JPS61126196A - Hydrocracking of hydrocarbon - Google Patents

Abstract

PURPOSE:To hydrocrack a hydrocarbon at an excellent desulfurization rate, denitrogenation rate, etc. while keeping a high hydrocracking activity for a long time, by hydrocracking the hydrocarbon with a crystalline catalyst compsn. after hydrotreatment with a specified pretreatment catalyst. CONSTITUTION:A hydrocrbon is hydrotreated with a pretreatment catalyst comprising 5-30% (by wt.; the same applies hereinafter) Group VI metal component (oxide) of the periodic table and 2-10% Group VIII metal component (oxide) supported on an inorg. oxide carrier such as silica. Then it is hydrocracked under conditions including a temp. of 350-450 deg.C, H2 partial pressure of 50-200kg/cm<2>, liquid space velocity of 0.1-5hr<-1> and H/hydrocarbon ratio of 500-3,500Nl/l using a crystalline catalyst compsn. comprising 5-95% crystalline aliminosilicate zeolite, 5-95% inorg. oxide, 1-20% said Group VI metal cmponent (oxide), 0-7% Group VIII metal component (oxide) and such an amt. of P and/or B component that the wt. ratio of P and/or B element to the Group VI metal component (oxide) is 0.01-0.08 and the wt. ratio of each of P and B elements to the Group VI metal component is less than 0.045.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for converting hydrocarbons, particularly a hydrocracking method, in which hydrotreatment is carried out in two stages.

Hydrocracking is an important means of obtaining useful light distillates from heavy oil, and during this reaction, impurities such as sulfur, nitrogen, and metals contained in heavy oil are removed. Therefore, there is also the effect that the quality of the heavy oil after removing the obtained light fraction is also improved. Energy issues are an important industrial issue, and the question is how to obtain the necessary amount from heavy crude oil, whose proportion in imported crude oil is increasing, such as light boiling point distillates and middle distillates, which are in high demand. This is a problem that needs to be solved.The hydrogen decomposition method provides one means of solving this problem, and is also a step in the utilization of unused resources such as shale. It is something.

(Prior art) In general, hydrocracking catalysts for hydrocarbons have dual functions: acid activity to cleave carbon-carbon bonds and hydrogenation activity to donate hydrogen to the cleaved olefin-type molecules. It is a catalyst, and acid activity is expressed by acidic points in the catalyst.
Hydrogenation activity is developed by supported metals.

Crystalline aluminosilicate zeolite (hereinafter sometimes abbreviated as zeolite) has a crystal structure in which silicon and aluminum are bonded together in an orderly manner, so the density of acidic points that appear at the contact points of both elements is higher than that of silica. This is much higher than inorganic compounds such as alumina, so zeolites are often used as a component of this catalyst.

However, zeolite has the disadvantage that its crystal structure is easily destroyed when it comes into contact with high-temperature hot water, resulting in a decrease in catalytic activity. Therefore, various improvement studies have been conducted to stabilize the crystal structure of zeolite against high-temperature hydrothermal water. For example, US Pat. No. 3,536,606, ai! 38672
No. 77 Mei-a-it, No. 4036739 Specification f 4C
G! , -v The sodium ions contained in the zeolite are partially exchanged with ammonium ions, and the zeolite is calcined in a steam atmosphere with the temperature, treatment time, and steam partial pressure controlled, and the remaining sodium in the zeolite is A method for obtaining stable and highly active zeolite by exchanging ions with ammonium ions and calcining is described. Also, U.S. Patent No. 36698
No. 73 describes a method for obtaining stable and highly active zeolite by ion-exchanging zeolite with alkaline earth metal ions or rare earth metal ions.

However, although the methods described in these US patent specifications improve the resistance of zeolite to high-temperature hydrothermal water, when the zeolite is loaded with certain metal components such as metals from group 6 of the periodic table, the crystal structure of the zeolite is destroyed. Therefore, there is a problem that sufficient catalytic activity cannot be expressed.

As mentioned above, the hydrocracking catalyst is a component with acid activity such as zeolite (a catalyst component that controls the decomposition action); (hereinafter referred to as a carrier together with a carrier such as alumina) and a hydrogenation-active metal component supported on it, and the hydrogenation-active metal component includes metals from groups 6 and 8 of the periodic table. metal components are used, especially at! When supporting Group 6 metal components, the crystal structure of zeolite tends to be destroyed. Therefore, the acidic sites of the zeolite are significantly reduced, making it impossible to obtain a highly active hydrogenolysis catalyst. Methods for supporting metal components include immersing the carrier in a solution containing metal components, kneading the carrier component with a solution containing the metal component, and ion-exchanging metal oxides with the carrier component. This tendency also exists in methods. Furthermore, the method described in the above-mentioned U.S. patent specification is industrially disadvantageous because it involves multiple adjustment steps, and even products ion-exchanged with alkaline earth metal ions still have insufficient hydrothermal stability. There is also.

U.S. Patent No. 3,706,693, Canadian Patent No. 972,308, and Canadian Patent No. 972,340 disclose that a carrier consisting of zeolite and an inorganic oxide such as alumina, a metal compound of Group 6 of the periodic table, and Contact with an aqueous solution containing a metal compound and phosphorus alcohol, in which the weight ratio of Group 6 metal compound calculated as elemental phosphorus to oxide is 0.05 to 0.5, and the initial pH value is 3.0 or less. The preparation of hydrocarbon conversion catalysts is described. As mentioned above, in these patents, the crystal structure of zeolite is destroyed by adding a large amount of phosphoric acid under strong dispersion conditions when supporting hydrogenation metal components, but in addition to hydrogenolysis activity, denitrification activity and intermediate It is stated that the selectivity for fractions can be improved. However, in these methods, the high decomposition activity of zeolite is intentionally lowered rather than destroying the crystal structure of zeolite, and the 5m point is observed when the hydrogenolysis activity is insufficient.

