JP2547115C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]   The present invention relates to a composition of a catalyst used for hydrotreating a hydrocarbon oil, in particular, a particle size.
And zeolite having a specified particle size distribution and alumina or aluminum having a specific pore distribution
A mixture of minerals and other materials is used as a carrier, and an active metal is supported on the mixture with good dispersibility.
Hydrolytic treatment catalyst composition and hydrotreating method using the catalyst composition
. [Conventional technology]   Conventionally, in general, in a method for hydrotreating a hydrocarbon oil, a refractory oxide carrier is used. One or more kinds of gold selected from the group of the 6B group of the periodic table and the 8th group of the periodic table
A catalyst supporting a genus is used.   For example, cobalt-molybdenum or nickel-molybdenum supported on alumina
Hydrogenation catalysts such as den-based catalysts are widely used.
Demetallization, deasphaltenation, hydrocracking, etc. are implemented for various purposes.
You.   The performance required of such a hydrotreating catalyst is high activity and its performance is high.
It is how long it can be maintained.   To do so, first, the active metal should be dispersed on the carrier in a large amount and highly highly.
Second, the metal contained in the raw hydrocarbon oil,
Gas for catalytic poisons with macromolecular structures of asphaltenes, sulfur and nitrogen
How to maintain the card function.   The first measure is to use a carrier having a high specific surface area,
As a countermeasure, the pore distribution of the catalyst is controlled, and
2) It has been proposed to add macropores to increase the diffusivity inside the catalyst.
It is currently being practiced.   Furthermore, in recent years, hydrorefining processes, especially processing of residual oils containing asphalt
In the case of a hydrorefining process, the feedstock is heavier, but demand is lighter and higher.
There is a growing demand for higher quality, and as a hydrodesulfurization catalyst,
There has been a demand for a catalyst that decomposes fuel oil or that has a high denitrification rate.
ing.   Here, when comparing the reactivity of desulfurization and decomposition, the decomposition reaction generally does not easily proceed
Hydrodesulfurization and hydrocracking reactions are competitively progressing on the same active site
Therefore, the relative reaction activity ratio between desulfurization activity and decomposition activity is almost constant in various reaction temperature ranges.
Indicates a value.   That is, under an operation in which the desulfurization rate, which is relatively high, is kept constant at 90%,
The decomposition rate also shows a substantially constant value, and it is not possible to expect any further decomposition activity.   Therefore, as a countermeasure, silica that has no desulfurization activity but exhibits decomposition activity,
By adding acid properties such as titania, the amount of acid increases at the same desulfurization rate Accordingly, there has been provided a catalyst for improving the decomposition activity. [Problems to be solved by the invention]   By the way, the conventionally provided catalyst has the following problems.   As a physical property of the catalyst, reducing the average pore diameter to obtain a high surface area is an activity.
This is good in increasing the dispersibility of the conductive metal. However, the metal of the macromolecule that is a catalyst poison
The small pores are easily closed by the components and the like.   Conversely, increasing the average pore diameter allows metal to accumulate inside the pores.
This is preferable in that respect. However, the surface area is small and the dispersibility of the active metal is poor.   Thus, it is extremely important to determine what average pore size should be used for activity and life.
Is a difficult problem.   On the other hand, as a countermeasure for hydroprocessing with a decomposition reaction,
As mentioned, addition of acid properties such as silica, titania and the like can be mentioned. But general
Metal oxides that form acidic sites when mixed with alumina
Since the affinity for Mo metal is weak, the amount of Mo metal increases with the increase in the amount of acid property added.
It has the disadvantage that the dispersibility is reduced and the desulfurization performance of the catalyst is reduced.   In addition, even if a metal oxide that forms an acidic point is added, particularly, the feed oil has a wide boiling point fraction.
In the case where the oil is composed of a heavy oil component having a large molecular weight or molecular weight, for example,
AR), there is a demand for lightening or whitening by decomposition.
There is a problem that it is extremely difficult to add.   Atmospheric pressure residual oil (AR) contains more than 50% of a vacuum residual oil (VR) fraction in composition.
This fraction undergoes hydrogenolysis and acidolysis on Mo metal or on acidic sites.
As it progresses, heavy components are sequentially decomposed and lightening proceeds.   However, in this case, the decomposition reaction can be easily lightened as much as the LGO fraction.
Although it does not proceed, it is mostly decomposed even if it is decomposed, to only about the VGO fraction of the primary product. For example,
When treating the vacuum residua, it is almost limited to decomposition products up to the VGO fraction. this child
What is once hydrogenolyzed (primary product) is extremely reactive thereafter
Means to reduce the yield of the desired light fraction selectively from heavy oil.
Waiting is very difficult with conventional catalysts.   The problem to be solved by the present invention is that the desulfurization activity is excellent and the decomposition activity is high. In other words, it is to develop a hydrotreating catalyst having both functions of desulfurization and decomposition.   More specifically, first, a sufficient and optimal average to increase the dispersibility of the active metal.
The purpose is to find the pore size and pore distribution. Second, it reduces the dispersibility of the active metal
No matter how acidic spots are given on the catalyst, and those that have been hydrogenated once more selectively
To provide a function of effectively obtaining a light fraction.   A further challenge is, of course, to provide the above catalysts with a longer service life in terms of economy.
And to provide high activity. [Means for solving the problem]   The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a specific flat
Acidic properties of alumina or alumina-containing carrier with uniform pore size and pore distribution
It is important to use a specific amount of zeolite having a specific particle size and particle distribution.
It is effective to solve the above problems, and when using this catalyst,
In a hydrotreating method consisting of two or more reaction zones,
Then, it is found that the activity can be stably maintained for a long period of time, and it is necessary to complete the present invention.
