JPS5947719B2 - Hydrocarbon conversion method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is suitable for the catalytic hydrodesulfurization of residual hydrocarbon oils having a total vanadium and nickel content of more than 120 ppmw without continuous or periodic replenishment of the catalyst present in the desulfurization reaction vessel during operation. Regarding the law.

Residual hydrocarbon oils generally contain significant amounts of sulfur compounds.

When these oils are used as fuel, the sulfur present in the sulfur compounds is converted to sulfur dioxide and emitted into the atmosphere.

In order to suppress air pollution as much as possible during the combustion of these oils, it is desirable to reduce the sulfur content.

This can be achieved by catalytic hydrodesulfurization of the oil.

For this purpose, processes with continuous or periodic replenishment of the catalyst present in the desulfurization reaction vessel during operation or without such replenishment can be applied.

For the sake of simplicity, the latter process, of which the process according to the invention is an example, is referred to in the present patent application as "catalytic hydrodesulfurization without catalyst supplementation".

Catalytic hydrodesulfurization of residual hydrocarbon oils involves certain problems that do not occur when this method is applied to hydrodesulfurization of hydrocarbon distillate oils.

These problems are exacerbated by the fact that many residual hydrocarbon oils, such as those obtained by distillation of crude oil under normal or reduced pressure, contain metal compounds, particularly vanadium and nickel compounds, which have a significant portion bound to asphaltins and asphaltenes. This is due to the fact that it contains high-molecular, non-distillable compounds.

During hydrodesulfurization asphaltenes and vanadium and nickel compounds tend to deposit on the catalyst particles.

A portion of the polymer compounds deposited on the catalyst particles is converted into coke.

The increasing concentration of vanadium, nickel and coke on the catalyst results in very rapid catalyst deactivation.

As the activity of the catalyst decreases, the temperature must be increased to maintain the desired desulfurization rate.

However, at high temperatures, the hydrocracking reaction begins to play a more important role, resulting in fuel oils with different qualities.

In order to extend the catalyst life, it has already been proposed to remove asphaltenes from the charge before desulfurization and then to mix the separated asphaltenes back with the desulfurization product.

However, this method of operation requires additional process steps,
That is, deasphaltenization is required, and there are also certain other drawbacks.

Therefore, a hydrodesulfurization method is selected in which the raw material is treated as it is, that is, the raw material containing asphaltene is treated.

However, the implementation of this process requires catalysts that have better resistance to deactivation than the catalysts currently being generally promoted for this purpose.

Catalytic hydrodesulfurization studies without catalyst supplementation of residual hydrocarbon oils with total vanadium and nickel contents exceeding 120 ppmw revealed that 1 with hydrogenation activity on a support was
It has been found that catalysts suitable for this purpose, consisting of one or more metals, must comply with a number of requirements regarding their particle diameter and porosity.

These requirements for optimal catalysts depend in part on the hydrogen partial pressure at which the hydrodesulfurization is carried out.

In this patent application, the most suitable catalyst for the hydrodesulfurization of residual hydrocarbon oil without replenishing the catalyst is one that desulfurizes a satisfactory amount of residual hydrocarbon oil before the catalyst exhibits rapid deactivation. It is meant to have a sufficiently long life span and an average activity high enough to yield a final product with the desired low sulfur content at satisfactory space velocities.

Optimal catalyst particles consisting of one or more hydrogenation-active metals supported on a support in the non-catalytic hydrodesulfurization of residual hydrocarbon oils with a total vanadium and nickel content of more than 120 ppmw The requirements regarding diameter and porosity are as follows.

First of all, the catalyst particles are quotient p/(d)°°″/Ji45X
10-'X (PH2)2<pAd)"'<9×10-
4×(PH2)2, where PH2 is the applied hydrogen partial pressure (p is nm, d is m, and represents PH2 pearl), and the ratio is should have an average particle diameter.

Furthermore, the catalyst has a total pore volume greater than 0.45 ml/9, and at least 0.4 ml/9 of the total pore volume is 0.7
It must be present in pores with a diameter greater than or equal to Xp and less than or equal to 1.7Xp.

Finally, the catalyst has (a) a coefficient of 20 or less of the total pore volume of 0.7
(b) not more than 20% of the total pore volume is present in pores with a diameter greater than 1.7Xp, and (c) less than 20% of the total pore volume 10 or less are present in pores with diameters greater than 100 nm.

It must have a sharp pore diameter distribution characterized by

The method of measuring d depends on the shape of the catalyst particles.

If the catalyst particles have a shape such that the particle diameter distribution of the catalyst can be determined by sieve analysis, d is determined as follows.

ASTM Standards, Part 30, pages 96-101 (AS
After performing a complete sieve analysis of each catalyst sample using a set of standard sieves as described in E.TM. If d is read from a graph plotted cumulatively as a function of the arithmetic average particle diameter of the sieve section in question, then d is the particle diameter corresponding to the 50th factor of the total weight.

This method can be used to determine d for spherical and granular materials and materials with similar shapes such as extrudates and pellets with a length/diameter ratio of 0.9 to 1.1. can.

Determination of d for extrudates and similar cylindrical materials for which the particle diameter distribution cannot be determined by pellet and sieve analysis with length/diameter ratios less than 0.9 or greater than 1.1 is as follows: implement.

Perform a complete length distribution analysis (if the length/diameter ratio is less than 0.9) or a complete diameter distribution analysis (if the length/diameter ratio is greater than 1.1) of each catalyst sample. d is then read from a graph that cumulatively plots the weight coefficient for each successive length and diameter section based on the total weight of the catalyst as a function of the arithmetic mean size of that section. This value corresponds to the 50th factor of weight.

After determining the complete pore diameter distribution of the catalyst sample, from 0 to 10
Regarding the 100n pore diameter range, the increase in pore volume observed in pores separated by 2 nm diameter intervals, and for each successive increase in pore volume that is less than or equal to a factor of 10 of the pore volume. , from a graph in which the quotient of the increase in pore volume and the corresponding pore diameter interval is cumulatively plotted as a function of the arithmetic mean pore diameter over the pore diameter interval, p
, p is 50 of the total quotient at 1100n
% of the pore diameter.