(Problems to be Solved by the Invention) The present inventors have previously discovered that the crystal structure of zeolite is not destroyed when a metal component of group IG6 of the periodic table is supported on a zeolite-containing carrier under specific conditions, and that the crystal structure of zeolite is not destroyed in this way. It was discovered that the prepared convex and convex catalyst composition with a specific composition exhibits high activity in the conversion of hydrocarbons, particularly in hydrocracking reactions.

A patent was issued (Japanese Patent Application No. 58-92680). This hydroprocessing catalyst will hereinafter be referred to as "1-Crystalline Catalyst Composition."As is clear from the following explanation, the term "1-Crystalline Catalyst Composition" herein does not mean that the entire catalyst is crystalline. , is used to mean that a substantial portion of the zeolite component in the catalyst exists with the zeolite crystal structure retained.

This crystalline catalyst composition not only hydrocracks light oils such as heavy naphtha and gas oil boiling fractions, but also hydrocracks five crude oils,
It also shows higher activity than previous catalysts in the hydrocracking reaction of heavy oil such as residual oil and vacuum gas oil into light oil.
This not only has an excellent dual function of acid activity for cleaving carbon-carbon bonds and hydrogenation activity for donating hydrogen to the cleaved olefin-type molecules, but also This is thought to be due to the excellent resistance to the above-mentioned impurities contained in. However, as a result of various studies, it has been found that even this crystalline catalyst composition tends to gradually reduce its hydrocracking activity due to excessive impurities in the feedstock oil if the reaction is carried out over a long period of time.

Of all the hydrocarbons, heavy oil such as crude oil and residual oil contains nitrogen compounds, sulfur compounds, and hydrocarbon compounds in addition to hydrocarbon compounds.
There are large amounts of metal compounds and asphaltenes containing them, and vacuum distillate oil contains large amounts of sulfur compounds and nitrogen compounds, and these impurities impair the hydrocracking activity of the catalyst. That means.

A-Voorhies, 6th W-P-CI
219 ('63) and Journal of Catal
ysis I(3,L P235), and the above-mentioned crystalline catalyst composition is no exception.

(Means for solving the problem) It is possible to regenerate the activity of a catalyst poisoned by such impurities by a normal regeneration method such as combustion, but the interval between regeneration treatments should be as long as possible. Desirably 1 As a result of extensive research into efficient hydrocracking methods, the present inventors have found that when hydrocracking the above-mentioned heavy oil into light oil, the oil is preliminarily treated in the presence of hydrogen. Under normal hydrofining conditions 1 Normal hydrofining (
in contact with a hydrotreating catalyst used in hydrorefining],
If the hydrocracking reaction is then carried out by contacting with a crystalline catalyst composition, it is possible to maintain an effective level of catalytic activity over a long period of time, increasing the operating momentum of the hydrocracking reaction, and providing an unparalleled idea. Ta.

That is, the gist of the present invention is to hydrogenate hydrocarbons with a pretreatment catalyst consisting of an inorganic oxide, a metal component of group 6 of the periodic table, and a metal component of group 8 of the periodic table, and then 5-95% by weight of aluminosilicate zeolite, 5-95% by weight of inorganic oxides, 1-20% by weight in terms of 1-decayed oxides, 0-7% by weight of 1-decay metal components in terms of oxides. , and the weight ratio of the Group 6 metal component calculated by converting the phosphorus component and/or boron component into phosphorus element and/or boron element dispersion is o. o
Hydrocracking of hydrocarbons, characterized by hydrogenolysis using a crystalline catalyst composition containing Kitamoto with a ratio of i~00OS and a ratio of each of phosphorus element and boron element less than 0.045. It lies in the method.

Examples of raw material hydrocarbons that can be treated in the method of the present invention include crude oil, residual oil, deasphalted oil obtained by solvent deasphalting treatment of crude oil or residual oil, and gas oil.

Examples include naphtha and vacuum gas oil.

The hydrotreating catalyst used in the first step will be hereinafter referred to as a pretreatment catalyst with respect to the crystalline catalyst composition used in the second step, but such a pretreatment catalyst is a normal hydrotreating catalyst, and for example, These include hydrodenitrogenation catalysts, hydrodesulfurization catalysts, hydrodemetalization catalysts, and hydrode-askartene catalysts. These catalysts are known in the art5 and their composition is usually based on an inorganic oxide support such as alumina, silica, titania, boria, zirconia, magnesia, or
Iron, phosphorus, antimony.

Any one of zinc, copper, manganese, or tin oxide
species or two or more refractory inorganic oxides and periodic table 6
Group metal components such as molybdenum.

It consists of chromium or tungsten and a metal component of group IIcB of the periodic table, such as cobalt or nickel, and further contains Li, Na,
K, Ca, Be, Ba, V, Nb.

Ag, Au, Cd, Pb, As, Bi, L
a, Ce, Ge.

Components such as halogen may be added.

Usually, the Group 6 metal component is about 5 to 30% by weight as an oxide,
Preferably from 8 to 20% by weight, with the Group 8 metal component being about 2 to 10% by weight as oxides, preferably from 3 to 7% by weight.

These pretreated catalysts usually have a surface area of about 50 to 400 g/11, preferably 200 to 3 oorrvi, about 0.3 to
1.0 ml/I.

It has a pore diameter.

The pretreatment reaction conditions are a temperature of about 340 to 400°C, a hydrogen partial pressure of 50 to 150/9/i, and a liquid hourly space velocity of about (12 to 5.5%).
Ohr, hydrogen to hydrocarbon oil ratio approximately 350-350O
Nl/l.