Reached.   That is, the present invention (1) 2 to 35% by weight of zeolite as carrier, alumina or alumina-containing material
65 to 98% by weight, and at least one Group 6B metal of the periodic table or
A hydrogenation active metal component of a metal belonging to Group 8 of the periodic table, (A) The characteristics of the alumina or alumina-containing material are as follows: Average pore diameter70-100Å, Pore volume having diameter of ± 10 ° of average pore diameter is alumina or alumina-containing
Of the total pore volume of the product85~ 98%, (B) The properties of the zeolite are Average particle size of 6 μm or less, Those having a particle diameter of 6 μm or less account for 70 to 98% of all particles of the zeolite, (C) The metal of Group 6B of the Periodic Table as an oxide is 2 to 30% by weight based on the weight of the catalyst.
0.5 to 20% by weight of the Group VIII metal as an oxide with respect to the catalyst, A hydrotreating catalyst composition for hydrocarbon oils, and (2) In the method for hydrotreating a hydrocarbon oil comprising two or more reaction zones,
Characterized in that the above-mentioned catalyst composition is used in a reaction zone after the reaction zone.
The gist is a method for hydrotreating hydrocarbon oil.   The zeolite that is a part of the support of the catalyst of the present invention is a natural or synthetic zeolite.
For example, faujasite X-type zeolite, faujasai
Y-type zeolite (hereinafter referred to as “Y zeolite”), chapasite-type zeolite
Mordenite zeolite, so-called ZSM zeolite containing organic cations (
As ZSM zeolite, ZSM-4, ZSM-5, ZSM-8, ZSM-
11, ZSM-12, ZSM-20, ZSM-21, ZSM-23, ZSM-3
4, ZSM-35, ZSM-38, and ZSM-43).
, Y zeolite, stabilized Y zeolite or ZSM-5 is preferred.   The atomic ratio Si / Al of the silicon element to the aluminum element in the zeolite is about 1
The above are preferred.   The cationic species of zeolite are ammonium or hydrogen type and zeolite.
In order to control the acid properties of the alkali metal,
ON, polyvalent metal ions of Group 8 noble metal ions such as magnesium, lanthanum
Ion-exchanged with metal ions such as platinum, ruthenium and palladium.
New   Alkali metal ions such as sodium in zeolites have a high content
Normally, the content is reduced to about 0.5% by weight or less with respect to the zeolite.
Is preferred.   As the above-mentioned Y zeolite or stabilized Y zeolite, use a known one.
Can be.   Y zeolite has basically the same crystal structure as natural faujasite
When expressed as an oxide, it can be expressed as the following composition formula. 0.7-1.1R_{2 / m}O ・ Al_TwoO_Three・ 3-5SiO_Two・ 7-9H_TwoO (Where R is Na, K, another alkali metal ion or alkaline earth metal ion
And m is its valence. )   Stabilized Y zeolites are described, for example, in U.S. Pat. Nos. 3,293,192; No. 402,996 are preferably used.   The stabilized Y zeolite has a high crystallinity by performing steam treatment at high temperature several times.
Shows remarkable resistance to deterioration.   The stabilized Y zeolite has R_{2 / m}O content of about 4% by weight or less, preferably about 1%
At% or less, the unit cell size is about 24.5 °.   The stabilized Y zeolite has an atomic ratio of Si / Al of about 3 to 7 or more.
Y zeolite.   These Y zeolites or stabilized Y zeolites are alkali metals or alkalis.
If the amount of lithium earth metal oxide is high, ion exchange is performed to
Potassium metal or alkaline earth metal oxide is removed before use.   ZSM-5 is disclosed in U.S. Patent Nos. 3,894,106 and 3,894,107.
No. 3,928,483; British Patent No. 1,402,981;
Those obtained by the synthesis method described in Japanese Patent No. 67522 are preferably used.   These zeolites have an average particle size of about 6 μm or less, preferably about 5 μm or less.
And more preferably about 4.5 μm or less.   In addition, this zeolite has a particle diameter of 6 μm or less with respect to all the zeolite particles.
About 70-98%, preferably about 75-98%, more preferably
About 80-98%.   If the average particle size is too large or the content of the large particle size is large,
During the preparation of the support, the amount of water absorbed and the crystallinity of the alumina and zeolite differ, and
The alumina and zeolite have different shrinkage rates during thermal calcination, and have a new ratio as pores in the support.
Relatively large meso or macropores occur. These large pores have a large surface area
Not only reduces the oil content, but also becomes a catalyst poison when treating residual oil.
Facilitates the internal diffusion of components, which in turn reduces desulfurization, denitrification and decomposition activity
The Rukoto.   In addition, the particle size of the zeolite in the present invention was measured by an electron micrograph.   The proportion of zeolite in the carrier is about 2 to 35% by weight, preferably about 5 to 3%.
0% by weight, more preferably about 7 to 25% by weight. The proportion of zeolite
If the amount is too small, the acid amount of the catalyst becomes small, and the decomposition activity and the dispersibility of the active metal are improved. If the ratio is too short, the hydrodesulfurization reaction will not be sufficient
.   As the alumina that is a part of the support, γ-alumina, χ-alumina, or η-alumina
Any one of alumina or a mixture thereof is suitable.   The alumina-containing material is obtained by blending a carrier substance in addition to alumina.
Composition, for example, silica, magnesia, calcium oxide, zirconium
A, one kind of refractory inorganic oxides other than alumina, such as titania, boria, hafnia, etc.