Mercury infiltration method applying a mercury pressure of 1 to 2000 bar (
Industrial and Engineering
gChemistry, Analytical Edi
tion 17, 787 (1945), H.L.
Ritter and C.

Nitrogen adsorption/desorption method (Analytical Chemistry 32
, 532 (1960), E. V. Ba I l
o u and 0. K.

Determination of the complete pore diameter distribution of the catalyst is carried out very successfully by the method described and published by Dooleyn.

In this case, the pore diameter distribution of the catalyst with pore diameters below 7.5 nm is preferably Journal of Ca-
J in lysis 10, 377 (1968)
,C,P.

The pore diameter distribution of the catalyst is calculated from the nitrogen desorption isotherm (assuming cylindrical pores) according to the method described by Broekhoff and J. H-de Boer and in the pore diameter range above 7.5 nm. is calculated by the following general formula:

Quotient p/(d)0・9 is 4.0 < p/d(d)0
The abovementioned catalysts meeting the requirement of °9<20.0 have already been described as novel compositions in our British Patent Application No. 56803/71 (full specification).

Accordingly, the present patent application consists of one or more hydrogenation-active metals supported on a carrier and commercially available.
ad) 0.9 is 45 X 10-5X (PH, 2) 2
<p/(d)0・9< 9 X 10-'
H,) 2, where PH2 is the applied hydrogen partial pressure, and a specific average particle diameter (a) of 0.45 yr.
having a total pore volume greater than tl/i, at least 0.4 TIL/g of the total pore volume being present in pores having a diameter of 0.7 x p or more and 1.7 x p or less;
Moreover, (a) 20 parts or less of the total pore volume exists in pores having a diameter smaller than 0.7Xp, and (b) 20 parts or less of the total pore volume has a diameter smaller than 1.7Xp. and (c) no more than 10% of the total pore volume is present in pores with a diameter greater than 1100 nm, where p is nm and d is m
A catalyst with a sharp pore diameter distribution characterized by m, PH in bar) is applied.

The present invention relates to a catalytic hydrodesulfurization process without catalyst replenishment of residual hydrocarbon oils having a total vanadium and nickel content of more than 120 ppmw.

The catalysts applied according to the invention are given within a pore diameter range that depends on the relationship given between their average pore diameter and average particle diameter at a given hydrogen partial pressure and on the average pore diameter of the catalyst. characterized by a pore diameter distribution.

It is essential that the average pore diameter used for catalyst characterization is determined according to the methods specified above for specific average pore diameter and specific average particle diameter, because the Using mean pore diameters and mean particle diameters determined by methods other than those specified above for specific mean pore diameters and mean particle diameters for characterization (e.g., using the quotient of pore volume and surface area) The average pore diameter calculated by multiplying by 4 or the average particle diameter calculated as the arithmetic mean) gives completely different results.

The relationship discovered between p, d and PH serves three different purposes.

Firstly, this relationship provides the possibility of determining the range of pH that should be selected in order to obtain good results with a catalyst with given p and d.

Furthermore, this relationship shows that d, which catalyst material should be selected according to the given p, in order to obtain good results at a given pH.
used to determine the range of

Finally, this relationship makes it possible to determine the range of p in which the catalyst material should be selected with a given d in order to obtain good results at a given pH.

The most suitable values for each of PH2, d and p within the ranges found depend inter alia on the composition of the hydrocarbon oil to be desulfurized.

The catalyst applied in the process of the invention is preferably 50 m
/,? with a surface area of 100 m2/g or more, and especially 100 m2/g
It has a surface area of more than

The catalyst used according to the invention preferably supports 1
0.5 to 20 pbw and especially 0.5 per 00 pbw
It consists of ~10 pbw nickel and/or cobalt and 2.5-60 pbw and especially 2.5-30 pbw molybdenum and/or tungsten.

The atomic ratio between nickel and/or cobalt on the one hand and molybdenum and/or tungsten on the other hand varies widely and is preferably from 0.1 to 5.

Examples of very suitable metal combinations in the present catalyst are nickel/tungsten, nickel 7 molybdenum, cobalt/molybdenum and nickel/cobalt/molybdenum.

The metals may be present on the support in the metallic state or in the form of their oxides or sulfides.

Catalysts according to the invention are selected in which the metal is present in the form of a sulfide on a support.

Sulfurization of the catalyst may be accomplished by any of the methods of sulfurization of catalysts that are well known in the art.

Sulfurization may be carried out, for example, by contacting the catalyst with a sulfur-containing gas, such as a mixture of hydrogen and hydrogen sulfide, a mixture of hydrogen and carbon disulfide, or a mixture of hydrogen and a mercaptan, such as butyl mercaptan.

Sulfidation may also be accomplished by contacting the catalyst 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 also contain further catalytically active metals and promoters, such as phosphorus, boronate and halogens such as fluorine and chlorine.

Very suitable supports for the present catalyst are oxides of elements of Groups I, II or III of the Well-known Table of Elements, or mixtures of these oxides, such as silica, alumina, magnesia, zirconia, thoria, boria. , hafnia, silica
They are alumina, silica-magnesia, alumina-magnesia and silica-zirconia.

The preparation of the catalyst used according to the invention involves a support having a pore diameter distribution and a specific average pore diameter such that after depositing the metal on the support a catalyst is obtained that meets the requirements of the invention. This is accomplished by depositing the metal as is or after the specific average catalyst particle diameter is increased or decreased.

The porosity of the finished catalyst is determined by the amount of metal loading applied.

In general, starting from a support with a given porosity, increasing the metal loading results in a catalyst with a lower porosity.

This phenomenon is due to relatively low metal loading, i.e. support 110
It only plays a minor role when metal loadings of about 20' pbw per 0 pb or less are applied.

This is because, at relatively low metal loadings, the porosity of the finished catalyst is determined primarily by the porosity of the support used, and furthermore, in producing the catalyst of the invention with relatively low metal loadings, the porosity of the finished catalyst is determined primarily by the porosity of the support used. This means that a support should be selected with a porosity that differs only slightly from the desired porosity of the catalyst.

