JPS6027714B2 - Hydrocarbon conversion methods - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the catalytic hydrodesulfurization of vanadium- and nickel-containing residual hydrocarbon oils without catalyst recharging.

A method of this type has already been described in our Hakama Seki Sho 48-65204 publication.

According to this publication, these catalysts are used for the purpose of exhibiting lifetimes and average activities above established minimum values if they are used in residual desulfurization processes in standard catalyst tests.

They have a total pore volume of 0.30' or more, of which less than 10% is filled by pores with a diameter of -10' or more, and the quotient p/(d}o.9 is 3 x 10-4 ×
(PH2)2mip/(d)0.9<17×10-4×(
It has a specific average peacock (p) and a specific average particle diameter (d) that satisfy (PH2)2.

Here, PH2 indicates the hydrogen partial pressure used (p: mm,
d: mm, PM2: crowbar). As shown in the above publication, 3×10-4×(PH2)2 or less or 17
Catalysts with a commercial p/(d) of 10-4 (PH2)2 or higher are tested in standard catalyst tests to meet the minimum life and average activity requirements stated in this publication. exhibits too long a lifespan and/or too low average activity. The catalyst life for hydrodesulfurization of vanadium- and nickel-containing residual hydrocarbon oils without catalyst recharging is relatively short because the catalyst exhibits a relatively high average desulfurization activity. The above publication is therefore actually based on a compromise between catalyst life and average desulfurization activity. Applicant's subsequent studies on catalyst lifetime and average desulfurization activity showed that if a residual hydrocarbon bottle is contacted with two or more different catalysts in succession, compared to methods using only one catalyst, It is shown that considerably improved results can be obtained.

The use of suitable combinations of two or more different catalysts provides improved activity and/or lifetime for each catalyst individually than the combination.

That is, more complete desulfurization occurs under the same conditions, and catalyst life increases when a certain level of desulfurization is maintained (the usual practice). However, these better results are only achieved if the catalyst used satisfies certain conditions regarding its porosity, particle size and volume ratio. In this patent application, the combination of two or more catalysts is considered to consist of catalyst 1 and catalyst U for simplicity.

Definition "Catalyst 1" means the second catalyst when a combination of two catalysts is used, and the last catalyst when a combination of two or more catalysts is used, and the definition "Catalyst 1" If a combination of two catalysts is used, the first catalyst and
When using a combination of two or more catalysts, the first ``second'' means all catalyst combinations except the last one.
, "last" is based on the direction of liquid flow over the catalyst combination). When a combination of two catalysts is used, the conditions regarding catalyst porosity, particle size, and volume ratio are as follows.

{a' The same conditions as for the catalyst according to the publication of the total pore volume and the pore volume occupied by pores with a diameter of 10 m or more apply to catalyst 1 and catalyst D', i.e., the total pore volume is 0.30 ship/ta or more, of which 1
0% or less is defined by a hole having a diameter of 10 plate m or more.

{b} Catalyst D'ma, quotient [pno(d)o・9) cat.
B is the condition 0.6×10-4×(PH2)2mi [p/(d
)0.9] cat. 0ku3ju6xlo-4×(PH2)
It has p and d that satisfy 2.

'c} Catalyst 1 is the quotient [p/(d)o・9]cat. 1 is condition 1.2×[p/(d)0.9] ground ○. Mi[p/(d
) 0.9] qt.・＜530×10-4×(PH2)
It has p and d that satisfy 2.

'd} Proportion of total contact volume occupied by catalyst m (
The food soot (volume %) is between 10 and 90%, and the following condition 4o
X Sanshu X・oo) 2×(P Rudder) Seminar Catalyst Day Capacity%
<3.

. X lord suzerain ×・oo) 2X (P rudder) satisfies li. Here SF is the sulfur content of the feedstock and SP is the desired sulfur content of the desulfurization product, each in weight percent.

When using a combination of two or more catalysts, the conditions regarding the porosity, particle size, and volume ratio of the catalysts are as follows:
substantially coincident with the side.

[e- The conditions described in 'a regarding the total pore volume and the ratio of the pore volume occupied by pores having a diameter of 10 mm or more to the total pore volume apply to the individual catalysts constituting the combination of catalyst 1 and catalyst 0. applicable to each of the following.

{f'[p/(d)o. 9] cat. Regarding 1 [c'
The conditions described in are applied to the average p/(d)o·9 of catalyst 1, which is determined by the weighted average of the p/(d)o·9 values of each of the individual catalysts constituting catalyst 1, and ( g) Each of the individual catalysts making up catalyst 1 has its respective quotient p/(d)o. 9 is [p/(d)o・9] cat.
It has p and d such that it is greater than or equal to b.

Therefore, this patent application is based on vanadium and nickel without recharging the catalysts such that hydrocarbon oil is continuously contacted with catalyst 1 and catalyst 0 that satisfy the conditions shown in 'a-(g) above. The present invention relates to a method for catalytic hydrodesulfurization of residual hydrocarbon oil. Quotient of catalyst 1 and catalyst RO p/
(d) When the conditions for o.9 are compared with the conditions for this quotient of catalysts applied in the above publication, many catalysts excluded in that publication are found to be applicable to the catalyst combination of the present invention. was found to be eligible and issued.

