 crystal waters). After diluting the mixture to 108 ml with water, it was used to saturate 16.51 g of the same alumina compacts as those used in the preparation of Catalyst I. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst K

A catalyst containing k, 3 parts by weight of cobalt and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows: In an aqueous solution containing 60.22 g of ammonium molybdate and 19-3 g of Arista H 2 O 2 , an aqueous solution of 63.7 g of cobalt nitrate (Co content: 20.25 wt.%) was stirred. After diluting with water to 2 x 0 ml, the mixture was used to impregnate 300 g of alumina extrudates obtained by extrusion of spray-dried alumina. After 20 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours. Catalyst L

A catalyst containing 3, 3 parts by weight of nickel and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows: In an aqueous solution containing 30.1 g of ammonium molybdate and 7.5 ml of 30% E 2 O An aqueous solution of 31.9 g of nickel nitrate (6 water of crystallization) was stirred. After diluting with water to 200 ml, the mixture was used to impregnate 150 g of spherical alumina particles obtained by the oil spray method. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours. The spherical alumina particles had the following properties: pore volume: 0.80 ml / g, pore volume in pores with a diameter of 0,0.7 xp and 1,1.7 xp: 0.58 ml / g, 2 area: 230 m / g % of the pore volume in the pores with a diameter of 9.7 xp: 18 #,% of the pore volume in the pores with a diameter = »1.7 xp: 10 #,% of the pore volume in the pores with a diameter =» 100 nm: 2.7 #, average specific pore diameter (p ): 22.0 nm, average specific particle diameter (d): 1.7 mm.

Catalyst M

A catalyst containing H, 3 parts by weight of cobalt and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

To an aqueous solution containing 20.0 g of ammonium molybdate and 20 g of 30 # HgOg was mixed with an aqueous solution of 21.2 g of cobalt nitrate (6 water of crystallization).

17,591 1 8

After diluting with water to 110 ml, the mixture was used to impregnate 100 g of the same spherical alumina particles as those used to prepare Catalyst L. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalysts N and 0

Two catalysts containing U, 3 parts by weight of nickel and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina were prepared as follows:

An aqueous solution of 38.6 g of nickel formate (2 water of crystallization) was mixed with an aqueous solution of 57.2 g of ammonium molybdate. After adding 65 ml of monoethanolamine, the mixture was diluted with water to 280 ml. This mixture was divided into two equal portions, and both portions were used to impregnate 1 to 2.5 g of spherical alumina particles that had been evaporated at 1 + 75 ° C and then calcined at either 500 ° C or 700 ° C for 3 hours. The spherical alumina particles were the same as those used for the preparation of catalysts L and M. Catalyst N was prepared using alumina particles calcined at 700 ° C; alumina particles calcined at 500 ° C were used as a support for the catalyst, after 15 minutes the impregnated materials were dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst P

The catalyst containing i +, 3 parts by weight of nickel and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

An aqueous solution of 8.1 g of nickel formate (2 water of crystallization) was mixed with an aqueous solution of 120 g of ammonium molybdate. After 13.5 ml of monoethanolamine was added to the mixture, it was diluted with water to 60 ml. This mixture was used to impregnate 60 g of the same vaporized, spherical alumina particles used to prepare Catalyst N. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst Q

11,600 g of an aqueous solution containing 2,628 g of sodium silicate (SiO 2 content: 26.5 wt.%) Was heated to 100 ° C. The pH of the solution was lowered from 11.6 to 6 by adding 1,160 ml of 6N HNO 2 with stirring over 30 minutes. Gelation occurred at pH 10.5. The resulting silica gel was aged for 1-10 hours at 140 ° C. 1 22 l + g of an aqueous solution containing 780 g of ΑΙζΝΟ ^^^ Η ^ Ο was added to the mixture over 5 minutes with stirring. The pH of the mixture was raised to h, 8 by the addition of 18,591 1 8 1 + 35 ml of concentrated ammonia over 20 minutes. After 20 minutes, the pH of the mixture was further raised to 5.5 by the addition of 20 ml of concentrated ammonia. The silica-alumina co-gel was isolated by centrifugation and washed six times with 15 ml of water until it contained no sodium. The gel was extruded into 1.5 mm extrudates. The extrudates were dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

377 g of this silica-alumina co-gel were mixed with 3,770 ml of 0.1 molar NH 4 NO 2+. The pH of this mixture was raised from h, 6 to 7 by the addition of 7.8 ml of concentrated ammonia. After 2 hours, the silica was filtered off, washed with 2 L of water and dried at 100 ° C.