However, at higher metal loadings, the effect of metal loading on porosity becomes more important, and applying high metal loadings makes it difficult to produce catalysts according to the invention starting from supports with too high a porosity. It serves as a means to

The porosity of the support is also affected by high temperature treatment in the presence or absence of water vapor.

The porosity of the carrier depends primarily on the method by which the carrier was manufactured.

Metal oxide type catalyst supports are usually prepared by adding one or more gelling agents to an aqueous solution or salts of the metals involved, so that the metals are precipitated in the form of a metal hydroxide gel; It is manufactured by molding it and baking it.

The gold layer hydroxide gel is usually aged for a period of time before molding.

During the manufacture of the carrier, there is ample opportunity to not affect the porosity of the carrier.

The porosity of the support finally obtained is influenced by, among other factors, the rate of addition of the gelling agent and the temperature applied during the formation of the gel, and H, among other factors.

The porosity of the support finally obtained can also be influenced by adding certain agents to the gel, such as phosphorus and/or halogen compounds.

When aged, the porosity of the final support is influenced by the aging time and temperature applied during aging, and also by H.

When producing mixed metal oxide supports, another important aspect regarding the porosity of the final support is whether the metal hydroxide gels are precipitated simultaneously or separately, e.g. one on top of the other. This is the way to do it.

The porosity of the finally obtained carrier is further determined by the carrier particle molding method 1.
It is influenced by the conditions applied during molding and the temperature applied during firing.

The porosity of the carrier particles during molding is influenced by, for example, the type and amount of catalytic agents and binders normally added during this stage of carrier manufacture, the addition of certain agents and small amounts of inert substances such as silica and/or zirconia. is affected by the addition of

If the carrier particles are formed by extrusion, the porosity of the final carrier is influenced by the extrusion pressure applied.

When using a spray drying method, the porosity of the carrier is influenced by the spray temperature and spray pressure applied.

The catalysts applied according to the invention may be made by any of the techniques for making multicomponent supported catalysts that are well known in the art.

It is not necessary that the catalytically active metal be deposited on the finished support; the metal may be combined with the support material during the manufacture of the support, for example before molding.

Bonding a catalytically active metal to a support during the early stages of catalyst production also has a significant effect on the porosity of the finished catalyst.

The catalyst applied according to the invention preferably involves one-stage or multi-stage co-impregnation of the support with an aqueous solution containing one or more nickel and/or cobalt compounds and one or more molybdenum and/or tungsten compounds. Produced by subsequent drying and roasting.

If the impregnation is carried out in several stages, the material may be dried and then calcined between successive stages of impregnation, if desired.

Drying and baking preferably at 50 to 150°C, respectively.
and carried out at a temperature of 150 to 550°C.

Examples of suitable water-soluble compounds of nickel, cobalt, molybdenum and tungsten used in the preparation of the present catalysts are nickel and cobalt nitrates, chlorides, carbonates,
formate and acetate, ammonium molybdate and ammonium tungstate.

Certain compounds may be added to the solution to increase the solubility of these compounds and stabilize the solution, such as ammonium hydroxide, monoethanolamine and sorbitol.

Alumina and silica-alumina are preferred as supports for the catalysts of the invention.

Very suitable supports are alumina particles prepared by spray-drying an alumina gel and subsequent shaping of the spray-dried microparticles into larger particles, for example by extrusion, and spherical alumina particles obtained by the well-known oil dropping method.

The latter method consists of forming an alumina hydrosil, mixing this hydrosil with a suitable gelling agent, and dispersing the mixture as droplets in an oil held in an ascending and descending manner until the droplets solidify. The droplets are held in oil until they become spherical hydrogel particles, which are then separated, washed, dried and baked.

A highly suitable silica-alumina support for the present catalyst is a cogel of aluminum hydroxide gel on silica hydrogel.

These cogels are preferably prepared by first precipitating a silica hydrogel from an aqueous solution containing silicate ions by adding a mineral acid, followed by adding a water-soluble aluminum salt to the mixture and then adding a compound that acts as an alkali. It is prepared by precipitating an aluminum hydroxide gel.

Preferably, the produced silica hydrogel is aged at elevated temperature for a period of time before continuing to produce the cogel.

The aging conditions, especially the aging time and aging temperature, have a great influence on the porosity of the final cogel.

The preparation of the catalyst according to the invention based on the above cogel may be carried out as follows.

The cogel is first formed, for example by extrusion, and the hydrogel particles are subsequently dried and baked.

The xerogel particles thus obtained are then neutralized with a nitrogen base and dried.

Finally, the catalytically active metal is deposited thereon by impregnating the support with one or more aqueous solutions containing salts of the metals concerned, and the composition is subsequently dried and calcined.

The preparation of the catalyst according to the invention based on the cogel described above may be further carried out by the following simplified procedure.

The catalytically active metal is bound therein by mixing the cogel with one or more aqueous solutions containing salts of the metals concerned, and the shaped composition is then dried and baked, for example by extrusion.

Catalytic hydrodesulfurization of residual hydrocarbon oils without catalyst supplementation is carried out preferably at elevated temperature and pressure and in one or more vertically arranged reaction vessels consisting of one or more fixed catalyst beds, above and below. or by passing a hydrocarbon oil in the presence of hydrogen in the radial direction.

The hydrocarbon oil to be desulfurized is completely or partially saturated with hydrogen and, in addition to the hydrocarbon phase and the catalyst phase, a hydrogen-containing gas phase is present in the reaction vessel.

Additionally, a portion of the liquid product, with or without dissolved hydrogen, hydrogen sulfide and/or hydrocarbon gas, may be recycled to the catalyst bed.

Hydrodesulfurization may be performed in a single reaction vessel or in two or more reaction vessels.

Generally, the hydrodesulfurization reaction vessel contains more than one catalyst bed.

The catalysts used in the separate catalyst beds and/or in the separate reaction vessels may differ from each other with respect to their p and/or d and/or chemical composition.

If several reaction vessels are utilized, all of these reaction vessels can be used simultaneously to carry out the desulfurization reaction.