Catalysts outside the scope of the above publications that are now eligible are 'a)
As catalyst 0, quotient [pno(d)o.9] ground. b is condition 0
．． 6×10-4×(PH2)2mi [p/(d)0.9]
cat. A catalyst having p and d that satisfies n<3×10-4×(PH2)2, [b' Assuming that the catalyst is 0, the quotient [p/(d)o・9)ca. B is the condition 17×10-4(PH2)2<[P/(d)0・
9] Catalyst having p and d such that C small D < 36 × 10-4 × (PH2)2 (this condition occurs when the hydrogen partial pressure is used at approximately 52% or less) [ c} When one catalyst is used as the catalyst 1, the catalyst 1 is the quotient [p/(d)o・9)c
The condition for 1st grade is 1.2 x 0.6 x 10-4 x (PH2) 2 mi [p/(d) 0.9] qt.・＜3×10-4×(PH
2) When one catalyst is used as the catalyst 1, 'd-, which has p and d satisfying 2, the quotient [p/(d
)o・9] cat. 1 is the condition 17×10-4×(PH2
)2ku [p/(d)o. 9] Legs. 1<530xlo-
Catalyst 1 with p and d satisfying 4×(PH2)2 In addition to the scope of the above-mentioned publication, the present invention is naturally subject to limitations with regard to the applied catalyst.

Catalysts available in the above-mentioned publications which are not eligible for application of this invention include, among others,
p/(d).

・9) Evil. B is the condition 17×10-4×(PH2)2>[
p/(d)0.9〕C skin 〉36×10-4×(PH
2) a catalyst with p and d satisfying 2 (this condition occurs when the hydrogen partial pressure is approximately 52 bar or more)'b} When one catalyst is used as catalyst 1 , quotient [p/(d)o. 9] cat. 1 is the condition 3×10-4×(PH2)2<[p/(d)〇. 9
] Earth.・<1.2×[p/(d)o. 9] Catalyst 1 with p and d that satisfy qto (this state is the catalyst RO, the quotient [p/(d)o9] skin.0 is the condition [p/(d)
)0.9) cat. □＞2.5×10-4×(PH2)
The method for measuring d (which occurs when a catalyst having p and d that satisfies 2) is used differs depending on the shape of the catalyst particles.

In the case of catalyst particles having a shape such that the diameter distribution of the catalyst particles can be determined by age analysis, d is measured as follows. A complete segmental analysis of a representative catalyst sample was performed using the AS
TM Standards Division 30 (ASTM-EII-61)”,
96-101 (1969), and then, for each successive segment, the weight percentage of that segment relative to the total weight of the catalyst sample is determined. Read d from the graph where it is cumulatively plotted as a function of the linear average diameter of the particles. That is, d is the diameter of particles corresponding to 50% of the total weight. This method is used to determine the d of spherical and granular materials and similarly shaped materials such as extrudates or pellets with a length-to-diameter ratio in the range 0.9 to 1.1. be able to. Extruded products, pellets, and similar cylindrical materials with a length-to-diameter ratio smaller than 0.9 or larger than 1.1, whose particle diameter distribution cannot be measured by segmental spectroscopy, are , the measurement of their d is performed as follows. Full length distribution tests (for length to diameter ratios less than 0.9) or full diameter distribution tests (for length to diameter ratios greater than 1.1) were performed on representative catalyst samples. Then, for each successive length and diameter section, read d from a graph in which the weight percentage based on the total weight of the catalyst sample is cumulatively plotted as a function of the linear average size of that section. That is, d is a value corresponding to 50% of the total weight.
After measuring the complete pore diameter distribution of the catalyst sample, read p from the following graph.

That is, for pore diameters in the range 0-10 mm, each successive pore volume increment that is less than or equal to 10% of the pore volume (provided that this increment is less than or equal to 10% of the pore volume) The quotient of the increment in pore volume and the corresponding pore diameter interval is calculated as the linear average pore size for the associated pore diameter interval. Read p from the graph where it is cumulatively plotted as a function of diameter. That is, p is 100n
The pore diameter corresponds to 50% of the total quotient in m. The complete pore diameter distribution of the catalyst was determined by the nitrogen adsorption/desorption method [E.V. Ballou and O.K.
0.K. Doolen, "Analytical Chemistry" (
AM1yticaIChemisthi) Volume 32, 532
page (196 Sanno)] using the mercury infiltration method [H. L. Ritter and L. C. Drake, Industrial and Engineering Chemistry (lnd.
&Eng・Chem・) Analysis Edition Volume 17, page 787 (19
40] can be carried out very suitably using a mercury pressure of 1-2000 bar.

In this case, the pore diameter distribution of the catalyst in the range of pore diameters below 7.5 nm is preferably determined by J.C.P. Bmekhoff and J.H. Debord. Japan/de enemy)
, “Catalysis Phenomena Magazine” (JomM1ofCablysis)
) Vol. 10, p. 377 (1968), calculated from the nitrogen desorption isotherm (assuming a cylindrical hole),
7. The pore diameter distribution of catalysts in the pore diameter range larger than the rule m is preferably calculated using the formula 15000: pore diameter (in mm)=absolute mercury pressure (in pearls).