Can be mixed in the alumina.   This alumina or alumina-containing material has an average pore diameter measured by a mercury intrusion method.
Is about70-100、, and those having a pore diameter of ± 10Å of the average pore diameter are alumina or
Is about the total volume of the alumina content85~ 98%.   Such an average pore diameter and pore distribution are suitable for hydrotreatment of hydrocarbon oils, especially hydrodesulfurization.
The reasons for the significant effect on activity and maintenance of activity in
Although there is no catalyst poison such as asphalt, resin and metal-containing compounds in the feedstock,
When attached to the catalyst surface, if the pore diameter is too small, the pores will be closed and the active sites of the catalyst
Is completely isolated.   On the other hand, the pore diameter is increased in the above specific range, and the pore size is increased as described above.
The catalyst poison adheres to the surface of the catalyst by maintaining a sharp pore distribution.
Does not completely block the pores and activates the hydrocarbon molecules and sulfur that subsequently reach the catalyst.
Can be presumed to be close to
Wear.   The proportion of alumina or alumina-containing material in the carrier is about 65 to 98% by weight, preferably
It is preferably about 70-95% by weight, more preferably about 75-93% by weight. Percentage
If the amount is too small, it is difficult to mold, and the desulfurization activity becomes poor.   The "total pore volume" of the alumina or alumina-containing material in the present invention actually exists
Since it is impossible to measure the entire volume of the pores, it is necessary to use a mercury porosimeter.
225Kg / cm^TwoAll pores with mercury absorption at G (60000 psig)
Refers to what is regarded as volume.   Further, the value of the "average pore diameter" of the alumina or alumina-containing material in the present invention Describes the relationship between the pressure of the mercury porosimeter and the amount of mercury absorbed by the catalyst from 0 to 4225.
Kg / cm^Two· Determined for G, 4225Kg / cm^Two・ 1/3 of the absorption amount in G
The average pore diameter was determined from the pressure when the absorption amount of No. 2 was indicated. In addition,
In light, the contact angle of mercury was 130 ° and the surface tension was 470 dyne / cm.
Was. The relationship between mercury porosimeter pressure and the corresponding pore size is already known.
You.   Next, a method for preparing the catalyst of the present invention will be described.   First, dry alumina or a gel containing alumina is prepared (first step).   Raw materials used include water-soluble compounds, such as water-soluble acidic aluminum compounds
Or a water-soluble alkaline aluminum compound, specifically, a sulfate of aluminum
, Chlorides, nitrates, alkali metal aluminates, aluminum alkoxides,
Other inorganic and organic salts can be used. In addition, water of metal components other than aluminum
The soluble compound may be added to the raw material solution as described above. In a concrete form,
Aqueous acid aluminum solution (concentration about 0.3-2 mol) and alkali aluminate solution
To a pH of about 6.0 to 11.0, preferably about 8.0.
To form a hydrogel or hydrosol in the range of
This suspension is added to the suspension for about 5 hours while appropriately adjusting the pH by appropriately adding near water, nitric acid or acetic acid.
Heat to 0-90 ° C. and hold for at least 2 hours. The precipitate is then filtered
The solution is separated and washed with ammonium carbonate and water to remove impurity ions.   The preparation of the alumina gel described here is based on the assumption that
In order to obtain the average pore diameter and pore distribution required for a physical catalyst, alumina or
Regulates preparation conditions such as temperature and time for precipitation and ripening of hydrates of alumina.
Perform while adjusting.   Next, a zeolite is prepared (second step).   Zeolites are commercially available or prepared by known methods.   If the particle size of a commercial product is large, it can be used by grinding.
You. When prepared by a known method, unless a binder is used after preparation,
Many are included in the range.   Thereafter, the alumina or alumina-containing material obtained in the first step and zeolite are mixed. A carrier is prepared by mixing (third step).   This mixing method is not particularly specified, and alumina or alumina-containing gel
Method of mixing zeolite (wet method) when preparing zirconia, dried alumina gel and zeolite
Kneading light powder (dry method), immersing zeolite in alumina compound solution
After immersion, an appropriate amount of a basic substance is added to form an alumina gel or an alumina-containing substance gel.
Methods such as deposition on zeolites can be used.   For example, in the dry process, alumina or a mixture of alumina-containing material and zeolite is used
Knead with a hopper. At that time, adjust the water content appropriately until the water content becomes moldable
You. Next, it is molded into a desired shape by an extrusion molding machine. Molding is performed according to the desired average pore size.
This is performed while adjusting the molding pressure in order to obtain the pore distribution. Molded product is about 100-14
Dry at 0 ° C for several hours, and bake at about 200-700 ° C for several hours to finish the carrier
.   The hydrogenation active metal component is supported on the carrier thus molded (fourth step)
).   The method for supporting the hydrogenation-active metal component on the carrier is not particularly specified.
Various methods are adopted. For example, in the impregnation method, the hydrogenation active metal component
Impregnation method of spraying a solution in which is dissolved on carrier particles, in a relatively large amount of impregnation solution
An immersion impregnation method of immersion and a multi-stage impregnation method of repeatedly contacting are used.   When two or more hydrogenation-active metal components are used, groups 6B and 8 of the periodic table may be used.
May be carried first or simultaneously.   Group 6B metals of the periodic table to be supported are chromium, molybdenum, tungsten and the like.
One or more selected from the group of Group 6B metals are selected and used. Preferred
Alternatively, molybdenum or tungsten may be used alone or in combination. Also desired
It is also possible to add a third metal according to.   The metals of Group VIII of the Periodic Table to be supported are iron, cobalt, nickel, and palladium.