It is also possible to use reactors alternately for desulfurization, in which case desulfurization is carried out in one or more reactors and the catalyst is transferred to another reactor.

Hydrodesulfurization of residual hydrocarbon oil without catalyst replenishment involves passing the hydrocarbon oil with hydrogen in an upward direction through a vertically arranged catalyst bed applying liquid and/or gas velocities such that expansion of the catalyst bed occurs. This is very suitably carried out by.

An attractive embodiment of the hydrodesulfurization of residual hydrocarbon oils without supplementation of other catalysts is to pass the hydrocarbon oil with hydrogen in an upward direction through a vertically arranged fixed bed and then pass a portion of the desulfurized product over the catalyst. This is an example of keeping the adiabatic temperature rise resulting from the hydrodesulfurization reaction below 20° C. by recycling to the bed and/or injecting hydrogen into the catalyst bed at various locations.

In the catalytic hydrodesulfurization of residual hydrocarbon oils without catalyst supplementation, catalyst particles having a specific average particle diameter of 0.5 to 2.5 mvt are generally used.

If the desulfurization is achieved by passing the hydrocarbon oil to be desulfurized together with hydrogen through a fixed bed of catalyst arranged vertically above or below, a catalyst with a specific average particle diameter of 0.6 to 2.0 mm; Preferably, particles are used.

The relationship discovered between p and d and PH2 allows the production of catalysts that exhibit optimal performance for the hydrodesulfurization of residual hydrocarbon oils at a given PH2.

If a catalyst or catalyst support is utilized in which d is not optimal with respect to p at a given PH2, then an optimal catalyst or catalyst support can be produced by adjusting d to p.

This can be achieved in a simple manner by increasing or decreasing the particle size of the catalyst or catalyst support (for example by bonding the particles with or without a binder or milling the particles).

The following problems arise when producing the optimal desulfurization catalyst according to the invention starting from certain catalysts or catalyst support materials.

If the optimum d corresponding to p of the material from which the catalyst has to be made at a given pH2 is too small, difficulties arise when using such small catalyst particles for catalytic hydrodesulfurization.

Agglomerates are preferably formed from small particles, in which case d is optimal with respect to p and PH2, and these agglomerates occupy more than 10% of the pore volume in pores with a diameter of more than 1100 nm. .

Preferably, small particles form aggregates in which pores with a diameter of more than 100 nm occupy more than 25% of the pore volume of the aggregates.

The use of these porous catalyst aggregates in the hydrodesulfurization of residual hydrocarbon oils provides the same benefits as using small optimal catalyst particles without the inherent drawbacks when using these small catalyst particles. provide.

The particles of choice are bonded to the agglomerates with or without binders in the presence of substances that are bonded to the agglomerates and then removed therefrom by evaporation, combustion, dissolution, leaching or other methods, and the agglomerates are exposed to 1100 nm. Porous catalyst or catalyst support aggregates are very advantageously produced from the particles by leaving satisfactory pores with diameters exceeding .

Compounds suitable for this purpose are cellulose-containing substances,
Compounds that are soluble in polymers and organic or inorganic solvents.

The reaction conditions applied to the hydrodesulfurization process according to the invention may vary widely.

Hydrodesulfurization is preferably carried out at a temperature of 300-475°C, 50-475°C.
Hydrogen partial pressure of 200 bar, space velocity of 0.1-10 pbw of fresh feed per pbv of catalyst per hour and space velocity of 150-200
Performed at a hydrogen/feed ratio of ONIH2/kg feed.

Temperatures of 350-445° C., hydrogen partial pressures of 80-180 bar, space velocities of 0.5-5 pbw of fresh feed per pbv of catalyst per hour and hydrogen/feed ratios of 250-1000 NIH2/kg feed are particularly preferred.

The present patent application is limited to the use of catalysts meeting certain requirements regarding catalyst quotient p/dPQ and pore diameter distribution in the non-replenishing hydrodesulfurization of residual hydrocarbon oils with vanadium and nickel contents exceeding 120 ppmW. .

Total vanadium and nickel content at most 120pp
The use of these catalysts for the non-catalytic hydrodesulphurization of residual hydrocarbon oils of mw is disclosed in our UK patent application 5.
6803/71 (complete specification).

It is very suitable that the hydrodesulfurization method according to the invention is preceded by a demetalization method.

As a result of demetalization, deactivation of the hydrodesulfurization catalyst is considerably suppressed.

The residual hydrocarbon oil used as feedstock for this bonding process should have a total vanadium and nickel content of at least <120 ppmw.

The demetalization of the residual hydrocarbon oil involved should be carried out in such a way that a product is obtained with a total vanadium and nickel content reduction of 120 ppmw or more.

The demetalization of the residual hydrocarbon oil is preferably carried out by introducing the hydrocarbon oil into one or more vertically arranged reaction vessels consisting of a fixed or moving bed of suitable catalyst particles at elevated temperature and pressure and in the presence of hydrogen. This is accomplished by passing it upward, downward or radially.

A very attractive example of a demetalization process involves passing hydrocarbon oil through a vertically arranged catalyst bed in which during operation fresh catalyst is periodically introduced at the top of the catalyst bed and spent catalyst is withdrawn from the bottom thereof. (demetallization in punker flow operation)
.

A very attractive embodiment of another demetallation process is in which there are several reaction vessels containing fixed catalyst beds that are alternately used for demetallation, and at the same time in one or more of these reaction vessels. This is a method of carrying out demetalization and replenishing the catalyst in other reaction vessels (demetallization in fixed bed switching operation →
.

If desired, demetalization may be accomplished by suspending a catalyst in the hydrocarbon oil to be desulfurized (demetallization in slurry phase operation).

An excellent catalyst for the demetallization of residual hydrocarbon oils is a catalyst containing one or more hydrogenation-active metals on a carrier, and which satisfies the following conditions:

(1) the pore volume is greater than 0.4 rrtl/g, (2) the percentage of the pore volume consisting of pores with a diameter greater than 100 nm(v) is less than 50, and (3) p and the quotient of d is greater than 10-0.15v.