The catalyst used as a catalyst in the process of this invention preferably has a total pore volume of 0.45 or more and a surface area of 100 or more, particularly 150 or more.

Furthermore, they are preferably quotient [p/(d)o. 9]c
at. 0 is the condition [p/(d)0.9]Cat. RoZIO
-4×(PH2)2.

In the hydrodesulfurization method of this invention, the quotient [p/(d)o
・9] cat. B is the condition 10-4×(PH2)2mi [p/(d)0.9] side. It is particularly desirable to use a catalyst that satisfies (b)<36×10-4×(PH2)2.

The catalyst also has a total pore volume of 0.45'/ta or more, of which at least 0.4'/ta has a diameter of 0.7×p.
and 1.7 x p, 'a) not more than 20% of the total pore volume is filled by pores with a value diameter of not more than 0.7 x p, and tb' not more than 20% of the total pore volume; is 1.7×
It has a sharp pore size distribution characterized by pores having a diameter of p or more.

As already mentioned above, a single catalyst or a combination of two or more catalysts can be used as catalyst 1 in the process of the invention.

Preferably, a single catalyst is used as catalyst 1 in this method. If a combination of two or more catalysts is used as catalyst 1, the catalysts constituting catalyst 1 may be mixed with each other in the desulfurization reactor or separated from each other (e.g. in a separate bed or separate bed). in). If a combination of two or more catalysts is used as catalyst 1, preferably the catalysts making up catalyst 1 are separated from each other in the reactor, in particular the quotient of each of the catalysts making up catalyst 1 is
/(d)o. 9 is smaller than that of the preceding catalyst;
That is, the quotient p/(d)o. 9 is to use a method that decreases according to the direction of liquid flow over the catalyst combination.

When a single catalyst is used as catalyst 1 and
Even when a combination of two or more catalysts is used, a catalyst with a total pore volume of 0.40 mm or more is desirable.

Catalyst 1 has a quotient [p/(d)o・9]cat. 1 is the condition [p
/(d)o. 9] Cat. 121.4×[p/(d)o
．． 9] qt. If p and d satisfy D, and in addition, if a combination of two or more catalysts is used as catalyst 1, then this The conditions are p/(d) of each individual catalyst constituting catalyst 1.

・Average p/(d) of catalyst 1 determined by weight average of 9 values
Applies to o.9. The catalyst used in the invention preferably contains 0.5-12 parts by weight, especially 0.5-10 parts by weight of nickel and/or cobalt and 2.5-60 parts by weight, especially 2.5-30 parts by weight. of molybdenum and/or tungsten based on 10 parts by weight of the carrier.

The atomic proportions of nickel and/or cobalt and of molybdenum and/or tungsten can vary within wide limits. However, it is preferably between 0.1 and 5. Examples of highly desirable metal combinations of the catalysts of this invention are nickelnotungsten, nickel/molybdenum, cobaltnomlybdenum, and nickel/cobaltnomlybdenum. The metal may be present on the support in metallic form or in oxide or sulfide form. It is desirable to use a catalyst of the invention in which the metal is present on the spoil body in its sulphide form. In addition to the above-mentioned catalytically active metals, other catalytically active metals and promoters such as halogens such as phosphorus, boron, fluorine, and chlorine may be included. Very suitable supports for this catalyst are oxides of the elements of groups B, M and W of the periodic table, such as silica, alumina, magnesia, zirconia or mixtures of these oxides, such as silica-alumina,
These include silica magnesia, alumina magnesia, and silica zirconia. Alumina and silica alumina are preferred as supports for this catalyst. The metal loading of most commercially available catalysts containing cobalt/molybdenum metal combinations is supported on alumina or silica-alumina as supports, and for hydrocarbon processing with hydrogen, typically about 15 parts by weight of metal per 100 parts by weight of support. section is recommended.