Group 8 metals such as metals, platinum, osmium, iridium, ruthenium, rhodium
One or two or more selected from the following are selected and used. Preferably, nickel or
Is cobalt alone or a combination of both.   The Group 6B and Group 8 hydrogenation active metal components include oxides and / or sulfides. It is preferable to carry it as it is.   The amount of such a hydrogenation-active metal component supported is 6B
The group metal is about 2-30% by weight, preferably about 7-25% by weight, more preferably about 1% by weight.
0 to 20% by weight, and the Group VIII metal is about 0.5 to 20% by weight, preferably about 1 to 20% by weight.
It is 12% by weight, more preferably about 2-8% by weight.   If the Group 6B metal is less than 2% by weight, the desired activity cannot be obtained.
If the amount exceeds the above range, the dispersibility is reduced, and at the same time, the cocatalytic effect of the Group VIII metal is not exhibited.   On the other hand, if the content of the Group VIII metal is less than 0.5% by weight, sufficient effects cannot be obtained.
If it exceeds 0% by weight, the amount of free hydrogenation-active metal components not bound to the carrier increases.   The carrier supporting the hydrogenation active metal component is separated from the impregnation solution, washed with water, and dried.
And firing. Drying and firing conditions may be the same as the conditions for the carrier described above.
.   Further, in addition to the above, the catalyst of the present invention has a specific surface area of about 200 to 400 m.^Two/ G,
The total pore volume is about 0.4 to 0.9 ml / g, and the bulk density is about 0.5 to 1.0 g / m
1, The side fracture strength is about 0.8-3.5Kg / mm, and the hydrocarbon oil has good
A catalyst for hydroprocessing is realized.   Table 1 shows the physical properties of the catalyst of the present invention described in detail above.   The above-mentioned catalyst of the present invention has low activity degradation and low severity reaction conditions,
A high desulfurization rate can be achieved even at a pressure.   When performing the hydrotreating, the catalyst of the present invention may be any of a fixed bed, a fluidized bed and a moving bed.
These types can be used, but fixed bed reactors should be used from the standpoint of equipment or operation.
Is preferred.   In the hydrotreating method of the present invention, for example, two or more reaction towers are connected.
When the hydrogenation treatment is performed in a plurality of reaction zones in combination, the above-described catalyst of the present invention is used in the second step.
By using it in the reaction zone after the first reaction tower, a high desulfurization rate is achieved.   In particular, when processing heavy oil containing asphalt etc., the purpose is to remove metals
The pretreatment catalyst (first hydrotreating catalyst) is used in the pre-stage (first stage) reaction zone,
By using the invented catalyst in the reaction zone of the second and subsequent stages, high desorption over a long period of time is achieved.
It is possible to maintain a high sulfur ratio and a decomposition ratio of a fraction of LGO or less.   The catalyst of the present invention is preferably subjected to pre-sulfurization prior to use in the method of the present invention.
No. Presulfurization can be performed in-situ in the reaction tower. That is, the present invention
The catalyst is mixed with a sulfur-containing hydrocarbon oil (for example, a sulfur-containing distillate) at a temperature of about 150 to 400 ° C.
Pressure (total pressure) about 15-150Kg / cm^Two, Liquid space velocity about 0.3-8.0Hr^-1
At about 50-1500 l / l in the presence of a hydrogen-containing gas.
After finishing the process, the above sulfur-containing distillate is switched to a feedstock oil (sulfur-containing hydrocarbon oil),
The operation is started by setting the operation conditions suitable for desulfurization of the steel.   As a method for the sulfuration treatment of the catalyst of the present invention, in addition to the above-described methods, hydrogen sulfide,
Either contact other sulfur compounds directly with the catalyst or
A method in which a substance added to an appropriate distillate is brought into contact with a catalyst or the like can also be applied.   The hydrocarbon oil in the present invention is obtained by atmospheric distillation or vacuum distillation of crude oil.
Light fractions, atmospheric distillation residues and vacuum distillation residues mean, of course, coker gas oil, solvents
Includes deasphalted oil, tar sands oil, shale oil, and coal liquefied oil.   The hydrotreating conditions in the method of the present invention depend on the type of feed oil, the desulfurization rate, etc.
The temperature can be appropriately selected, but the temperature is about 320 to 450 ° C and the pressure is about 15 to 200K.
g / cm^Two, A hydrogen-containing gas ratio of about 50 to 1500 l / l, a liquid hourly space velocity of about 0.1 to 1
5Hr^-1It is preferable that The hydrogen concentration in the hydrogen-containing gas Is preferably in the range of about 60 to 100%. [Action]   In the catalyst of the present invention, the support is composed of zeolite and alumina or an alumina-containing material.
Therefore, silica and oxygen atoms, the main constituent elements of zeolite, are converted to aluminum.
Chemically forms with the aluminum atom on the metal to form a new acidic site,
To improve the dispersibility of the reactive metal component.   In the method of the present invention, such a catalyst of the present invention is converted into a hydrocarbon comprising a plurality of reaction zones.
By using it after the second reaction zone of oil hydrotreatment,
Depending on the dispersibility of the components, high desulfurization rates and decomposition rates can be obtained.   At this time, zeolite is required for cracking reaction of heavy oil such as residual oil under normal pressure or residual pressure under reduced pressure.
Hydrogenolysis in the former reaction zone (first reaction zone)
The resulting product, the VGO fraction, can be selectively cracked again.   That is, the molecules heavier than the VGO fraction have a molecular diameter even if the reactivity is high.
It is too large to reach the acidic point of the zeolite. On the other hand, the first reaction area
Primary hydrocracking products that have already reacted in the
The acid point of the site can be reached, and the acid point can be selectively used.   As a result, in the method of the present invention using the catalyst of the present invention, the conventional alumina alone or silica is used.