The above-mentioned silicon alumina (9.5 wt.% Dry matter) was used as a support for a catalyst containing 2 parts by weight of nickel and 16 parts by weight of molybdenum per 100 parts by weight of silicon alumina. The catalyst was prepared as follows:

An aqueous solution of 108 g of ammonium molybdate was mixed with an aqueous solution of 23 g of nickel formate (2 crystalline waters). After adding 70 ml of monoethanolamine, the mixture was diluted with water to 500 ml. This mixture was used to impregnate 386 g of the above silicon alumina (365 g of dry matter). After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst R

A catalyst containing 1 part by weight of nickel and 8 parts by weight of molybdenum per 100 parts by weight of silicon alumina was prepared as follows:

An aqueous solution of 5.5 g of ammonium molybdate was mixed with an aqueous solution of 11.6 g of nickel formate (2 water of crystallization). After adding 1 + 5 ml of monoethanolamine, the mixture was diluted with water to 500 ml. This mixture was used to impregnate 388 g of the same silicon alumina used to prepare Catalyst Q. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst S

A catalyst containing 1 +, 3 parts by weight of cobalt and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

An aqueous solution containing 6.02 g of cobalt as cobalt nitrate was mixed with an aqueous solution containing 15.25 g of molybdenum as ammonium molybdate and 0.5 mol per molybdenum atom. After diluting with water to 130 ml, the mixture was used to saturate 1U0 g of alumina. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

19 591 1 8

Catalysts T and U

116.25 kg of an aqueous solution containing 26.25 kg of sodium silicate (SiO 2 content: 26.5 wt.%) Was heated to 1 + 0 ° C. The pH of the solution was lowered to 6 by the addition of 6N HNO 2 over 30 minutes with stirring. The resulting silica geol was aged for 1U0 hours at 10 ° C with stirring. 30 L of an aqueous solution containing 7.66 kg of AliO 2 -H 2 O at 1 + 0 ° C was added to the mixture over 5 minutes with stirring. After stirring for another 10 minutes, the pH of the mixture was raised to i +, 8 by the addition of 25 ammonia. After 10 minutes, the pH of the mixture was further raised to 5.5 · The silica-alumina co-gel was separated by centrifugation and washed with water at 60 ° C until it contained no sodium.

h, 6 kg of this silica-alumina co-gel (II + w / w dry matter) were treated three times with 5 L of 0.1 M NH 4 NO 2, washed with water and filtered off.

The above-mentioned silicon alumina (12.3 wt.% Dry matter) was used as a support for two catalysts, each containing 1 part by weight of nickel and 8 parts by weight of molybdenum per 100 parts by weight of silicon alumina. The catalysts were prepared as follows: 3,661 g of a silica-alumina co-gel (U50 g of dry matter) was beaten for 10 minutes. Then, 1.15 g of nickel formate (2 water of crystallization) was added and the material was beaten again for 5 minutes. An aqueous solution of 66.3 g of ammonium molybdate was added and the mixture was beaten for 1 hour. Catalysts T and U were obtained from this product by extrusion into 1.3 and 1.6 mm extrudates. The extrudates were dried at 100 ° C and calcined at 500 ° C for 3 hours.

Catalyst V

A silica gel was prepared from a solution of 1,500 g of sodium silicate (Si (^ - content: 26.5 wt.%) In 5,000 ml of water by lowering the pH of this solution from 11.6 to 6.0 by adding 6 N HNO The silica gel was aged for 2b hours at 100 DEG C. A solution of k37.2 g of Al (NO3) 3.9H2O in 900 ml of water was added to the silica gel, and the pH of the mixture was raised from 3 by adding 300 ml of concentrated ammonia. 15 to 6. The silica-alumina joint gel thus obtained was filtered off and washed with water until it contained no sodium, dried at 120 ° C, calcined for 3 hours at 500 ° C and crushed to particles with a d of 0.76 mm.

The pH of the mixture of 99 g of the above-mentioned silica-alumina particles and 1,000 ml of 0.1 molar NH 4 NO 2 was raised from 0.5 to 7.0 by the addition of concentrated ammonia. Silicon alumina was filtered off and dried at 20,591-1820 ° C. This silicon alumina (95.6 wt.% Dry matter) was used as a support for a catalyst containing 1 part by weight of nickel and 8 parts by weight of molybdenum per 100 parts by weight of silicon alumina. The catalyst was prepared as follows:

An aqueous solution of 2.95 g of nickel formate (2 crystals of water) was mixed with an aqueous solution of 13.7 g of ammonium molybdate and monoethanolamine.