In the experiments on which the above-mentioned publication is based, on the one hand the relationship between the porosity and particle size of the catalyst and the hydrogen partial pressure used, and on the other hand the relationship between vanadium- and nickel-containing residual hydrocarbon oil without catalyst refilling. The suitability of these catalysts for the hydrodesulfurization process was mentioned and it was expected that the metal loading described above would give the most favorable results also for this application.
As can be seen in the examples of the above publication, the metal loading of the cobalt-molybdenum catalyst varies only between 13.3 and 16.1 parts by weight per 100 parts by weight of the support.
Subsequent studies show that the metal loading of these catalysts can be greatly reduced without compromising their suitability for desulfurization of residual hydrocarbon oils. In this way, for example 10
For 0 parts by weight of alumina, 2. A catalyst containing 5.5 parts by weight of cobalt and 5.5 parts by weight of molybdenum has p, d, P
1.2 for the same 100 parts by weight of alumina; 4. Box weight part cobalt and 10. It was found to have the same suitability for desulfurization of residual hydrocarbon oils as catalysts containing $1.00 parts by weight of molybdenum. The discovery that it is possible to use lower metal loadings than was thought until recently is of course very important from the point of view of catalyst production costs. A good low metal loading can result in saving metal and simplifying carrier manufacturing. When the process according to the invention of catalysts containing cobalt and molybdenum supported on alumina or silica-alumina as support is used, it follows from the above point that 5 - 1 of metals per part by weight of support 10 is used.
It is desirable to select a catalyst containing parts by weight of . This advantage of low metal loading can of course also be applied in the process according to the above publication if a catalyst containing cobalt molybdenum supported on alumina or silica-alumina is used. The catalyst applied to this invention is manufactured by supporting a suitable metal on a carrier having such a specific average porosity, and after the metal is supported, it can be used as it is or with a specific average porosity so as to satisfy the conditions of this invention. Catalysts can be obtained by increasing or decreasing the diameter. The preparation of this catalyst is preferably carried out by co-impregnating the support in one or more steps with an aqueous solution consisting of one or more nickel and/or cobalt compounds and one or more molybdenum and/or tungsten compounds, The composition is then dried.

When drying the composition, the drying is usually done at 100 pm and 15 pm.
Physically bound water is removed from the composition, and condensation is typically carried out at a final temperature of between 450 and 55 qo.
By heating the composition to between 0 qo and maintaining the composition at this final temperature, the metal salts decompose during power firing of the composition to form the corresponding metal oxides. The nickel and cobalt compounds used in the production of this catalyst are finally nitrates. Ammonium molybdate and ammonium tungstate are currently used as molybdenum and tungsten compounds. It has been found that significant thermal effects occur during the evaporation of this composition and that this effect adversely affects the activity of the final catalyst.

For the production of highly active catalysts, it is therefore important to keep the thermal effects during these forces as small as possible. One of the causes of the large thermal effect during power oxidation is the simultaneous decomposition of nitrate and ammonium compounds. This thermal effect during decomposition can be avoided by using nickel or cobalt formide instead of nitrate during catalyst preparation. Other ways to reduce as much as possible the thermal effects that occur during the build-up are to use the build-up very carefully, for example by increasing the heating rate slowly or by heating in stages. Localized heating of the composition during stressing, which adversely affects the activity of the final catalyst, ensures effective heat removal during stressing, e.g. by passing a high velocity gas stream over the material to be polished. , which can be largely avoided by covering the material with a figuratively thin layer. For information on the methods by which the porosity of the mortar material can be influenced and more specific details of the preferred method of preparing this catalyst, reference is made to Hakama Kaisho No. 48-165204, which is discussed in detail. ing.

The process for catalytic hydrodesulfurization of residual hydrocarbon oil without catalyst recharging preferably involves flooding the hydrocarbon oil and raising it at elevated pressure through two or more vertically disposed fixed beds in the presence of hydrogen. , to pass downward or radially.

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

The hydrodesulfurization process of this invention is carried out in a single reactor or in two or more reactors.

If the process of the invention is carried out in one reactor,
It should contain at least two catalyst beds, of which a first catalyst bed (along the direction of liquid flow) and possibly one or more immediately following catalyst beds as catalyst 1 above. The final catalyst bed (along the path of liquid flow) and possibly one or more immediately following catalyst beds containing one catalyst or combination of catalysts as defined above are defined as catalyst 0. Contains a catalyst. If the process of the invention is carried out in two or more reactors, the first reactor and possibly one or more immediately following reactors contain catalyst 1, the last reactor and possibly one or more immediately following reactors contain catalyst 1; One or more immediately following reactors contain zero catalyst. The catalysts applied to the individual catalyst beds and/or the individual reactors differ from each other in their chemical composition. The specific average particle size of the catalyst used in this invention is generally 0.
5-2.5 legs, preferably 0.6-2. It is an enemy. In order to achieve a good catalytic performance at a given p and PH2, the value d required in this invention is too small for practical application in the manner described in the above-mentioned publication. Desulfurization takes place in the presence of a porous mass made of small catalyst particles. The reaction conditions used for the hydrodesulfurization of this invention can vary within a wide range.

Hydrodesulfurization is preferably carried out at a temperature between 300 and 475 qo, a hydrogen partial pressure of 50-200 bar per unit time,
It is carried out at a space velocity of 0.1 to 1 part by weight of fresh feed per unit catalyst volume and a hydrogen/feed ratio of 150-200 skin IQ/feed k9. Especially 350-450q
o temperature, hydrogen partial pressure of 70-18 rules, 0.2-5
Parts by weight of feedstock/capacity of catalyst/hourly space velocity, 250-
A hydrogen/feed ratio of 100 plates IH2/feed k9 is desirable. In the hydrodesulfurization of this invention, it is very suitable to carry out a demetallization treatment as a pretreatment.