A catalyst using an alumina-containing carrier such as silica-alumina and titania-alumina is used.
The yield of light oil such as LGO can be greatly improved as compared with the conventional treatment method used.   In addition, in a conventional catalyst, when mixing alumina and zeolite, aluminum is used.
Because zeolite or silica is more hydrophobic than alumina, alumina and zeolite
Are different in moisture content (adsorbed water ratio, water absorption ratio, etc.)
New meso and macro pores are generated, and in some cases,
And many problems, such as cracks, were pointed out.   In the catalyst of the present invention, in order to minimize such a difference in shrinkage, zeolite
Not only the content but also the average particle size is reduced to 6 μm or less,
The restriction that the particle size of μm or less should be 70-98% of the total zeolite particles should be added.
This suppresses the formation of meso and macropores during firing.   As a result, the amount of zeolite itself increased, the dispersibility of zeolite improved, Enables new acidic sites to be increased by chemical bonding of mina with aluminum atoms
.   Further, in the catalyst of the present invention, as the alumina or alumina-containing material, the average pore
Diameter70-100細孔 The pore volume with a diameter of ± 10
Of alumina or alumina content85~ 98% sharp pore distribution
From catalyst poisons such as asphalt, resin, and metal-containing compounds in the feedstock
Prevents pores from being clogged when attached to the catalyst surface and activates hydrocarbon molecules and sulfur
Enhances the approach to and demonstrates high performance.   As described above, the catalyst of the present invention and the method of the present invention have remarkably high activity in both desulfurization and decomposition.
Useful hydrogenation process using the catalyst composition is a useful catalyst composition for improving
It is a logical method.   The “hydrotreating” in the present invention means, as described above, hydrocarbon oil and water.
Treatment by contact with hydrogen, comparatively less severe hydrorefining of reaction conditions, comparison
Refining, hydroisomerization, hydrodealkylation with some highly severe decomposition reactions
And the reaction of hydrocarbon oils in the presence of other hydrogen.   For example, hydrodesulfurization, hydrodenitrification of distillate and residual oil of atmospheric distillation or vacuum distillation
Including hydrogen and hydrogenolysis, and hydrogen in kerosene fraction, gas oil fraction, wax and lubricating oil fraction
And purification. 〔Example〕   Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.   The catalysts obtained in Examples 1 to 8 and Comparative Examples 1 to 3 described below were hydrodehydrogenated under the following conditions.
Evaluated by the relative activity evaluation test for sulfur decomposition, and the results were
Shown. Relative activity evaluation test for hydrodesulfurization / decomposition:   For catalysts A to H (Example) and catalysts Q to S (Comparative Example),
The relative activity of hydrodesulfurization / decomposition reaction for heavy oil was measured using a fixed bed type
On the 25th day (using the reaction tube, the product has a low sulfur content at the beginning of the reaction,
In order to stabilize the increase, the day was set to 25 days. )) The residual sulfur content (% by weight) of the reaction product
The desulfurization rate (%) and the decomposition rate (%) of the residual oil under normal pressure were evaluated.   The cracking rate is the rate of decrease after the reaction treatment of components with higher boiling points than the predetermined cut temperature in the feedstock.
It was defined as the decomposition rate and was calculated using the following equation.   The properties and test conditions of the directly removed heavy oil are as follows.   Properties of heavy oil (Arabian heavy direct removal heavy oil, AH-DDSP);     Sulfur content (% by weight) 0.62     Nitrogen content (% by weight) 0.15     Nickel (ppm) 12     Vanadium (ppm) 16   Test condition;     Reaction temperature (° C) 400     Reaction pressure (Kg / cm^Two・ G) 145     Liquid space velocity (Hr^-1) 0.2 Example 1 (Production method of catalyst A) (First step) Preparation of dried alumina gel;   6.4 liters of ion-exchanged water is placed in a 20 liter plastic container, and 1.89 kg of aluminum is added.
Sodium acid solution (Na_TwoO: 17.4%, Al_TwoO_Three: 22%)_Two
O_Three8.29 kg of a liquid containing 5% was prepared.   Next, 21 g of a 50% gluconic acid aqueous solution was added and stirred, and 8.4%
An aqueous solution of minium was added rapidly until a pH of 9.5 was reached. The amount added at this time is 8
. It was about 3 kg. The liquid temperature at the time of preparation was room temperature.   The white slurry-like preparation liquid was left to stand for one night, and then dehydrated with Nutsche.
The mixture was washed with water in an amount of 5 times the amount of the prepared solution with aqueous ammonia.   The alumina hydrate cake obtained in this manner is made of Al_TwoO_Three7.5-8 in concentration
%, Impurity Na_TwoO is 0.001%, SO_Four ^-2Was 0.00%. (Second step) Preparation of Y zeolite;   A commercially available Y zeolite (SK-41Na type, manufactured by Linde, USA) was used.   In use, crush Y zeolite to a particle size of about 2.5 μm and a particle size of 6 μm.
m or less particles were obtained at about 85% of the total Y zeolite particles. (Third step) Preparation of carrier;   10% by weight on a dry basis of the crystalline Y zeolite obtained in the second step based on the carrier
Until it reaches the water content that can be molded with a kneader.
It was kneaded well while drying.   Next, it was molded into a columnar shape having a diameter of 1/16 inch by an extrusion molding machine.   Molding is performed while adjusting the molding pressure to obtain the desired average pore diameter and pore distribution.
Was.   The molded pellets are dried at 120 ° C. for 3 hours and then fired at 450 ° C. for 3 hours.