After diluting with water to 175 ml, the mixture was used to saturate 98 g of the above-mentioned neutralized silicon alumina. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst W

A catalyst containing 3.8 parts by weight of cobalt and 9.5 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

An aqueous solution of 9 x 10 g of cobalt nitrate (6 water of crystallization) was mixed with an aqueous solution of 876 g of ammonium molybdate and 1,000 ml of 30% H 2 O 2. After diluting with water to 3,500 ml, the mixture was used to impregnate 5,000 g of 1.5 mm alumina extrudates. After 30 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst X

A catalyst containing 1 *, 3 parts by weight of nickel and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

An aqueous solution containing 2.13 kg of nickel nitrate (6 water of crystallization) was mixed with an aqueous solution of 2.01 kg of ammonium molybdate. After adding 6 L of 25 # ammonia to the mixture, it was diluted with water to 11 L. This mixture was used to impregnate 10 kg of alumina. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Catalyst Y

A catalyst containing 1 +, 3 parts by weight of nickel and 10.9 parts by weight of molybdenum per 100 parts by weight of alumina was prepared as follows:

An aqueous solution of 30.71+ g of nickel formate (2 crystal waters) containing monoethanolamine was mixed with an aqueous solution of 1 + 1 +, 13 g of ammonium molybdate and containing monoethanolamine. After diluting with water to 190 ml, the mixture was used to impregnate 220 g of alumina. After 15 minutes, the impregnated material was dried at 120 ° C for 18 hours and calcined at 500 ° C for 3 hours.

Desulphurisation hydrogenation tests Residual hydrocarbon oil with a total vanadium and nickel content of 2 l + 5 ppm, a C 1-4 asphaltene content of 7.2 wt.% And a sulfur content of 2.1 wt. sulfur by catalytic hydrogenation without catalyst replenishment and using catalysts AY. For this purpose, oil, together with hydrogen, was passed downwards through a cylindrical solid catalyst bed at a temperature of 2020 ° C, a partial pressure of hydrogen ranging from U0 to 200 bar, a gas removal rate of 0.25 m 2 / kg fresh feed and a volume flow rate of M5 kg oil / kg catalyst per hour. The catalysts were used in the form of their sulfides.

The efficiency of the catalyst in the desulphurisation hydration of residual hydrocarbon oils without catalyst replenishment can be described by the age and average activity of the catalyst, defined as follows:

The age of the catalyst (expressed in kg feed / kg catalyst) is the maximum amount of residual oil that can be desulfurized by hydrogenation with the catalyst before rapid deactivation occurs in the catalyst.

The average activity (expressed as kg feed / kg catalyst-1/2 t / h (w / w)) is the activity of the catalyst at the point where half the age of the catalyst has been reached.

The results of the desulfurization hydrogenation experiments together with the properties of the catalysts used are shown in Table I. The average specific pore diameter (p) of the catalysts was calculated from the total pore diameter distribution determined by the nitrogen adsorption / desorption method combined with the mercury penetration method mentioned above.

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The criteria for evaluating the optimum catalyst under the conditions used in these desulphurisation hydrogen tests are: the catalyst age must be at least 2,500 kg feed / kg catalyst and the average activity must be at least 1.5 kg 1/2 feed / kg catalyst per hour (weight-Ji S) '.

Experiments 1-2U (with catalyst ages> 2,500 and k ^ eg ^ ^ m> 1.5) are the desulfurization hydrogenation experiments of this invention. The catalysts used in these experiments meet the requirements for the optimum catalyst expression p / (d) ^ '^ and the pore diameter distribution.

Experiments 25-35 (in which the ages of the catalysts are 4. 2,500 and / or 4.1, 5) are desulfurization hydrogenation experiments which are outside the scope of this invention. In which experiments the catalysts used do not meet at least one of the requirements for the optimum catalyst expression p / (d) * and the pore diameter distribution. The catalysts used in experiments 25 ~ 33 do not satisfy the condition: U, 5 x W ~ k (P f ^ p / (d) ° '9 9 x 10_U (P „) 2.