If the desulfurization according to the invention is preceded by demetalization, it is preferred that the demetallization is carried out in a puncher flow operation or fixed bed switching operation and the desulfurization in a conventional fixed bed operation.

Examples of raw materials used in the hydrodesulphurization process according to the invention (with or without a preceding demetalization process) are crude oil and residues obtained by distilling crude oil under normal and reduced pressure.

The feedstock to be desulfurized should contain less than 50 ppmw and especially less than 25 ppmw alkali metals and/or alkaline earth metals.

If the content of alkali metals and/or alkaline earth metals in the raw material is too high, it is reduced, for example by desalting the raw material.

The invention will now be elucidated by the following examples.

Example 1 Production of Catalyst Catalyst A A catalyst containing 4.7 pbw of cobalt and 11.4 pbw of molybdenum per 100 pbw of alumina was produced as follows.

An aqueous solution of 1051 g of ammonium molybdate (the ammonium molybdate used in the examples of this patent application contained 54.3% by weight molybdenum) was mixed with an aqueous solution of 1163.9 g of cobalt nitrate hexahydrate.

After adding 350 ml of 25% aqueous ammonia, the mixture was diluted with water to a volume of 3800 ml.

This mixture was made into a 1.5 mm alumina extrusion molded product.
It was used to impregnate g.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

Catalyst B A catalyst containing 4.7 pbw of cobalt and 11.4 pbw of molybdenum per 100 pbw of alumina was prepared as follows.

An aqueous solution of 35.1 g of ammonium molybdate was mixed with an aqueous solution of 38.9 g of cobalt nitrate hexahydrate.

After adding 10 rrLl of 25% aqueous ammonia, the mixture was diluted with water to a volume of 125TLl.

This mixture was made into a 15 mm alumina extrusion molded 166.9 mm.
It was used to impregnate g.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then fired at 500°C for 3 hours.

Catalyst C A catalyst containing 4.7 pbw of cobalt and 11.4 pbw of molybdenum per 100 pbw of alumina was prepared as follows.

An aqueous solution of 29.9 g of ammonium molybdate was mixed with an aqueous solution of 33.1.9 g of cobalt nitrate hexahydrate.

After adding 10 ml of 25% aqueous ammonia, the mixture was diluted with water to a volume of 108 rI'll.

This mixture was added to L5myn alumina extrusion molding 142.
:Used to impregnate.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then fired at 500°C for 3 hours.

Catalyst and E Two catalysts containing 3.8 pbw of cobalt and 9.5 pbw of molybdenum per 100 pbw of alumina were prepared as follows.

876g ammonium molybdate and 30% H2O21
Cobalt nitrate hexahydrate 940g of aqueous solution of 0007711
was mixed with an aqueous solution of

After diluting the mixture with water to a volume of 3450 ml, it was used to impregnate 0.8 mm alumina extrudates 5001.

After 30 minutes, the gold-soaked material was dried at 120°C for 18 hours and then fired at 500°C for 3 hours.

A part of the catalyst obtained in this way was crushed to 0.2 mm.
Catalyst E having d was prepared.

Catalysts F and G Aqueous solution containing 5.256 kg of sodium silicate (SiO2
Content: 26.5% by weight) 23.2kp was warmed to 40°C.

2200 ml of 6N nitric acid was added over 30 minutes with stirring to reduce the pH of the solution from 11.1 to 6.

The obtained silica gel was aged at 40°C for 24 hours.

2448 g of an aqueous solution containing 1528 g of A I (NOs) s·9H and having a temperature of 40° C. were added to this mixture over a period of 5 minutes with stirring.

After stirring for an additional 10 minutes, 25% aqueous ammonia was added to raise the pH of the mixture to 4.8.

After 10 minutes the pH of the mixture was further increased to 5.5 (total aqueous ammonia consumption was approximately 900 ml).

The silica-alumina co-gel was washed with water until it contained no sodium.

The gel was extruded into 1.5 mm extrudates.

The molded product was dried at 120°C and then baked at 500°C.

620 g of this silica-alumina cogel was mixed with 0.1 mol of N.
H4N03 solution 6.21 and 25% ammonia water 15T
Neutralized with ll.

The silica-alumina was separated, washed with water, and then dried at 120°C.

2 pbw of nickel per 100 pbw of silica-alumina
The above silica-alumina (95% by weight dry matter) was used as a support for two catalysts containing 16 pbw of molybdenum and 16 pbw of molybdenum.

These catalysts were manufactured as follows.

Nickel formate dihydrate 37.7f! An aqueous solution of 176.4 g of ammonium molybdate was mixed with an aqueous solution of 176.4 g of ammonium molybdate.

After adding 110 TLl of monoethanolamine to the mixture, the mixture was diluted with water to a volume of 700 rul.

630 g of the above silica-alumina (dry matter 598.5
This mixture was used to impregnate g).

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

A part of the catalyst F thus obtained was crushed to a size of 0.5 m.
Catalyst G was prepared with d of m.

Catalyst H Aqueous solution containing sodium silicate 26.25]i (SiO2
116.25 kg (content 26.5% by weight) was warmed to 40°C.

The pH of the solution was lowered to 6 by adding 6N nitric acid over 30 minutes with stirring.

The obtained silica gel was heated at 40°C with stirring for 14 hours.
Aged for 0 hours.

Contains Al(NO3)3.9H207,66kg, 40
An aqueous solution 301 having a temperature of 0.degree. C. was added to this mixture over a period of 15 minutes while stirring.

After stirring for an additional 10 minutes, 25% aqueous ammonia was added to raise the pH of the mixture to 4.8.

After 10 minutes, the pH of the mixture was further increased to 5.5.

The silica-alumina cogel was separated by centrifugation and washed until free of NaI-IJ.

This cogel (12.4% dry matter) was prepared with 2 pbw of nickel and 1 molybdenum per 1100 pb of silica-alumina.
It was used as a support for a catalyst containing 6 pbw.

The catalyst was manufactured as follows.

Silica-alumina co-gel 10010O8 dry matter 125
g) was kneaded for 10 minutes.