Thus, a carrier was obtained. (4th step) loading of metal;   The molybdenum component [(N
H_Four)₆Mo₇O_{twenty four}・ 4H_TwoO] impregnated with an aqueous solution, dried at 120 ° C. in air,
It was baked at 450 ° C.   Next, the nickel component [Ni (NO_Three)_Three
・ 6H_TwoO] dipped again in an aqueous solution, dried in air at 120 ° C.,
Heat at a rate of 0 ° C / min, and further from 350 to 600 ° C at a rate of 5 ° C / min.
It was heated and then calcined at 600 ° C. for about 4 hours to obtain Catalyst A. Examples 2 to 4 (Preparation of Catalysts B to D)   Except that in the third step, Y zeolite was mixed at a dry ratio of 20% by weight.
In the same manner as in Example 1, catalyst B (Example 2) was obtained.   Furthermore, in the third step, Y zeolites having average particle diameters of 1.7 μm and 3.9 μm were used.
Catalyst C (Example 3) and Catalyst D (actual)
Example 4) was obtained.   Table 2 shows the composition of catalysts A, B, C, and D and the relative activity evaluation of desulfurization and decomposition. Example 5 (Preparation of catalyst E) (First step) Preparation of dried alumina-containing gel;   An aqueous solution of sodium hydroxide (NaOH 278 g, distilled water 2) was added to 2 liters of distilled water at room temperature.
l) and an aqueous solution of aluminum sulfate (396 g of aluminum sulfate, 1β of distilled water).
After that, the pH was adjusted to 8.5 to 9.2 with an aqueous sodium hydroxide solution or a nitric acid solution.
Thereafter, the mixture was heated to 85 ° C. and left to mature for about 5 hours.   Add sodium silicate solution (No. 3 water glass (SiO_Two35-38%, Na_TwoO
35.5 g (17-19%), 500 g of distilled water). At this time, the pH of the solution
The mixture was adjusted by adding a nitric acid solution to about 8.5, and aged at a liquid temperature of 85 ° C. for about 5 hours.
.   The resulting slurry is filtered off and the separated precipitate is reconstituted with a 2.0% ammonium carbonate solution.
After mudification, it was filtered again.   The above ammonium carbonate solution until the sodium concentration of the solution becomes 6 ppm or less.
, And then dehydrated and dried with a pressure filter.   In this way, silica gel is deposited on the alumina gel particles to form a gel cake.
Prepared.   The second to fourth steps were performed in the same manner as in Example 1 to obtain Catalyst E. Examples 6, 7 (Preparation of catalysts F and G)   In the first step, titanium chloride TiCl was used instead of water glass._Four31.1 g or boric acid
Except that 13.1 g of sodium was used, the same procedure as in Example 5 was carried out.
Same as Example 1 except that an aqueous solution of cobalt nitrate was used instead of the aqueous solution of nickel acid
Was performed in the manner described above.   The second and third steps were performed in the same manner as in Example 1 to obtain catalysts F and G. Example 8 (Preparation of catalyst H)   The first step was performed in the same manner as in Example 5, and the second and third steps were performed in the same manner as in Example 1. Fourth step (metal loading);   The carrier obtained through the first to third steps was added to the carrier so as to be 15% by weight in terms of oxide.
Impregnated with an aqueous solution of ammonium ribate to support the Mo component,
C., and calcined at 450.degree.   Next, nickel nitrate and cobalt nitrate were added so as to be 2.5% by weight in terms of oxides.
Immersed simultaneously in a mixed solution of
At a rate of 10 ° C./min, and further at a rate of 5 ° C./min from 350 to 600 ° C.
And then calcined at 600 ° C. for about 4 hours to obtain Catalyst H.   Table 3 shows the compositions of the catalysts E to H and the evaluation of the relative activities of desulfurization and decomposition. Comparative Example 1   Except that the second and third steps were omitted for use as a carrier of alumina alone,
In the same manner as in Example 1, catalyst Q was obtained. Comparative Example 2   In the third step, using the crystalline Y zeolite obtained in the second step as a carrier standard
Except for mixing at a dry ratio of 40% by weight, a method similar to that of Example 1 was used.
Then, catalyst R was obtained. Comparative Example 3   In the second step, commercially available Y zeolite is ground to a mean particle size of about 9.0 μm.
, Except that particles having a particle size of 6 μm or less obtained about 60% of the total Y zeolite particles.
In the same manner as in Example 1, catalyst S was obtained.   Table 4 shows the composition of the comparative catalysts Q to S and the relative activity evaluation of desulfurization and decomposition.   The catalysts obtained in Examples 9 to 14 and Comparative Example 1 described below were converted to hydrogen under the following conditions.
Evaluation of the relative activity of hydrodesulfurization and denitrification was conducted.
Show. Evaluation of relative activity of hydrodesulfurization and denitrification:   For each of Catalysts I to N (Example) and Catalyst Q (Comparative Example),
Relative activity of hydrodesulfurization / denitrification reaction for oil is fixed bed type reaction with inner diameter 14mmφ
Using a tube, on the 25th day (the product has a low sulfur content at the beginning of the reaction, but increases with the number of days)
In order to stabilize, it was set to 25 days. )), The residual sulfur content (% by weight) of the reaction product
The desulfurization rate (%) and the denitrification rate (%) determined from the residual nitrogen content (% by weight) were evaluated.   The properties and test conditions of the vacuum gas oil are as follows.   Properties of vacuum gas oil (Arabian light vacuum gas oil, AL-VGO);     Sulfur content (% by weight) 2.45     Nitrogen (% by weight) 0.084   Test condition;     Reaction temperature (° C) 350     Reaction pressure (Kg / cm^Two・ G) 50     Liquid space velocity (Hr^-2) 0.4 Example 9 (Preparation of catalyst I)   The first, third, and fourth steps were performed in the same manner as in Example 1 (catalyst A).