In the catalyst used in Experiment 32, W is less than 0.1 k ml / g of pore volume in pores with a diameter of at least 0.7 x p and at most 1.7 x p and more than 20% of the pore volume is in pores with a diameter of more than 1.7 x p.

The catalyst X used in Experiments 33 and 3 is less than 0.1 U ml / g of pore volume in pores with a diameter of at least 0.7 xp and not more than 1.7 xp, more than 20% of the pore volume in pores with a diameter of more than 1 x 7 xp and more than 10% of the pore volume in pores with a diameter of more than 100 nm.

In the catalyst used in Experiment 35, Y is less than 0.1 U ml / g of pore volume in pores with a diameter of at least 0.7 xp and not more than 1.7 xp, more than 20% of the pore volume in pores with a diameter of less than 0.7 xp and more than 10% of the pore volume in pores with a diameter greater than 100 nm.

The effect of the pressure Pjj ^ on the catalyst performance is clear from a comparison of the following experiments:

Experiments 1 and 25 with catalyst A Experiments * +, 5 and 26 with catalyst C Experiments 6 and 27 with catalyst D Experiments 8 and 28 with catalyst F Experiments 17 and 29 with catalyst N Experiments 22 and 30 with catalyst S.

25 5 91 1 8

Catalysts A, C, D, F, N and S, which meet the requirements for the pore diameter distribution of the optimum catalyst and have the optimum efficiency for the desulphurisation hydrogenation of residual oils with a Pj value of 1 *, 5 X 10'11 (P) 2 £ p ( d) 0.9 ^ 9 X 10_1 + (P) 2 H2 H2 (experiments 1, U, 5, 6, 8, 17 and 22) are less suitable for this purpose with a P value,. .. H2 which does not satisfy the condition U, 5 x 10_i + (P) 2 ± r p / (d) ° '9 ^ 9 x ^ 0 ~ k (P f H2 H2 (experiments 25-30).

Example II

the complete pore radius distribution of the two Ni / Mo / Al 2 O 2 catalysts (catalysts I and II) was determined by the nitrogen absorption / desorption method combined with the mercury penetration method. Tables II and III show the percentage of pore volume in the pores with a given pore radius:

Table II Catalyst I

Pore radius, nm_% of pore volume 0-1 9.9 1- 2 9.3 2- 3 7.0

3- k 6, U

* »- 5 5.7

5- 6 5, T

6- 7 5.1 7- 8 5.1 8- 10 7.0 10-15 9.0 15-20 3.8 20-50 3.8> 50 22.2 pore volume: 0.78 ml / g 2 surface area: 238 m / g 26 591 1 8

Table III Catalyst II

Pore radius, nm_% of pore volume 0- 1 6.4 1- 2 6.4 2- 3 7.2 3- 4 5.6 4- 5 3.1 5- 6 3.1 6- 7 7.9 7.0- 7 .5 6.3 7.5- 8.0 6.4 8.0- 8.5 6.4 8.5- 9.0 6.3 9.0- 9.5 5.6 9.5- 10.0 5.5 10-15 7, 9 15-20 1.6 20-50 3.2> 50 11.1 pore volume: 0.63 ml / g 2 surface area: 133 m / g

The average pore diameters of catalysts I and II were determined by three different methods, each of which is used as such in practice.

Method 1 Calculated from the formula: „, 4 x pore volume ^„ 3

Pore diameter and = ---; - x 10 area

Method 2

Read from a curve drawn using a complete pore radius distribution in which, in the pore diameter range 0 to 100 nm, for each pore volume increase less than or equal to 10% of the pore volume, the quotient of the pore volume increase and the corresponding pore diameter interval is plotted against the linear average pore size. pore split and read from the point where the curve reaches its maximum.

27,591 1 8

Method 3

Read from a curve drawn using a complete pore radius distribution in which, for each pore volume increase of 0 to 100 nm for each pore volume increase of less than or equal to 10 # of pore volume, the quotient of the pore volume increase and the corresponding pore diameter interval is plotted cumulatively ; the pore diameter is read from a point corresponding to a total of 50 # at 100 nm.

The following average pore diameter values for Catalyst I are obtained by different methods.

By the method 1: 13.1 nm

With method 2: not determinable because there is no detectable maximum in the curve

By Method 3: 7.6 nm

The following average pore diameter values for Catalyst II are obtained by different methods.

By the method 1: 18.9 nm

By Method 2: 16.0 nm

By Method 3: 13.6 nm.