Subsequently, 7.87 g of nickel formate dihydrate was added and kneaded again for 5 minutes.

Add a small amount of water to ammonium molybdate 3 containing H20□
Aqueous solution of 6.8.1 (H2O2/MO molar ratio: 0.25
) was added and the mixture was kneaded for 1 hour.

The product was extruded into 1.2 mm extrudates.

The molded product was dried at 120°C for 18 hours and then heated to 50°C.
It was baked at 0°C for 3 hours.

Catalyst (1) A catalyst containing 4.3 pbw of nickel and 10.9 pbw of molybdenum per 1100 pb of alumina was prepared as follows.

An aqueous solution containing 11.9 g of molybdenum as ammonium molybdate and 7.1 g of H2O2 (H20□/M).

Molar ratio: 0.5) as nickel nitrate and nickel 4.7
It was mixed with an aqueous solution containing 3 g.

After diluting the mixture with water to a volume of 110 ml, it was used to impregnate alumina 11 (Bi').

After 15 minutes, the impregnated material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

The alumina used as a carrier was obtained by extrusion of spray-dried alumina.

This alumina molded product had the following properties.

Pore volume: Q, 68 m, 17 g Pore volume in pores with a diameter of 0.7Xp or more and 1.7Xp or less: 0.56 rnl/9 Surface area:
250 m”/i 0,7 X % of pore volume in pores with diameter smaller than p: 9% 1,7 X % of pore volume in pores with diameter larger than p: 4% % of pore volume in pores with a diameter greater than 100 nm: 2,0% Specific mean pore diameter (p): 13. Onm Specific mean particle diameter (d): 1.5 mrn Catalyst J Alumina 100 pbw A catalyst containing 4.3 pbw of cobalt and 10.9 pbw of molybdenum was prepared as follows.

Ammonium molybdate 28.6. ? and 30% H2O
228.4 ml of cobalt nitrate hexahydrate 30
, , l was mixed with an aqueous solution of .

After diluting the mixture with water to a volume of 108 ml, the catalyst ■
The same alumina extrusion used in the production of 142.
3.9 was used to impregnate.

After 15 minutes, the impregnated material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

Catalyst K A catalyst containing 4.3 pbw of cobalt and 10.9 pbw of molybdenum per 100 pbw of alumina was prepared as follows.

60.22g ammonium molybdate and 30%H
An aqueous solution containing 193 g of 2O2 was mixed with 63.7 g of cobalt nitrate.
(Co content: 20.25% by weight).

Alumina extrudate 3 obtained by extruding the spray-dried alumina after diluting the mixture with water to a volume of 240 ml
It was used to impregnate 00g.

After 20 minutes the impregnated material was dried at 120°C for 18 hours and then calcined at 500°C for 3 hours.

Catalyst L A catalyst containing 4.3 pbw of nickel and 10.9 pbw of molybdenum per 1100 pb of alumina was prepared as follows.

30.1g ammonium molybdate and 30% H202
An aqueous solution containing 7.5rnl of nickel nitrate hexahydrate was mixed with 31.0ml of nickel nitrate hexahydrate.
1 was mixed with an aqueous solution of 1.

The mixture was diluted with water to a volume of 200 rul and then used to impregnate 150 g of spherical alumina particles obtained by the oil drop method.

After 15 minutes the impregnated material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

The spherical alumina particles had the following particles.

Pore volume: 0.80ml/,! il', volume of pores with a diameter of 0.7Xp or more to 1.7Xp or less: 0
．． 58 m1/j; l, surface area: 230 m1g, % of the volume of pores with a diameter smaller than 0.7Xp:
18%, % of the volume of pores with a diameter greater than 1,7 X p: 10%, % of the volume of pores with a diameter greater than 1100n:
2.7%, specific average pore diameter (p): 22. Onm.

Specific average particle diameter (d): 1.7 myn.

Catalyst M A catalyst containing 4.3 pbw of cobalt and 9 pbw of molybdenum IO per 1100 pb of alumina was prepared as follows.

Ammonium molybdate 20. l and 30%H20□2
The aqueous solution containing 0 g was mixed with an aqueous solution of 21.2 g of cobalt nitrate hexahydrate.

After diluting the mixture with water to a volume of 110 ml, the same spherical alumina particles IoOg as used for the preparation of the catalyst were added.
was used to impregnate.

After 15 minutes, the impregnated material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

Catalysts N and O Two catalysts containing 4.3 pbw nickel and 10.9 pbw molybdenum per 1100 pb alumina were prepared as follows.

An aqueous solution of 57.29 g of ammonium molybdate was mixed with an aqueous solution of 38.6 g of nickel formate dihydrate.

After adding 65 TLl of monoethanolamine, the mixture was diluted with water to a volume of 280 ml.

The mixture was divided into two equal parts and each was steamed at 475°C followed by 3 hours at 500°C or 7°C.
Spherical alumina particles baked at 00°C 142.
It was used to impregnate i.

The spherical alumina particles were the same as those used in the preparation of catalyst and M.

Alumina particles fired at 700°C were used to produce Catalyst N, and alumina particles fired at 500°C were used as a carrier for Catalyst O.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

Catalyst P A catalyst containing 4.3 pbw of nickel and 10.9 pbw of molybdenum per 1100 pb of alumina was prepared as follows.

An aqueous solution of 120 g of ammonium molybdate was mixed with an aqueous solution of 8.1 g of nickel formate dihydrate.

After adding 13.5 ml of monoethanolamine, the mixture was diluted with water to a volume of 60 vtl.

This mixture was used to impregnate 60 g of the same steam-treated spherical alumina particles used to prepare catalyst N.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

Catalyst Q 11,600 g of an aqueous solution (SI02 content: 26.5% by weight) containing 2,628 g of sodium silicate was warmed to 40°C.

The pH of the solution was lowered from 11.6 to 6 by adding 1160 Wll of 6N nitric acid over 30 minutes while stirring.

Gelation occurred at pH=10,5. The obtained silica gel was aged at 40°C for 140 hours.