The pretreatment reaction involves passing hydrocarbon oil and hydrogen in an upward flow through a fixed bed or fluidized bed packed with a catalyst, passing the hydrocarbon oil and hydrogen in a downward flow through a fixed bed, or carbonizing into a fixed bed or fluidized bed packed with a catalyst. A conventional method can be used, such as passing hydrogen oil as a downward flow and hydrogen as an upward flow.

Furthermore, prior to treatment of hydrocarbon oil, the catalyst composition may be pre-sulfurized by passing hydrogen sulfide gas or sulfur-containing oil such as kerosene into the catalyst bed. Such pretreatment catalysts are usually used for denitrification and desulfurization.

Demetallization and deaeration of 7-artene occur simultaneously.

At the temperature and pressure levels normally used in pretreatment processes, organic nitrogen compounds in the feedstock oil are usually substantially converted to ammonia.

Also, organic sulfur compounds are usually substantially converted to hydrogen sulfide. The metal compound is adsorbed in the pretreatment catalyst and decomposed by hydrogen donation, depositing the metal in the pretreatment catalyst.

Asphaltene is also adsorbed on the pretreatment catalyst, decomposed and reduced by receiving hydrogen donation, lowering the carbon/hydrogen ratio, and reducing the carbon/hydrogen ratio.
Further, nitrogen compounds, sulfur compounds, and metal compounds contained in asqualtene are reduced by the above reaction.

If the ammonia gas generated in the pretreatment process passes directly to the crystalline catalyst composition in the subsequent step, it is expected that because it is basic, it will be adsorbed to the acid active sites of the crystalline catalyst composition, and it will also occur in the same way. The hydrogen sulfide produced is Jour
a1ofCatalysis Volume 1, Issue 3, 4235
As described on page 1, it was thought that the alumina in the catalyst would be adsorbed to form M-8 bonds, resulting in a decrease in the activity of the catalyst, but according to research conducted by the present inventors, the Of course, if ammonia and hydrogen sulfide generated during the treatment process are removed and the resulting oil is passed along with fresh hydrogen to the crystalline catalyst composition to carry out the hydrocracking reaction, an effective level of catalyst activity can be maintained for a long period of time. However, by passing the product oil and gas generated in the pretreatment process directly to the solidified catalyst composition to perform a hydrocracking reaction, it is more effective than when no treatment reaction is performed. It has been found that a level of catalytic activity can be maintained for a much longer period of time. This indicates that the crystalline catalyst composition has greater resistance to ammonia and hydrogen sulfide than to organic nitrogen and sulfur compounds.

Therefore, in a hydrocracking reaction using a combination of a pretreatment catalyst and a crystalline catalyst composition in a subsequent step, it is not necessary to remove the product gas generated in the pretreatment process.

The thus pretreated product oil is hydrotreated using a crystalline catalyst composition. The pretreated catalyst and the crystalline catalyst composition may be packed in one reactor in layers or may be packed in separate reactors.

This crystalline catalyst composition (described in %Yen Show No. 58-92680) contains 5 to 95% of crystalline aluminosilicate zeolite.
Weight%, porous refractory inorganic oxide from 5 to 95% by weight 1 portion is 1 to 203f in terms of oxide Weight% 1 Group 8 metal component of the periodic table is 0 to 7% by weight in terms of oxide %, and the weight ratio of the Group 6 metal component calculated as phosphorus element and/or boron element to oxide is 0.01 to 0.08, and phosphorus element and boron element A crystalline catalyst composition for hydrocarbon conversion, characterized in that the catalyst comprises the crystalline aluminosilicate zeolite and the inorganic oxide, each in a proportion of less than 0.045. When supporting a Group 6 metal component on a carrier, the weight of the Group 6 metal compound containing a 1J46 metal compound and a phosphorus compound and/or a boron compound, calculated as phosphorus element and/or boron element versus oxide. The above carrier is brought into contact with a solution having a ratio of 0.01 to 0.08, a ratio of each of phosphorus element and boron element of less than 0.045, and a PU value of 3.3 to 6.0. It can be prepared by supporting a Group 6 metal compound and a phosphorus compound and/or a boron compound on a carrier. The details of this crystalline catalyst composition will be described below.

A crystalline catalyst composition is a composition in which a metal component of Group 6 of the periodic table and a compound of phosphorus and/or boron are supported on a carrier consisting of crystalline aluminosilicate zeolite and an inorganic oxide as a matrix or host. , or in addition to these, a metal component from group 8 of the periodic table is supported.

The crystalline aluminosilicate zeolite (sometimes abbreviated as zeolite) used in this catalyst is ion-exchangeable, and may be either natural or synthetic. Jiasite X-type zeolite, faujasite Y-type upper secondary zeolite, chabanite-type zeolite, mordenite-type zeolite, so-called ZSM-based zeolites containing organic cations) (ZSM-based zeolites include ZSM-4 and ZSM-5.

ZSM-8, ZSM-1 1, ZSM-12, ZSM-
20, ZSM-21, ZSM-23. ZSM-34.

ZSM-35. ZSM-38, ZSM-43 ft Dokaari, January 11, 1980, Japan Technology and Economy Center Publishing Department, "Recent Progress in Zeolite Technology and Applications Comprehensive Collection", pp. 46-57, edited by Hiroshi Takanan et al. February 1, 1975
Japan "Zeolite" published by Kodansha, pages 46-47,! #Detailed in the specification of 1982-70828 etc. )and so on.