It can be seen from this example that different methods for determining the average pore diameter of a catalyst lead to widely varying results. Method 3 is used to determine the average specific pore diameter (p) according to the invention.

Example III

A complete sieve analysis was performed on a crushed Ni / Mo / Al 2 O 2 catalyst with a particle diameter between 0.115 and 1.10. The results of this sieve analysis are shown in Table IV.

Table IV

Sieve No. Particle Diameter- Weight- # Avg. particle- Cumulative (US mesh) range, mm_ diameter, mm_weight - # _ 16—18 1.00-1.19 1.0 1.10 100.0 18-20 0.81 »-1.00 2.3 0 .92 99.0 20-25 0.71-0.8U 3.5 0.77 96.7 25-30 0.59-0.71 5.2 0.65 93.2 30-35 0.50- 0.59 5.5 0.55 88.0 35-1 * 0 0.1 * 2-0.50 6.6 0.1 * 6 82.5 l * 0-l * 5 0.35-0, 1 * 2 8.1 0.38 75.9 1 * 5-50 0.297-0.35 7.1 0.32 6 ?, 8 50-60 0.250-0.297 9.3 0.27 60.7 60-70 0.210-0.250 8.9 0.23 51.1+ 70-80 0.177-0.210 8.5 0.19 1 * 2.5 80-100 0.11 * 9-0.177 9.9 0.165 3l +, 0 100-120 0.125-0.11 * 9 10.8 0.13 2l +, 1120-11 * 0 0.105-0.125 13.3 0.115 13.3 28 591 1 8 The average particle diameter of this catalyst was determined by two different methods, both of which are used in practice.

Method 1

Calculated as a linear average of the formula:

Particle diameter = —-- 'where and d ^ represent the diameter of the smallest and largest particle.

Method 2

Read from a curve drawn by complete sieve analysis in which the percentage by weight of each successive sieve fraction, calculated on the total weight of the catalyst sample, is plotted cumulatively as a function of the linear mean diameter of that sieve fraction; the particle diameter is read from a point corresponding to 50% of the total weight.

The following average particle diameter values for this catalyst are obtained by different methods.

By the method 1: 0.61 mm

By method 2: 0.225 mm.

It can be seen from this example that different methods for determining the average particle diameter of a catalyst lead to widely varying results. When determining the average specific particle diameter (d) according to the invention, method 2 is used.

Claims (4)

29 591 1 8 A process for the catalytic removal of sulfur by hydrogenation of catalyst-free residual hydrocarbon oils with a total vanadium and nickel content of more than 120 ppm, carried out at a temperature of 300 to 475 ° C under a hydrogen partial pressure of 50 to 200 bar at a flow rate of 0.1 to 10 parts by weight of fresh feed. per part of catalyst per hour and with a hydrogen / feed ratio of 3 0.15-2.0 m 2 H 2 / kg of feed and using a catalyst consisting of one or more metals with hydrogenation activity on the surface of the support and having an average specific pore diameter (p, nm) and the average specific particle diameter (d, mm) that the quotient p / (d) ° '9 satisfies the condition: 4.5 x 10'U (P) 2 ^ p / (d) °' 9 ^ 9 x 10_U (P) 2 , H2 H2 in which Pjj ^ is the partial pressure of hydrogen used (Pjj ^> öar) and the pore volume of the catalyst is more than 0.45 ml / g, whereby at least 0.4 ml / g of the pore volume is in pores with a diameter of at least 0.7 xp and up to 1.7 xp and pore diameter the distribution is sharp, characterized in that a) less than 20% of the pore volume is in pores with a diameter of less than 0.7 xp, b) less than 20% of the pore volume is in pores with a diameter of more than 1.7 xp, and c) less than 10 % of the pore volume is in pores with a diameter greater than 100 nm. Process according to Claim 1, characterized in that the surface area of the catalyst is more than 50 m / g, preferably more than 100 m / g. Process according to Claim 1 or 2, characterized in that the catalyst contains 0.5 to 20 parts by weight, preferably 0.5 to 10 parts by weight of nickel and / or cobalt and 2.5 to 60 parts by weight, preferably 2 , 5-30 parts by weight of molybdenum and / or tungsten per 100 parts by weight of carrier. Process according to Claim 3, characterized in that the atomic ratio in the catalyst between nickel and / or cobalt on the one hand and molybdenum and / or tungsten on the other is 0.1 to 5.