1224 g of an aqueous solution containing A,l(NO3)s.9H20781 was added to this mixture over 5 minutes with stirring.

435 ml of concentrated ammonium water was added over 20 minutes to raise the pH of the mixture to 4.8.

After 20 minutes, add 20ml of gold ammonia water to reduce the mixture's pH.
n was further increased to 5.5.

The silica-alumina cogel was separated by centrifugation and washed 6 times with 157 g of water each time until sodium free.

The gel was made into a 1.5 van extrudate. 1 molded item
It was dried at 20°C for 18 hours and then baked at 500°C for 3 hours.

377 g of this silica-alumina co-gel was added to 0.1 mo#NH
4N033770 m.

Adjust the pH of this mixture by adding 7.8 ml of concentrated ammonia water.
increased from 4.6 to 7.

After 2 hours, the silica alumina was taken out, washed with 21 parts of water, and dried at 100°C.

The above silica-alumina (94.5% by weight dry matter) was mixed with 2 pbw of nickel per 100 pbw of silica-alumina.
and was used as a support for a catalyst containing 16 pbw of molybdenum.

The catalyst was manufactured as follows.

A 2.1 M aqueous solution of nickel formate dihydrate was mixed with an aqueous solution of 108 g of ammonium molybdate.

After adding the monoethanolamine 707111, the mixture was diluted with water to a volume of 5007711.

This mixture was mixed with the above silica-alumina (dry substance 365
．． @) Used to impregnate 386 g.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then fired at 500°C for 3 hours.

Catalyst R Silica-alumina 100 pbwa Re-nickel 1 pb
A catalyst containing w and 8 pbw of molybdenum was prepared as follows.

An aqueous solution of 11.6 g of nickel formate dihydrate was mixed with an aqueous solution of 54.5 g of ammonium molybdate.

After adding 45 ml of monoethanolamine, the mixture was diluted with water to a volume of 500 ml.

This mixture was prepared using the same silica as used in the preparation of Catalyst Q.
This was used to impregnate 388 g of alumina.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

Catalyst S A catalyst containing 4.3 pbw of cobalt and 10.9 pbw of molybdenum per 1100 pb of alumina was prepared as follows.

An aqueous solution containing 15.25 g of molybdenum as ammonium molybdate and 0.5 mol of H2O2 per Mo is used as cobalt nitrate and cobalt 6.02. ? mixed with an aqueous solution containing

The mixture was diluted with water to a volume of 1307 rLl and then used to impregnate 140 g of alumina.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then fired at 500°C for 3 hours.

Catalyst T and U: An aqueous solution containing 26.25 kg of sulfur silicate (S
t02 content: 26.5% by weight) 116.25 kg were warmed to 40°C.

Add 6N nitric acid over 30 minutes with stirring to adjust the pH of the solution.
was lowered to 6.

The obtained silica gel was heated at 40°C with stirring for 14 hours.
It was aged for 0 hours.

A l (No 3) 3/9H207,66! 9
An aqueous solution 30Al' containing 30.degree. C. and having a temperature of 40.degree. C. was added to the mixture in 5 minutes with stirring.

After stirring for an additional 10 minutes, 25% aqueous ammonia was added to raise the pH of the mixture to 4.8.

After 10 minutes, the pH of the mixture was further increased to 5.5.

The silica-alumina co-geno was separated by centrifugation and washed with water at 60°C until sodium-free.

4.6 kg of this silica-alumina cogel (dry substance 1
4 wt.

The above silica-alumina (12.3% by weight dry matter) was mixed with nickel lpbw per 100 pbw of silica-alumina.
and 8 pbw of molybdenum as a support for each of two catalysts.

The catalyst was manufactured as follows.

Silica-alumina co-gel 3661. ? (=dry substance 45
1) was kneaded for 10 minutes.

Subsequently, 14.15 g of nickel formate dihydrate was added and kneaded again for 5 minutes.

An aqueous solution of 66.3 g of ammonium molybdate was added and the mixture was kneaded for 1 hour.

Catalysts T and U were obtained from this product by extrusion into 1.3 mm and 1.6 mm extrudates, respectively.

The molded product was dried at 100°C and then baked at 500°C for 3 hours.

Catalyst V Silica gel was produced by adding 6N nitric acid to an aqueous solution (S102 content 26.5% by weight) containing 1500 g of sodium silicate in 50001 nl of water to lower the pH of this solution from 11.6 to 6.0.

The silica gel was aged at 100°C for 24 hours.

AI (NO3) s ・9H204 in 900ml of water
A solution containing 37.2 g was added to the silica gel.

Add 300 ml of concentrated aqueous ammonia to bring the pH of the mixture to 3.
．． Increased from 15 to 6.

The silica-alumina cogel thus obtained was distributed door to door.
Washed with water until sodium disappeared.

The gel was dried at 120°C, baked at 500°C for 3 hours, and ground into particles with d of 0.76 mm.

The T)H of the mixture of 99 g of the above silica-alumina particles and 1000 ml of 0.1 mol N)LiNOs was increased from 45 to 7.0 by adding concentrated aqueous ammonia.

The silica-alumina was separated and dried at 1208C.

This silica-alumina was used as a support for a catalyst containing 1 pbw of nickel and 8 pbw of molybdenum per 1100 pb of silica-alumina (95.6% by weight dry matter).

The catalyst was manufactured as follows. An aqueous solution of ammonium molybdate 13.79 and monoethanolamine is mixed with nickel formate dihydrate 2.9! 1 of an aqueous solution.

After diluting the mixture with water to a volume of 175 ml, it was used to impregnate the neutralized silica-alumina 91 described above.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then fired at 500°C for 3 hours.

Catalyst W A catalyst containing 3.8 pbw of cobalt and 9.5 pbw of molybdenum per 100 pbw of alumina was prepared as follows.

876g ammonium molybdate and 30% H2O21
000ml of cobalt nitrate hexahydrate 940S
was mixed with an aqueous solution of

After diluting the mixture with water to a volume of 350'Oml,
It was used to impregnate 1.5 mm alumina extrudate 5001.

After 30 minutes, the gold-soaked material was dried at 120°C for 18 hours and then baked at 500°C for 3 hours.