Atsuko number ratio S of silicon element to aluminum element contained
i /AJ is about 1 or more, and the cation exchange capacity is about 0. 3
meq/,9 or more is preferred. The cationic species of these zeolites are NH4+ or t-type, and they are combined with alkaline earth metal ions such as Mg w' Ca , Ba -rare earth metal ions such as La. If Ce, group 8 metal ions of the periodic table, such as CO++, Ni++, Pd+1, etc., are present in large quantities, the catalytic activity will be reduced, so it is usually preferable that the amount is about 0.5% by weight or less based on the zeolite. The appropriate amount of zeolite to be blended (on a dry matter basis, including ion-exchanged metals) is about 5 to 95Ji% by weight, preferably about 10 to 80% by weight, based on the final catalyst composition. If the amount is too small, the decomposition ability as a catalyst will be low, and if the amount is too large, the amount of other components will be reduced, making it unsuitable as a hydrocracking catalyst.

Alumina is used as a refractory inorganic compound blended as a matrix in this crystalline catalyst composition.

Silica-alumina, titania-alumina, zirconia
Alumina and silica-titania-alumina are preferred. The content of alumina in the matrix is preferably about 20% by weight or more based on the matrix. In addition, the surface area of the matrix is suitably at least about 307 FL''/I or more. The matrix is effective in improving the strength of the catalyst and the selectivity of the hydrogenolysis reaction,
It also lowers catalyst prices. The amount of matrix incorporated is about 5 to 95% by weight, preferably about 2% by weight, based on the final catalyst composition.
o-Q9o% by weight, if the matrix is not added or the amount is too small, the reaction selectivity will be reduced and a large amount of undesirable gas and coke will be produced5, while if the amount is too large, other The amount of the components blended is small, making it unsuitable as a hydrocracking catalyst.

The hydrogenation metal component to be added to the crystalline catalyst composition is a metal from Group 6 of the periodic table, such as molybdenum.

There are tungsten and chromium; group 8 metals include cobalt and nickel, which belong to the iron group; and platinum, palladium, etc., which belong to noble metals. Group 8 metals do not necessarily need to be blended. A suitable amount of the hydrogenation metal component is about 1 to 20% by weight of the Group 6 metal component in terms of oxide based on the final catalyst composition.

Preferably about 1-15! The Group 8 metal component is about 0 to 7% by weight in terms of oxide.

The preferred amount of the iron group metal component is about 1 to 5% by weight, and the preferred amount of the noble metal component is about 0.1 to 2% by weight. Although these metal hydride components are in the form of water-soluble compounds or metal hydroxides when they are supported, most of them are in the form of metal oxides (some are in the form of simple metals) because they are fired afterwards. ), and may be sulfurized when or during use in a hydrocarbon conversion reaction, so some or all of them may become metal sulfides.

The crystalline catalyst composition further contains K IJ or boron. Both may be contained.

The content of phosphorus in the final crystalline catalyst composition is such that the weight ratio of elemental phosphorus to Group 6 metal component calculated as oxide in the catalyst is less than 0.045, preferably from about 0.010 to (1
043, and the boron content is approximately 0.010 to 0.
．． It is 043. However, when using phosphorus and boron together,
The ratio of this total is o,oi~0.08. A phosphorus compound or a boron compound is used as an essential component in the step of supporting a Group 6 metal component on a carrier, as described below.

It enters the catalyst. Like the metal hydride components, even if the phosphorus and boron components are water-soluble compounds when supported on the carrier, most of them become oxides or simple elements (free phosphorus or boron) during subsequent calcination. it is conceivable that.

In order to produce a crystalline catalyst composition, it is not just a matter of mixing the above-mentioned components in their desired amounts;
The preparation method also needs to be carried out under specific conditions. In other words, when a group 6 metal component of the periodic table is supported on a carrier made of zeolite and inorganic oxide (IJ lux), a group 6 metal compound and a phosphorus compound and/or a boron compound containing arsenic and/or First, the weight ratio of the G6 group metal compound converted as an oxide to 1 boron element is 0401 to 0.
In the ratio of 0.08, the ratio of each of the phosphorus element and the boron element is less than 0.045.

Preferably, the ratio is about o, oio to 0.043, and the initial MpH value is about 3.3 to 6.0, preferably about 4.0 to 5.
The solution of No. 5 and the above carrier are brought into contact and supported. That is, only a portion of the phosphorus compound and the boron compound may be used, or both may be used.

If the ratio of the phosphorus compound to the Group 6 metal compound or the ratio of the boron compound to the Group 6 metal compound is too low or too high, the crystal structure of the zeolite will be destroyed. The ratio is almost the same as that carried.

If the pH value of the solution is too low, the crystal structure of the zeolite will be destroyed, and if the pH value is higher than about 6.0, the metal compound will precipitate, making it impossible to support it uniformly on the carrier. The pH value of the solution varies depending on the purity of the metal compounds, phosphorus, and boron compounds used, but it can also be controlled by changing the concentration of these compounds or adding acid. Compounds containing both a Group 6 metal and phosphorus or boron (e.g. phosphomolybdic acid or tanges) IJ acid acts both as a Group 6 metal compound and as a phosphorus or boron compound. Water-soluble Group 6 metal compounds can be used, examples of which include ammonium paramolybdate, molybdic acid, ammonium molybdate, phosphomolybdenum oxide/monicum, phosphomolybdenum powder, ammonium tungstate, tungstic acid, and tungstic anhydride. , tungstophosphoric acid, ammonium chromate, chromic acid, etc. Water-soluble phosphorus compounds and boron compounds can also be used. Phosphorus compounds include phosphorus powder, phosphorus &.

Hypophosphorous acid, phosphomolybdic acid, phosphomolybdenum dispersion/
Examples of boron compounds include monicum, phosphotungsten powder, and ammonium phosphotungsten dispersion, and boron compounds include boron oxide, ammonium borate, boron oxide, boron chloride, and boron heptafluoride. In order to support these Group 6 metal compounds and phosphorus or boron compounds on the carrier, the solution containing these compounds may be brought into contact with the carrier by a conventional method, for example, by immersing the carrier in the solution.