As a result of demetallization, the deactivation of the desulfurization catalyst combination is reduced and its lifetime is increased as a result. Demetallization of the residual hydrocarbon oil is preferably carried out in the presence of hydrogen and a catalyst. Demetallization involves passing the hydrocarbon oil upward and downward through one or more vertically arranged reactors containing fixed or moving catalyst beds at elevated temperatures and pressures in the presence of hydrogen. Or very well done by communicating radially. In a highly preferred embodiment of demetallization, the hydrocarbon oil is passed through a vertically arranged catalyst bed into which, during operation, fresh catalyst is introduced intermittently from the top of the catalyst bed and used. The spent catalyst is removed from its bottom (demetallization by bunker flow method).

Another highly preferred embodiment of the demetalization process includes several reactors containing fixed catalyst beds, which reactors are used alternately for the demetalization process. Demetallization takes place in one or more of these reactors and the catalyst is recharged in the remaining reactors (fixed bed swing method).
gprinciple)).

Demetallization, if desired, is then carried out by suspending the catalyst in the hydrocarbon oil to be demetalized (demetalization by slurry phase process). Catalysts suitable for demetalization of residual hydrocarbon oils are:
A catalyst containing one or more metals with hydrogenation activity supported on a support. If demetallization is carried out prior to the desulfurization of this invention, the demetallization is preferably carried out by bunker flow or fixed bed swing techniques, and desulfurization is effectively carried out on two or more conventional fixed beds. As already mentioned, the demetalization of vanadium- and nickel-combined residual hydrocarbon oils results in an increase in the lifetime of the catalyst combination used for the hydrodesulfurization of the demetallized oils.

In the catalytic hydrodemetallization of vanadium- and nickel-containing residual hydrocarbons followed by desulfurization of the demetalized oil of the present invention, the following equation is derived. Earth = (1.05±0
．． 20)×M,x(L,/L2)o. 5 Here M, and M
2 represents the metal content in the non-demetallized and demetalized oils, respectively, and L and L represent the lifetime of the desulfurization catalyst when used in the non-demetalized and demetalized oils, respectively.

In deriving this equation, the following limitations may be taken into account. ○} Metal content in hydrocarbon oil before demetallization (
M,) can vary from 25 to 1500 breastw (parts per million weight).

'2} The lifetime (L) of the desulfurization catalyst combination used in the demetalized oil can vary between 2000 and 1600 field hours.

'3} Metal content in hydrocarbon oil after and before demetallization (
The quotient of earth and M,) can vary between 0.75 and 0.10.

■ The product of the metal content (M,) of the hydrocarbon oil before demetallization and the lifetime (-) of the desulfurization catalyst combination used in the demetalized oil can vary between 2 x 1 and 3 x 1.

The above relationship between L, , L2, M, and M2 can be used for pretreatment of catalytic hydrodemetallization of feedstock during the hydrodesulfurization of residual hydrocarbon oil of this invention for a certain period of time. It can be determined to what value the metal content of the feedstock should be reduced in order to extend the life of the desulfurization catalyst combination within the reactor.

In this way, by performing catalytic demetallization before desulfurization,
Deactivation of the desulfurization catalyst combination is suppressed and its lifespan is extended as a result.

This means that if a previously catalytically demetallized feedstock is treated with a fixed volume catalyst combination, the lifetime of that catalyst combination will be longer than that of a non-demetalized feedstock treated with the same volume catalyst combination. This means that it is larger than when Therefore, by performing catalytic demetalization as described above, the feedstock is contacted with more catalyst volume than if no demetalization was performed. This is because although the specific capacities of the combinations of desulfurization catalysts are the same, in the former case, a certain amount of demetalization catalyst is additionally used. Subsequent studies on the catalytic demetalization of vanadium and nickel combined hydrocarbon residual oils of this invention followed by catalytic hydrodesulfurization of the demetallized oils using a combination of two desulfurization catalysts have shown that the total catalyst capacity is If a part of the desulfurization catalyst combination is replaced with a demetalization catalyst while the desulfurization level remains constant, and conditions 1 to 6 below are added, the life of the desulfurization catalyst combination will be further increased while maintaining the desulfurization level at a constant level. It can be stretched. 1 The combination of desulfurization catalysts is the only two single desulfurization catalysts where the first is catalyst 1 and the second is catalyst 0.

2 The residual hydrocarbon oil used as a raw material is 12
The wind w has a total vanadium, nickel content.

3 The demetalization catalyst as catalyst 0 satisfies the following conditions, a
The catalyst consists of one or more metals with hydrogenation activity on a support.

b p/d>3.5-0.0, where v is the white fraction of the pore volume filled by pores with a diameter of 10 m or more relative to the total pore volume.

c Total pore volume is 0.40'/ta or more, d Specific surface area is 100'/ta or more, but the catalyst quotient p
/d is 3.5 - 0.0 is larger, and at most 10
With p and d such that -0.15v, the catalyst must also satisfy the following conditions:

e Nitrogen pore volume is 0.60'/ta or more, f specific surface area is 150/ta or more, g P is regular plate or more, 4 Catalyst 0 has a larger total pore volume than Catalyst 1.

5 Catalyst 0 and Catalyst 1 have the following relationships p, d, and v.

[p/(d)o・9)Cat. .

〉1.2×{[p/(d)o. 9] Cat.・-0.8
(v.