Catalyst X A catalyst containing 4.3 pbw of nickel and 10.9 pbw of molybdenum per 100 pbw of alumina was prepared as follows.

An aqueous solution of 2.01 kg of ammonium molybdate was mixed with an aqueous solution of 2.13 kg of nickel nitrate hexahydrate.

After adding 61 parts of 25% aqueous ammonia, the mixture was diluted with water to a volume of 111 parts.

This mixture was used to impregnate 10 kg of alumina.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then fired at 500°C for 3 hours.

Catalyst Y A catalyst containing 4.3 pbw of nickel and 10.9 pbw of molybdenum per 1100 pb of alumina was prepared as follows.

An aqueous solution of 44.1:1 ammonium molybdate containing monoethanolamine was mixed with an aqueous solution of 30.74 g of nickel formate dihydrate containing monoethanolamine.

The mixture was diluted with water to a volume of 190 ml and then used to impregnate 220 g of alumina.

After 15 minutes, the gold-soaked material was dried at 120°C for 18 hours and then fired at 500°C for 3 hours.

Hydrogenation Deflow Experiment A residual hydrocarbon oil with a total vanadium and nickel content of 245 pbw1C5-asphaltene content of 7.2% by weight and a sulfur content of 2.1% by weight was obtained as an atmospheric distillation residue of Caribbean crude oil. Catalytic hydrodesulfurization was carried out without catalyst replenishment and using catalyst AY.

For this purpose a temperature of 420°C, a hydrogen partial pressure varying from 40 to 200 bar, 25 ONN/kg of fresh raw material.
Outlet gas velocity of 4.35 to 9 oil per kg of catalyst per hour
The oil was passed down with hydrogen through a cylindrical fixed catalyst bed at a space velocity of .

The catalyst was used in its sulfide state. The performance of a catalyst for hydrodesulfurization of residual hydrocarbon oil without catalyst replenishment is described in terms of catalyst life and average activity (K average) defined as follows.

Catalyst life (expressed in 9 catalyst per kg feedstock) is the maximum amount of residual oil that can be hydrodesulphurized over the catalyst before the catalyst exhibits rapid deactivation.

The average activity (expressed in kg feed/kg catalyst/hour/(S weight %) sky) is the activity of the catalyst at the point when half of the catalyst life is reached.

Table 1 shows the results of the hydrodesulfurization experiment and the properties of the catalyst used.

The specific mean pore diameter (p) of the catalyst was calculated from the overall pore diameter distribution determined by the nitrogen adsorption/desorption method combined with the mercury infiltration method, as described previously.

The criteria for a catalyst that should be optimal under the conditions applied in these hydrodesulfurization experiments are as follows.

Catalyst life is at least 2500kg raw material/kL! The catalyst should have an average activity of at least 1.5 kg feed/kg sieved (wt% S)2.

Runs 1-24 (where the catalysts have a lifetime of over 2500 and average > 1.5) are hydrodesulfurization experiments according to the present invention.

The catalyst used in these experiments was p/(d)"'
and according to the requirements regarding the optimal catalyst pore diameter distribution.

Runs 25-35 (where the catalyst has a lifetime shorter than 2500 and/or an average of <1.5) are hydrodesulfurization runs outside the scope of the present invention.

The catalysts used in these experiments did not meet at least one of the requirements regarding p/(dP9 and optimal catalyst pore diameter distribution.

In experiments 25-33, the catalyst used was 45 x 1
05X (PH2)” p/(d)”99 X 10
'(PH2)2 requirements are not met.

The catalyst W used in Experiment 32 had a diameter of 0.4
Pore volume less than yd/g and more than 20% in pores with diameter greater than 1.7×p.

Catalyst It has a pore volume of more than 20% in pores and more than 10% in pores with a diameter greater than 1100n.

Catalyst Y used in Experiment 35 had a value of 0.7×p or more to 1.
0.4 Fril in pores with a diameter of 7Xp or less
pore volume smaller than /9, 20% more pore volume in pores with diameter smaller than 0.7 have

The influence of PH2 on catalyst performance is evident when comparing the following experiments.

Runs 1 and 25 with catalyst A Runs 4.5 and 26 with catalyst C Runs 6 and 27 with catalyst R Runs 8 and 28 with catalyst F Runs 17 and 29 with catalyst N Runs 22 and 30 with catalyst S Optimal catalyst pores According to the requirements regarding the diameter distribution and 4
5 X 10-5X (PH2)”< p /(d7
Catalyst A showing optimal performance for hydrodesulphurization of residual oils at PH2 (Experiments 1.4.5.6.8.17 and 22) meeting the requirement of ``9 < 9 X10-4 x (PH2)2 , C, D, F, N and S are 45 X 10-5X (PH2)2< p/(dP9
At PH2, which does not satisfy the requirement of < 9X 10-'×(PH2)2 (Experiments 25-30), it is relatively unsuitable for this purpose.

Claims (1)

[Scope of Claims] In a catalytic hydrodesulfurization process without catalyst replenishment of residual hydrocarbon oils having a total vanadium and nickel content exceeding 1 120 pprrw, one or more metals having hydrogenation activity supported on a carrier or more, and 1) 45X10-5X(PH)2<p/(d)0.9<
The ratio average satisfies the following conditions: 9 x 10-4 x (P)2, where PH2 is the applied hydrogen partial pressure (expressed in bars) and d is the specific average particle diameter (expressed in mm). 2) at least 0.4 ml/g of the total pore volume is p
A total pore volume that is present in pores having a diameter that is not more than 30 factors smaller than the value of p and not more than 70 factors larger than the value of p, and the total pore volume exceeds 0.45 ml/ji,
and 3) a sharp pore diameter distribution in which a) less than a factor of 20 of the total pore volume is present in pores with diameters smaller than a factor of 70 of the value of p, and b) a factor of 20 of the total pore volume.
C) a factor of 10 or less of the total pore volume is present in pores with a diameter greater than 100 nm; A catalytic hydrodesulfurization process that involves applying a catalyst with a sharp pore diameter distribution.