Various methods can be used, including a method of kneading the carrier and a solution, a method of dropping the solution onto the carrier, and a method of ion exchange by immersing the carrier in the solution. The carrier brought into contact with the solution may be molded or unmolded.

Aiin of the crystalline catalyst composition can be prepared by a conventional method except that the above-mentioned Group 6 metal compound and phosphorus or boron compound are supported on the carrier. Supporting the Group 8 metal component on the carrier can also be carried out by a conventional method, for example, by contacting the component with a solution containing the Group 8 metal compound as the carrier. That is, it is immersed in a solution containing a Group 8 metal compound as a carrier.

Methods such as dropping the solution onto a 9% carrier obtained by kneading the carrier and the solution, or immersing the carrier in the solution to perform ion exchange can be used. Supporting the Group 8 metal component on the support is the 6th group metal component.
It may be carried out at the same time as supporting the group metal component, or may be carried out before or after supporting the group 6 metal component. When the Group 8 metal compound is brought into contact with a solution carrier and supported on the Group 8 metal component carrier, examples of Group 8 metal compounds that can be used include water-soluble compounds 1, such as cobalt or nickel nitrates and sulfates. , fluoride, chloride, bromide, acetate,
Carbonated salts, phosphates, palladium chloride, chloroplatinic acid, etc.

The Group 8 metal component does not necessarily need to be blended.

A carrier consisting of zeolite and a matrix can be prepared, for example, by thoroughly mixing zeolite and hydrogel of i-trix component, removing water, and molding the mixture into an appropriate size. In addition, kneading of a carrier and a solution containing a metal hydride component, etc. is carried out by mixing the zeolite, matrix component hydrogel, and a solution containing a metal hydride component, etc., stirring thoroughly, removing moisture, and molding. You can prepare more traps. The molded product thus prepared is usually dried, fired, and further (when supporting metal hydride components, etc., dry and fire after supporting those components. When supporting metal hydride components two or more times, Usually, it is preferable to dry and sinter each time a metal hydride component is supported.Drying is usually carried out at room temperature to about 150°C, especially about 100 to 120°C.
It is preferable to hold the temperature at a temperature of about 5 hours or more, especially about 12 to 24 hours, and the firing is usually carried out at about 350 to 600°C, especially about 400 to 500°C.
Preferably, the temperature is maintained at 50° C. for about 3 hours or more, particularly about 12 to 24 hours.

The crystal structure of the zeolite in the crystalline catalyst composition thus prepared was determined by Xls diffraction analysis with diffraction angles characteristic of the zeolite (2I0, e.g. 6.2° and 15.7° for faujasite Y-base zeolite). It can be confirmed by the intensity of the crystal peak of K, but it can be more easily confirmed by measuring the surface area by the nitrogen adsorption method. In other words, zeolite has a significantly larger surface area than the matrix and metal components, so if the zeolite crystal structure in the catalyst is kept stable, the catalyst will have a large surface area, and if the crystal structure is destroyed, the surface area will decrease. This is because the amount decreases significantly.

The reaction conditions for the subsequent water accumulation treatment step are a temperature of approximately 350 to 45
0℃, hydrogen partial pressure about s O ~ 200 to 9/+! .

A liquid hourly space velocity of about 0.1 to 5 hr and a hydrogen to hydrocarbon oil ratio of about 500 to 350 ONI/l are preferred. Prior to treatment of hydrocarbon oil, the catalyst composition may be pre-sulfurized by passing hydrogen sulfide gas or sulfur-containing oil such as kerosene into the catalyst bed. In addition, the reaction can be carried out by conventional methods such as passing hydrocarbon oil and hydrogen in a downward flow through a fixed bed packed with a catalyst, or passing hydrocarbon oil in a downward flow and hydrogen in an upward flow to a fluidized bed containing a catalyst. I can do it.

The crystalline catalyst composition acts as a hydrocracking catalyst.

(Effects of the Invention) According to the present invention, hydrocarbons are first hydrotreated using a specific pretreatment catalyst, and then hydrotreated using a specific crystalline catalyst composition. Hydrocarbons can be hydrocracked while maintaining activity. This long-term high hydrocracking activity is achieved by using a crystalline catalyst composition blended into the catalyst while maintaining the zeolite crystal structure as a hydrotreating catalyst in the subsequent step, and by using this in combination with a pretreatment catalyst. brought about. In other words, in the crystalline catalyst composition used in the latter step, the crystal structure of the zeolite blended therein is maintained without being nearly destroyed, so the acid activity of the zeolite is sufficiently expressed, and the supported metal components are highly concentrated. Because it is well dispersed and supported near the acidic point of zeolite, hydrogenation activity is expressed.

By using it in combination with a pre-treatment catalyst, it can be used in the conversion reaction of hydrocarbons, especially in the hydrocracking reaction, for a long period of time at extremely low temperatures.
Shows high activity. In addition, the method of the present invention maintains high hydrocracking activity over a long period of time, and the catalytic activity is extremely high compared to when using conventional catalysts, making it possible to process heavy oils that are difficult to process using conventional catalysts. Even residual oil containing as-7-artene, metal, sulfur, nitrogen, etc. can be treated. In addition, in the method of the present invention, the desulfurization rate, denitrification rate,
Demetallization, etc., is also maintained at a relatively high level for a long period of time.

(Example) The present invention will be further explained below with reference to Examples.