Then, Catalyst I was prepared by the following method. (2nd step) Preparation of metal ion exchange type zeolite;   Using a commercially available Y zeolite (SK-41Na type manufactured by Linde, USA) as follows:
Prepared.   The ion exchange of zeolite is carried out first with NH_FourAnd then metal ion exchange
Was carried out.   First, NH_FourPreparation of type Y zeolite was carried out in a 1000 ml Erlenmeyer flask.
Take 150 g of Na-Y zeolite and add 1N-NH_Four750m of Cl aqueous solution
About 1 liter was added and stirred at 70 ° C. for 3 hours. After that, the exchange liquid is decanted.
And a new exchange solution was added. Repeat this operation six times, and finally wash thoroughly, The drying was performed by filtration (Step A).   Next, NH_FourMetal ion exchange of type Y zeolite is performed using a 1000 ml triangular
150 g of NH4 type Y zeolite was placed in the flask, and a 1N aqueous cation solution (1 N
-LaCl_Three), Add about 750 ml, and attach a reflux condenser.
It was immersed in a regulated water bath. Exchange liquid is removed by decantation about every 3 hours
New replacement fluid was added. This operation is repeated 10 times, and finally, it is thoroughly washed.
This was performed by overdrying (step B).   By the step B, the lanthanum ion exchange rate was 76.1%. Examples 10 to 14 (Preparation of catalysts J to N)   1N-LaCl of the second step_ThreeInstead of the aqueous solution, 0.01N-Pt (NH_Three)
_FourCl_TwoAqueous solution, 0.015 N-Ru (NH_Three)₆Cl_ThreeAqueous solution, 0.01N- [P
d (NH_Three)_FourCl_TwoPerformed in the same manner as in Example 9, except that an aqueous solution was used,
Catalyst J (Example 10), catalyst K (Example 11), and catalyst L (Example 12) were obtained.
The ion exchange rates were 72.6%, 63.1%, and 66.8%, respectively.   Further, instead of Y zeolite in the third step, ZSM-5, mordenite was used.
Catalyst M (Example 13) and Catalyst N (actual)
Example 14) was obtained.   Table 5 shows the compositions of catalysts J to N and comparative catalyst Q, and the relative activities of desulfurization and denitrification.
Show.   As is clear from Tables 2 to 5, the catalyst A of the present invention (Example 1) was a zeolite.
Effect of increasing desulfurization activity and decomposition activity as compared to Comparative Catalyst Q (Comparative Example 1) containing no
It is found that there is a fruit and the denitrification activity is also improved.   Regarding their catalytic activities, when treating reduced-pressure gas oil as compared with direct removal heavy oil,
In this case, it can be seen that the effect of containing zeolite is more remarkably recognized.   Furthermore, for catalysts I to L obtained by ion exchange of various metals, the effect of Zeola on the activity
It can be seen that good results that further promote the effect of the inclusion of iron are obtained.   Further, catalysts M and N using ZSM-5 and mordenite instead of Y zeolite (
Similar effects were observed in Examples 13 and 14).
It turns out that it shows the characteristic excellent in.   The catalyst obtained in Examples 15 and 16 and Comparative Examples 4 to 6 described below was hydrogen under the following conditions.
Evaluation of the relative activity of hydrodesulfurization and the durability test for metal deposition
Shown in the examples. Evaluation test for relative activity of hydrodesulfurization:   About catalysts O and P (Example) and catalysts T to V (Comparative Example),
Relative activity of hydrodesulfurization against residual pressure using a fixed-bed reactor with an inner diameter of 14 mm
On the 20th day (the product has a low sulfur content at the beginning of the reaction, but it increases and stabilizes with the number of days)
Therefore, day 20 was set. ) The residual sulfur content of the reaction product (% By weight) determined from the (% by weight).   The properties and test conditions of the normal pressure residual oil are as follows.   Properties of atmospheric residual oil (Arabian heavy atmospheric residual oil, AH-AR);     Sulfur content (% by weight) 4.3     Nickel content (ppm) 30     Vanadium (ppm) 96   Test condition;     Reaction temperature (° C) 390     Reaction pressure (Kg / cm^Two・ G) 105     Liquid space velocity (Hr^-1) 1.0 Durability test for metal:   Instead of Arabian heavy atmospheric resid, heavy oil with ultra-high metal content (Boscan Oil) was tested for durability against metal deposition.   The durability was evaluated based on the number of days (desired) that the desulfurization rate in the produced oil was able to withstand before dropping to 20% (
The life was evaluated by the amount of deposited metal.   Properties of heavy oil (Boscan crude);     Specific gravity (15/4 ° C) 0.9994     Sulfur content (% by weight) 4.91     Nitrogen content (% by weight) 0.57     Viscosity (50 ° C.) (cSt) 5315     Pour point (° C) +10.0     Nickel (ppm) 110     Vanadium (ppm) 1200     Residual carbon (% by weight) 16.4     Asphaltene (weight%) 12.9   Reaction conditions;     Reaction temperature (° C) 395     Reaction pressure (Kg / cm^Two・ G) 105     Liquid space velocity (Hr^-1) 0.5     Hydrogen / oil ratio (Nm^Three/ Kl) 1780 Examples 15 and 16 (Preparation of catalysts O and P)   The aging time is adjusted in the first step, and the molding pressure is adjusted in the third step to adjust the average fineness of alumina.