-v, )}6 The proportion of catalyst 0 in the combined catalyst of catalysts 0, 1 and 0 is at least 10%v.

The catalytic hydrodesulfurization method for residual hydrocarbon oil using a catalyst that satisfies the conditions a to g above is disclosed in Tokkōki No. 49-44004, JP-A-50-86503, and JP-A-51-535.
It is described in Japanese Patent Laid-open No. 04 and Japanese Patent Application Laid-Open No. 51-55791.

This patent application also relates to an improved process for the catalytic hydrodesulfurization of vanadium- and nickel-containing residual hydrocarbon oils without catalyst recharging (hereinafter referred to as "the improved process of this invention"), In this method, hydrocarbon oil is continuously contacted with single catalyst 1 and single catalyst B, which catalysts satisfy the following conditions.

'al Both catalysts have a total pore volume of 0.30'/ta or more, and the percentage (v) of the pore volume occupied by pores with a diameter of 10 or more plates to the total pore volume is less than or equal to 10. , tb'catalyst river ma quotient p/(d)o. 9 is the condition 0.6×10
-4×(PH2)2mi [p/(d)0.9]cat. ○
Specific average pore size (p) and specific average particle size (d) that satisfy <36×10-4×(PM2)2
{c' The proportion of the combined catalyst volume of catalysts 1 and RO occupied by catalyst RO (volume % of catalyst U) is 10 and 90
Between %, condition 4oX (subject MiX・oo) 2×(P place)
Volume % of semi-catalyst n<3.

Satisfy oX (mi husband X・oo) 2X (P ground) li. where SF is the sulfur content of the feedstock and SP is the desired sulfur content of the desulfurization product (p: mm, d: mm, P
H2: Bar, SP and SF: %W). Conditions 2-6 above
An improvement is made in that catalytic hydrodemetallization using a demetalization catalyst having 0 is carried out prior to desulfurization.

Examples of demetallizing catalysts include the above-mentioned Tokkan Sho 49-44004, Tokkan Sho 50-86503, and Tokkan Sho 51-5.
Examples thereof include the catalysts described in Japanese Patent No. 3504 and Japanese Patent Application Publication No. 55791/1983.

As examples of feedstocks for the process of the invention, crude oil and residual oil obtained by distilling crude oil under normal pressure or reduced pressure can be used.

Residues obtained during the distillation of products obtained by thermal and catalytic cracking of heavy hydrocarbon oils may also be treated with this invention. The invention is illustrated in the following examples.

Example 1 Each catalyst (catalysts A-M) was used separately and at the same time
Eleven combinations of two different catalysts were used in the hydrodesulfurization of five vanadium- and nickel-containing residual hydrocarbon oils (oils A-E) without catalyst reloading.

Desulfurization of oils involves treating these oils at elevated temperatures and pressures in the presence of hydrogen.
The process was carried out through two cylindrical fixed catalyst beds in a downward direction. The experiment was performed three times. In each of the three experiments, the same oil was desulfurized under the same conditions and with the same volume of catalyst to the same product sulfur content (SP).

In one of the three experiments, the first catalyst bed was
The second bed contains a catalyst defined as Catalyst D.

Both catalyst beds in the remaining two experiments contained exclusively either catalyst 1 or catalyst 0. In the desulfurization experiment, the initial temperature was 360±50q0.
, a space velocity of 0.7 k9/1/h, a gas velocity of 600 NI/k9, and a hydrogen partial pressure of 75 to 150.

The temperature must be gradually increased during the experiment in order to obtain a product with a constant sulfur content. Desulfurization experiments were terminated when temperatures above 420 oo had to be used to obtain a product with the desired sulfur content. The composition and properties of the catalyst used in its sulfide form are listed in Table A.

Examples of the manufacturing method of the nine catalysts used in this experiment can be found in our Japanese Patent Application Laid-Open No. 48-65204, which describes the manufacturing method of these catalysts in detail. Catalysts B* and D
The preparation of * was carried out in the same manner as described for catalysts B and D, except that the metal loading used in the preparation of B* and D* was lower. The five residual oils in this test are described in more detail below. The results of the desulfurization experiments are listed in Table B. Oil A Total vanadium obtained as residual oil from atmospheric distillation of Middle Eastern crude oil, nickel content 7.0% and sulfur content 4. weight% of oil.

Oil B Total vanadium obtained as residual oil from atmospheric distillation of Middle East crude oil, nickel content 6. % by weight of oil.

Oil C An oil with a total vanadium, nickel content of 110 feet w and a sulfur content of 5.2% by weight obtained as a vacuum distillation residual oil of an atmospheric distillation residual oil of Middle East crude oil.

Oil D Total vanadium obtained as residual oil from atmospheric distillation of Caribbean crude oil, nickel content 22 Momomisaki w and sulfur content 2
．． weight% of oil.

Oil B: Total vanadium obtained by demetallization of Oil D, nickel content: 13 ■ dish w and sulfur content: 1. base weight% oil.