In the following examples, Examples 1 to 1O show preparation examples of crystalline catalyst compositions used in the later steps of the method of the present invention, and Comparative Examples 1 and 2 show preparation examples of comparative catalysts for crystalline catalyst compositions. .

Example 1 The following two types of impregnating support solutions A and BftiJ1 were combined.

Impregnation iA: Ammonium paramolybdate 2641 was dissolved in distilled water lj, and then phosphoric acid 28.5F was added thereto and stirred to uniformly dissolve.

The pH of the produced solution was 4.6, and the weight ratio of phosphorus element to molybdenum-containing compound (hereinafter abbreviated as P/MoO3) as an oxide was 0.04.

Impregnation liquid B: Nitrate & nickel 27211 in 750 g distilled water
was added and dissolved.

Separately, H"W's Faujatite Y-type zeolite 450y and alumina hydrogel 10.5'Kg (alumina content 1050.!i+) were sufficiently kneaded and mixed, and after removing water, a diameter of about 1.6 The molded product was extruded into a cylindrical shape with a length of 716 inches and a length of 310 m.The molded product was dried at 120°C for 24 hours.

A zeolite-alumina catalyst carrier was then produced by calcining at 550°C for 12 hours.

The surface area of this carrier was measured using a nitrogen adsorption method and was found to be 340 rrl/l. The impregnating support solution A was gradually dropped onto this carrier to impregnate the entire catalyst particles. After the completion of dropping all the impregnating liquid, it was left to stand for 1 hour, dried at 120°C for 24 hours, and then baked at 500°C for 12 hours. Subsequently, impregnating liquid B was added dropwise to this catalyst carrier in the same manner to impregnate it, dried at 120°C for 24 hours, and then calcined at 450°C for 12 hours. The chemical composition of the catalyst F-1 prepared in step 5 was as follows. (Metal components are expressed as amounts converted as metal oxides, phosphorus and boron are expressed as amounts converted as elements, and ion-exchanged metal components are expressed as elements. The same applies hereinafter.) MoO3
11,9 JIJI part NiO3,9'P 0.5 part by weight zeolite 27.11 rrl/11. As a result of X-ray diffraction analysis, the zeolite crystal structure was confirmed.

Comparative Example 1 The following impregnated and supported liquid C was prepared in place of the impregnated and supported liquid A in Example IK.

Impregnation support solution C: 264 g of ammonium paramolybdate was dissolved in 1 liter of distilled water. The pH of the solution was 6.3, and the solution did not contain phosphorus.

A catalyst was prepared in the same manner as in Example 1 except that impregnated support liquid C was used instead of impregnated support liquid A.

The composition of this catalyst F-2 was as follows.

MoO312, 4 parts 1 part Ni0 4.3’ P None Zeolite 25.0 parts by weight Alumina 58.3 parts by weight.

Catalyst F-20P/Mo 03 weight ratio is 0, surface area is 1
47m/? Moreover, in the results of X-ray diffraction analysis, no crystal structure peak could be confirmed.

Comparative Example 2 In place of the impregnated and supported liquid A in Example 1, the following impregnated and supported liquid was prepared.

Impregnated support liquid D: 264.9% ammonium paramolybdate was dissolved in M distilled water 11, and then phosphorus fi171J'
was added to this and stirred to dissolve uniformly.

The pH of the solution was 2°0, and the P/Mo03 weight ratio was 0.
It was 25.

A catalyst was prepared in the same manner as in Example 1, except that impregnated support solution A was replaced with impregnated support solution A.

The composition of this catalyst F-3 was as follows.

Mo 03 11.9 parts by weight NiO 3,6# P 3.0 # Zeolite 24.51 Alumina 57.0 parts by weight Catalyst F-3 has a P/MoO3MoO3 weight ratio of 52, a surface area of 115 ml, and an X-ray diffraction analysis. As a result, it was not possible to confirm the peak of the crystal structure.

Example 2 Impregnation support liquid Et! ! : Mixed.

Impregnated support liquid E: 1.51 K + 7 molybdic acid 2271 was dissolved in distilled water. The pH of the solution is 3.3, P/
The quantitative ratio to MoO3- was 0.018.

A catalyst was prepared in the same manner as in Example 1, except that impregnated and supported solution E was used instead of impregnated and supported MA.

The composition of this catalyst F-4 was as follows.

MoO3 12.5 parts by weight Ni0 3.7' P 0.221 Zeolite 25.11 Alumina 58゜5I Catalyst F 4 I) P / MoO3 weight ratio is 0.0
18. The surface area was 304 cm/y.

Example 3 An impregnated support solution F was prepared.

Impregnating support liquid F: Dissolve ammonium paramolybdate 264I in distilled water, and then add 264I of ammonium paramolybdate. ! 4! Ml was added to the solution and stirred uniformly to dissolve.

The pH of the solution is 5-0% B/MoO3! quantity ratio) t 0.
It was 043.

A catalyst was prepared in the same manner as in Example 1, except that impregnated support liquid F was used instead of impregnated support liquid A.

The composition of this catalyst F-5 was as follows.

MoO 312.3 parts by weight Ni0 4.0' B O, 531 Zeolite 25.01 Alumina 58.21 Catalyst F-50B /Mo 03 weight ratio is 0.043. The surface area was 284 cm/I.

Example 4 An impregnated support liquid G was prepared.

Impregnated support g! LG: Distilled water 1.21 phosphomolybdenum i
! ! 227.9 and then boric acid 45,! i'
was dissolved. The pH of the solution is 3.511, the P/MoO3 weight ratio is 0.018, and the B/MoO3Jft ratio is 0.0.
It was 42.

A catalyst was prepared in the same manner as in Example 1 except that impregnated support solution G was used instead of impregnated support mA.

The composition of this catalyst F-6 was as follows.