The hole diameters were 95 ° (Example 15) and 75 ° (Example 16).
Molybdenum component [(NH_Four)₆Mo₇O_{twenty four}・ 4H_TwoO]
An aqueous solution is impregnated with the nickel component [Ni
(NO_Three)_Three・ 6H_TwoO] In the same manner as in Example 1 except that the aqueous solution was impregnated.
Thus, catalysts O and P were obtained. Comparative Examples 4 to 6 (Preparation of Catalysts T, U, V)   The aging time is adjusted in the first step, and the molding pressure is adjusted in the third step.
A pore volume of 90% having a pore diameter of 60 ° and an average pore diameter of ± 10 ° (relative to alumina) (
Comparative Example 4), 140 °, 80% (Comparative Example 5), 85 °, 60% (Comparative Example) 6), and in the fourth step, the molybdenum component [
(NH_Four)₆Mo₇O_{twenty four}・ 4H_TwoO] impregnated with an aqueous solution to become 4% by weight in terms of oxides.
Nickel component [Ni (NO_Three)_Three・ 6H_TwoO] except that it was impregnated with an aqueous solution
In the same manner as in Example 1, catalysts T, U, and V were obtained.   Composition of catalysts O, P and comparative catalysts T, U, V, relative activity evaluation of hydrodesulfurization and gold
Table 6 shows the durability evaluation against metal deposition.   As is clear from Table 6, the present invention has a specific average pore diameter and a specific range.
Catalysts 0 and P having pore distributions in Examples (Examples 15 and 16) have reduced metal tolerance values.
Can maintain high desulfurization activity without inducing (in other words, short life)
You can see that   If the pore size is too small as in Comparative Catalyst T (Comparative Example 4), the metal tolerance
And the pore distribution is sharp as in Comparative Catalyst U (Comparative Example 5).
Also have large pores, and even if the pores are appropriate as in Comparative Catalyst V (Comparative Example 6),
If the distribution is broad, the desulfurization rate is small and satisfactory performance may not be obtained.
I understand. Example 17, Comparative Examples 7 to 9   Relative life test of hydrodesulfurization active metal components for Arabian light atmospheric residue
A catalyst having the physical properties shown in Table 7 as a first-stage catalyst (first hydrotreating catalyst)
In the latter-stage catalyst, the medium was used in Example 1 (Catalyst A), Comparative Example 1 (Catalyst Q),
Using W), the first and second catalysts were combined at a volume ratio of 30/70 vol%, respectively.
The desulfurization activity was evaluated for the catalyst system that was used.   The reaction conditions at this time were as follows.   Reaction conditions;     Reaction temperature (℃) Temperature at which the sulfur content of the produced oil becomes 0.3% by weight     Reaction pressure (Kg / cm^Two) 105     Liquid space velocity (Hr^-1) 0.25   FIG. 1 shows the change over time of the reaction temperature obtained by the evaluation test of this example.
Table 8 shows the properties of the product oils obtained by the respective catalyst systems when the temperature reached 385 ° C.
Each is shown in comparison. 〔The invention's effect〕   As described in detail above, according to the catalyst of the present invention, zeolite having a specific particle size and specific
Use a carrier in which alumina or alumina-containing material having a pore distribution is mixed at a certain ratio.
As a catalyst for hydrotreating hydrocarbon oils with both desulfurization and cracking activities
It is excellent and can maintain its excellent activity for a long time.   In the hydrotreating step of a hydrocarbon oil having a plurality of reaction zones,
Use of the above catalyst of the present invention after the reaction zone reduces the permissible content of catalyst poisons.
It is not necessary to reduce the reactivity due to hydrogenation in the first reaction zone.
However, it is possible to hydrotreat with high efficiency.
Good response to lighter and higher quality product hydrocarbon oils.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph for demonstrating the effects of the catalyst and the method of the present invention. In hydrotreating a hydrocarbon oil in two stages, the catalyst compositions of Examples and Comparative Examples were used. The relative life test in the case where the first hydrotreating catalyst was used in the first stage and used in the second stage was
FIG. 3 is a diagram in which the horizontal axis is plotted as the number of days and the vertical axis is plotted as the reaction temperature such that the sulfur content in the reaction product oil is 0.3% by weight. 1: First hydrotreating catalyst / Example 17 catalyst (volume ratio 30/70) 2: First hydrotreating catalyst / Comparative Example 8 catalyst (volume ratio 30/70) 3: First hydrotreating Catalyst / Comparative Example 9 catalyst (volume ratio 30/70)

Claims (1)

Claims: (1) As a carrier, 2 to 35% by weight of zeolite and 65 to 98% by weight of alumina or an alumina-containing material, and at least one metal of Group 6B of the periodic table or a periodic material on the carrier. (A) The characteristics of the alumina or the alumina-containing material are as follows: the average pore diameter is 70 to 100 mm, and the average pore diameter is ± 10 mm. 85-98% of the total pore volume of the pore volume of alumina or alumina-containing substance having, (B) the characteristics of the zeolite has an average particle size of 6μm or less, 70 the following particle size 6μm of zeolite all the particles (C) 2 to 30% by weight, based on the catalyst, of the Group 6B metal as an oxide, and 0.5 to 20% by weight of the Group 8 metal as an oxide, based on the catalyst; Charcoal characterized by being Hydrocarbon oils for hydroprocessing catalyst composition. (2) A method for hydrotreating a hydrocarbon oil comprising two or more reaction zones, wherein the catalyst composition according to (1) is used in a reaction zone after the second reaction zone. Hydrotreating method.