Demetallization of oil D is carried out at elevated temperature and pressure in the presence of hydrogen through a vertically disposed fixed bed of demetallization catalyst. The metal removal catalyst contains 0.5 parts by weight of nickel and 2.5 parts by weight of vanadium based on 10 parts by weight of the silica carrier. It contained parts by weight of Table A Table B Table B (continued) Table I Table 0 Table m Among the experiments in Table B, only the experiment 1-XV is the desulfurization experiment of this invention.

Other experiments in the table are for comparison. Experiment 1
In 1XV, each catalyst combination satisfying the conditions related to porosity and particle size was used;
The conditions specified for "Volume % of catalyst 0" are also satisfied.

Compare the lifetimes of each of the catalyst combinations used in Experiments 1-XV and the individual catalyst lifetimes used in related experiments 1'-XV' and 1''-XV'' listed in the last column of Table B. For example, the improvement in catalyst life achieved by using the catalyst combinations of this invention is clearly visible. Experiments A-D,
A′-〇 and A″-〇′ are also listed in Table B for comparison.

Although two catalyst combinations are used in experiments A-D, they do not meet the specified conditions.

In Experiments A, B and C the catalyst had a quotient of p/(d)o. 9
is used as catalyst 1, which is too small, and in experiment D the catalyst has a quotient of p/(d)o. 9 is used as catalyst 0 which is too large. The lifetimes of each of the catalyst combinations used in experiments A-D and listed in the last column of Table B are the same as those of the individual catalysts used in the corresponding experiments A'-D' and A''-D''. Applications of these catalyst combinations show that there is an improvement in catalyst life with respect to the individual application of one of the two catalysts in the combination, but an improvement in catalyst life with respect to another application of the other catalyst in the combination. The lifetimes of the catalyst combinations used in Experiments 1 and 1 and listed in the last column of Table B are compared with those of the catalyst combinations used in Experiments C and B. A comparison between them clearly shows the great influence of the results when Catalyst 1 and Catalyst D are used.

Example 0 This example illustrates the above-mentioned "specific example of the improved method according to the present invention."

The catalyst combination consisting of demetalization catalysts (catalysts 1, 11 and 40), a first desulfurization catalyst (catalyst A) and a second desulfurization catalyst (catalyst D) produces two vanadium- and nickel-containing residual carbonizations without catalyst recharging. It was used for hydrodemetallization of hydrogenated oils (oils D and F) followed by hydrodesulfurization.

Furthermore, a catalyst combination consisting of two desulfurization catalysts A and D,
and also, each of these two catalysts was separately used for the desulfurization of two oils without catalyst recharging, oil demetallization/desulfurization or desulfurization alone using hydrogen at elevated temperature and pressure. The oil was passed downward through three cylindrical vertically arranged fixed beds. The experiment was conducted four times each (fombyfo
ur) It was done.

In each of the four experiments, the same oil was run under the same conditions, the same volume of catalyst, and the same sulfur content of the product (SP 0.5% w in all experiments).

In one of the four experiments, the first catalyst bed contained a demetalization catalyst shown below as Catalyst 0, the second catalyst bed contained a desulfurization catalyst shown below as Catalyst 1, and the third catalyst bed contained a demetalization catalyst shown below as Catalyst 1. The desulfurization catalyst shown below is contained as catalyst 0.

In the three remaining experiments, the three catalyst beds were catalyst 1 and catalyst 0.
or only catalyst 1 or catalyst 0.

In the desulfurization experiment, the initial temperature was 360℃, 5℃, and the space velocity was 0.7k9.
/1/h, gas speed 60 states IH2/k9, hydrogen partial pressure 10
It is carried out at 0 or 150 bar. To produce a product with a constant sulfur content, the temperature must be gradually increased during the experiment. The desulfurization experiment is terminated when a temperature of 420 qo is applied to obtain a product with the desired sulfur content.

Demetallization is carried out at a constant temperature of 42,000 °C and hydrogen partial pressure and gas velocity applied for desulfurization.

In the case of demetalization prior to desulfurization, the space velocity of the entire catalyst system is 0.
．． The amount is 7×9 no/h. The catalyst was applied in sulfide type.

Desulfurization catalysts A and D have already been described in Example 1. The composition and properties of demetalization catalysts 1, 11 and 40 are given in Table C. Information regarding the production of Catalysts 1 and 11 is given in the Examples of Tokukan Sho 49-44004, which describes the production of these catalysts in detail. Catalyst 40 is a demetallizing catalyst within the scope of Tokubatsu Sho 49-44004. This catalyst is produced by soaking an alumina support in an aqueous solution containing vanadium oxalate and nickel nitrate, and then drying and straining the composition. Of the two residual oils used in the experiments, oil D has already been described in Example 1.

Oil F is described below. Experimental results are given in Table D.

Oil F is a total vanadium oil with a nickel content of 41 w and a sulfur content of 2.0% w. This oil is obtained as a residual oil from the atmospheric distillation of Caribbean crude oil.

Table 0 Table D Among the experiments in Table ○, only the experiment XW-X value is a demetalization/desulfurization experiment corresponding to the "improved method of the present invention".