MO0311,9-1 part NiO4,0' P 0.21# B O,501 Zeolite 25.01 Alumina 58.5# The surface area of this catalyst F-6 is 320 rrl, /11. P
/MoO3! The weight ratio was 0.018, and the B/MoO3 weight ratio was 0.042.

Example 5 The same H-type 7-Osiasite Y-type zeolite used in Example 1 was cation-substituted using a lanthanum chloride aqueous solution to produce La7-Oujasite Y-type zeolite. This zeolite water glass and silica-alumina sol obtained from aluminum sulfate were thoroughly mixed, extruded into a cylindrical shape with a diameter of about 1.6 m (1715 inches) and a length of 3 cm in the same manner as in Example 1, and dried. Perform firing, La7
A siasite Y-type zeta-silica alumina catalyst support was produced. The surface area of this carrier is 360 m/Jl
Met.

Further, an impregnating support liquid H1k was prepared.

Impregnated support liquid H: distilled water 750-cobal nitrate) 272
．． 9 was added and dissolved.

7 Aujasite YW zeolite - the above La faujasite Y type zeolite instead of the alumina catalyst carrier -
A catalyst was prepared in the same manner as in Example 1, except that a silica-alumina catalyst carrier was used and impregnated carrier solution H was used instead of impregnated carrier solution B. The composition of this catalyst F-7 (the zeolite is expressed as lanthanum-free) was as follows.

Mo 03 10.6 parts by weight Coo
3.5' P O, 45, 1 part salt La
3.0 zeolite
24.7 Silica 43.3 1 Alumina 14.4 The surface area of catalyst F-7 is 315 rrj/I, P/
The MoO3 weight ratio was 0.042.

Example 6 The H+ faujasite Y-type zeolite used in Example 1 was converted into a palladium ammonia complex Pd(NH3)2(
Cation replacement was performed using j2 solution. The palladium concentration in the zeolite after cation exchange was measured to be 0.
It was 56% by weight.

Separately, titanium sulfate solution (content 525 as Ti02,
? ) was added dropwise little by little to bring the temperature to H7.0, and the resulting precipitate was thoroughly washed with distilled water.

A titanium hydrogel was obtained. Also, aluminum sulfate solution (
AA! The content of 525II) as 203 was similarly neutralized with aqueous ammonia and thoroughly washed with water to obtain an alumina hydrogel. Both of these hydrogels and the above H+ are partially Pd”
pd++-H+ type 7 Augiasite Y type zeolite substituted with + is thoroughly kneaded, moisture is removed, and a diameter of about 1
．． It was extruded into a cylindrical shape with a diameter of 6 wx (1/16 inch f) and a length of 3 m. This Nariya product was dried at 120°C for 24 hours.

Then, by firing at 550°C for 12 hours, Pd++
-H+ type faujasite ym zeolite-alumina titania based catalyst support was produced. The surface area of this carrier is 2
85. It was ml/11.

For this catalyst carrier! ! Use the same method as Example 1! i5!
Example 1 Same impregnated support solution AIk as in application 1: impregnated support,
The catalyst was dried and calcined, and then impregnated and supported with the same impregnated and supported liquid H used in Example 5, dried and calcined to prepare a catalyst. The composition of this catalyst F-8 (expressed on the assumption that the zeolite does not contain palladium) was as follows.

Mo 03 14.7 Part by weight Coo
3.8'PdO,
141 P 0.621 Zeolite 24.2 Parts by weight Titania 2.8.5 #Alumina
28.0 # The surface area of this catalyst F-8 is 254m/iP/Mo 03
The weight ratio was 0.042.

Example 7 Impregnated supported gLI4tll was developed.

Impregnation support liquid technique: ammonium paratungstate (NH4) in distilled water. W1□04□・5H2048,
59ft11! ! Then 5.71 g of phosphoric acid was dissolved.

This 1li(F) pH*, 5. P/WO3-1 ratio) 1
It was 0.042.

An H+ base rough auger size Y-type zeolite-alumina catalyst carrier was produced in the same manner as in Example 1, and impregnated with the above-mentioned impregnated carrier liquid Ift. That is, the above-mentioned impregnated and supported solution I is dropped onto the catalyst carrier and supported, and dried at 120° C. for 3 hours. Further, an impregnated and supported solution I'tlI is prepared in the same manner, and the impregnated and supported solution I is again impregnated and supported and dried.

In this way, impregnation and loading was repeated a total of 5 times, and finally VCl2
It was dried at 0°C for 24 hours, and then fired at 500°C for 12 hours. Next, a catalyst was prepared by impregnating and supporting the impregnated support liquid B on this catalyst substrate in the same manner as in Example 1, followed by drying and calcining. The composition of this catalyst F-9 was as follows.

Wo, 11.3 parts by weight NiO4, O P O, 48 # Zeolite 25.3 # Alumina 58.9 # The surface area of catalyst F-9 is 298/11. The P/WO3 weight ratio was 0.042.

Example 8 An impregnated support liquid Jt-111 was prepared.

Impregnation support liquid J: Distilled water 1.5I and Lintungster 1R
Dissolve P2O5・24WO3@nH2O1111.

Then, Hou ff145N was dissolved. E)H of solution is 3
．． 3%P/WO3 weight ratio is 0.012, B/W 0.
1 to 0.043.

A catalyst was prepared in the same manner as in Example 1, except that impregnated support liquid J was used instead of impregnated support liquid A.

The composition of this catalyst F-10 was as follows.

WO31L5 Part by weight NiO3,8' p 0.14' B O,491 Zeolite 25.2 1 Alumina 58.9 1 Catalyst F-1017) Surface area kt 312 m”/II
The P/W03 weight ratio was 0.012, and the B/WO1 weight ratio was 0.043.