Other experiments are for comparison. In the -X leg of Experiment

Catalyst combinations applicable to experiments A comparison of the lifespans of /0 clearly shows that the catalyst lifespan is longer when the combination of catalysts corresponding to the "improved method of the present invention" is applied. Appropriate Catalyst Combination 1/0' Experiment XK
(and this experiment is within the scope of this patent application), but the catalyst 0 quotient p/(d) of 0.9 is too small to satisfy the conditions of "improved method of this invention".

Experiments XW'-XK' are also experiments that fall within the scope of this patent application. Experiments XW', XW'' and X... in Table D are the same as experiments XK', XK'' and K''
, XW' and XN'' are the same.

Claims (1)

[Claims] 1. A method for catalytic hydrodesulfurization of residual hydrocarbon oil containing vanadium and nickel without recharging a catalyst, comprising:
The hydrocarbon oil is continuously contacted with catalyst I and catalyst II, and each catalyst in the combination consisting of catalyst I and catalyst II has a total pore volume of 0.30 ml/g or more and a diameter of 1.
The pore volume occupied by pores of 00 nm or more is 10% or less of the total pore volume, and the method is characterized by the following: (a) The specific average pore diameter (p
) and the specific average particle diameter (d) are their quotient p/(d)^0^. ^
9 is the following condition: 0.6×10^-^4×(P_H_2)
^2≦[p/(d)^0^. ^9] Catalyst II≦3+6×1
(b) When the combination of catalyst I and catalyst II consists of two catalysts, p and d of catalyst I are the quotient p /(d
)＾0＾． ^9 is the following condition: 1.2 x [p/(d)^0^. ＾9〕Catalyst II≦[p/(
d) ^0^. ＾9〕Catalyst I≦5＋30×10＾−＾4×
(P_H_2)^2. On the other hand, if the combination of catalyst I and catalyst II consists of more than two catalysts, [p/(d)^0^. ＾9] The above conditions regarding catalyst I are such that p/(d
)＾0＾． The average p/(d) of catalyst I obtained as a weighted average of the values of ^9. (c) apply to ＾9;
The proportion occupied by catalyst II of the total catalyst volume (volume % of catalyst II) is between 10% and 90% and under the following conditions: 40 x ((S_F - S_P) / (S_F) x 10
0)^2×(P_H_2)^-^2≦Capacity% of catalyst II≦
300×((S_F-S_P)/(S_F)×100)
and (d) Catalyst I and Catalyst II. If the combination consists of more than two catalysts, p and d of each catalyst of which catalyst I is made up
is the quotient p/(d)^0^. for each of these catalysts. ^9 is [p/(d)^0^. ^9] be larger than catalyst II (p: nm, d: mm, P_H_2: bar, S_P and S_F are weight %). 2. A method for catalytic hydrodesulfurization of vanadium and nickel-containing residual hydrocarbon oil without recharging the catalyst, comprising:
The hydrocarbon oil is brought into continuous contact with a single catalyst I and a single catalyst II, wherein these catalysts meet the following conditions: (a)
Both catalysts have a total pore volume of 0.30 ml/g or more, and the percentage (v) of the pore volume occupied by pores with a diameter of 100 nm or more relative to the total pore volume is 10 or less: (b ) Specific average pore size (p) and specific average particle size (p) of catalyst II
d) is its quotient p/(d)^0^. ^9 is the next condition: 0
．． 6×10^-^4×(P_H_2)^2≦[p/(d
)＾0＾． ＾9] Catalyst II≦3+6×10＾-＾4×(P
_H_2) It must be something that satisfies ^2, (c)
The proportion of catalyst II in the total catalyst volume of catalysts I and II (capacity % of catalyst II) is between 10% and 90%, and the following conditions: 40 × ((S_F−S_P)/(S_F) × 1
00)^2×(P_H_2)^-^2≦Capacity% of catalyst II
≦300×((S_F−S_P)/(S_F)×100
)^2×(P_H_2)^-^2, where S_F is the sulfur content of the feedstock and S_P is the desired sulfur content of the desulfurization product. ) (p: nm, d: mm, P_H_2 : Bar, S_P
and S_F: weight %), the following conditions are met and the demetalization catalyst is
The method is characterized in that catalytic hydrodemetallization is carried out using The conditions are met: a the catalyst consists of one or more metals with hydrogenation activity on the support, b p/d>3.5-0.02v, c the total pore volume is greater than 0.40 ml/g , d the specific surface area is greater than 100 m^2/g, but the quotient p
/d is greater than 3.5-0.02v and at most 10
If the catalyst has p and d such that -0.15v,
The catalyst must further meet the following conditions: e nitrogen pore volume greater than 0.60 ml/g, f
Specific surface area is greater than 150 m^2/g, and g p
is larger than 5 nm; c. Catalyst 0 has a larger total pore volume than Catalyst I;
D. p, d and v of catalyst 0 and catalyst I are under the following conditions: [p
/(d)^0^. ^9] Catalyst 0>1.2×{[p/(d
)＾0＾． ^9] Catalyst I-0.8 (v_0-v_1)}
and e) The proportion occupied by catalyst 0 of the total catalyst volume of catalysts 0, I and II is at least 10% by volume.