Example 9 Two coats of impregnated support UK, L were prepared.

For impregnating support solution: Dissolve 52.8N of paramolybdenum-identified ammonium in 200 tnl of distilled water, then add phosphorus a
l! 5.7 F was dissolved. The DH of the solution is 3.4゜P
/Mo03 weight ratio was 0.039.

Impregnation support solution L: 54 nickel nitrate in 150 mj distilled water
．． ? was added and dissolved.

Separately, aluminum sulfate 137011 (content as alumina 210.9) was dissolved in distilled water 51, and aqueous ammonia was gradually added dropwise while stirring vigorously to bring the pH to 7.
．． OK. With further vigorous stirring, H''W Forjanite ym Zeotite 90j+ is thoroughly mixed.

After sufficiently warming, impregnating and supporting liquid K is added thereto, and the mixture is sufficiently kneaded. Thereafter, it is dried at 120° C. to remove moisture, and extruded into a cylindrical shape with a diameter of about L 6 I@ (1/16 inch) and a length of 3 chicks. This molded product is 120
℃ for 24 hours and then calcined at 550℃ for 12 hours. Gradually drop the impregnated support liquid onto this catalyst substrate,
The entire catalyst substrate was impregnated. The entire impregnated carrier solution was left to stand for 1 hour after the completion of dropping, dried at 120°C for 24 hours, and then heated at 45°C.
A catalyst was prepared by calcining at 0° C. for 12 hours. This catalyst F-
The composition of No. 11 was as follows.

MoO310, 3 parts by weight Ni0 4.2' P O, 4# Zeolite 25.5# Alumina 59.61 The surface area of catalyst F-11 is 282 m'/1. P/M
The oO3 weight ratio was 0.039.

Example 1O H+ type mordenite type zeolite) 450# and alumina hydrogel 10.5kliF (alumina content 1050
．． 9) is sufficiently cross-mixed to remove moisture, and then extruded into a cylindrical shape with a diameter of about 1.6 wi (1/16 inch) and a length of 3 mm. This molded product was dried at 120°C for 24 hours and then calcined at 550°C for 12 hours to produce a zeolite-alumina catalyst carrier. The surface area of this carrier was 242/I.

A catalyst was prepared in the same manner as in Example 1 except that the above catalyst carrier was used instead of the catalyst carrier used in Example 1. child,
The composition of catalyst F-12 was as follows.

MoO 311.5 Jl parts Ni0 3.8 g p 0.5 1 Zeolite 25.3# Alumina 58.9 M parts The surface area of catalyst F-12 is 225 rd/l, P/
The MoO3 density ratio was 0.043.

Comparative Example 3 Using the catalyst F-1 prepared in Example 1, a hydrogenolysis reaction of atmospheric residual oil was carried out. The properties of the atmospheric residual oil used in anti-EK were as follows.

Specific gravity, 15/4°C 0.9492 Pour point, °C
io,.

Viscosity, cSt (50'C) 138.6 residual carbon,
wt% 7.88 sulfur content,'
2,97 Nitrogen #0.
12 Asquartene content, wt% 1.89Ni content, wt ppm 7v'
27 Vacuum fractionation properties (value converted to normal pressure) Initial boiling point, 'C182 50vol 1% point, 'C470 The reaction was carried out using a flow reactor under the following reaction conditions.

Catalyst amount 15 ml Raw material oil/liquid space velocity 0.3 hr-' Reaction pressure (hydrogen pressure) 105 to 9/cd Reaction temperature
400° C. Hydrogen//ll ratio 267 ONj/j In this comparative example, the number of reaction days was not limited to 15 days, but one reaction was continued for a long period of 150 days or more.

Clogging on the 15th day after the start of the reaction and 0 decomposition rate on the 150th day (the decomposition rate is approximately 343°C for the fraction above 650'F)
(650°F) or less. same as below. ) was as follows.

15th day 0 29.5% 150th day 0 minute 9.0% Example 11 Hydrocracking reaction of atmospheric residual oil was carried out by combining catalyst F-1 prepared in Example 1 with pretreated catalyst A. .

The properties of the pretreatment catalyst Af) used are as follows.

Chemical composition Ni0 5.0% by weight MoO320,
5' AJ203 Remaining amount aIB Physical specific surface area 131 cc/I Pore volume 0.367 cc/1 Average pore diameter 87A The same normal pressure residual oil used in Comparative Example 3 was passed through the pretreatment catalyst together with hydrogen, and then The entire product was then passed through catalyst F-1.

The reaction using the pretreatment catalyst was carried out under the following conditions.

Catalyst amount 15 mj Raw oil liquid space velocity 0.6 hr-'' Reaction pressure (hydrogen pressure) 105 Yu/cd Reaction temperature 400°C Hydrogen/oil ratio 2670 Nil/II catalyst F-1
The reaction was carried out under the following conditions.

Catalyst amount 157FL1 raw material/l1lf1. Space velocity 0. ．． 6hr-' Reaction pressure (hydrogen pressure) 105 Yu/d Reaction temperature 400°C Hydrogen/oil ratio 267 ONl/1 0 total decomposition rate on the 15th and 150th day after the start of the reaction,
The desulfurization and denitrification cables were as follows.

(Decomposition rate) (Desulfurization) (Denitrification cable) 15th day 0 20.0% 85% 60% 150th day Clogging, 0% 80% 50% Note that the liquid space velocity in this example is the pretreatment catalyst and catalyst F-1, the total amount is 0.3 hr.

Example 12 By combining catalyst F-1 prepared in Example 1 with pretreated catalyst B, a hydrocracking reaction of atmospheric residual oil was carried out.

The properties of the pretreatment catalyst B used were as follows.

Chemical composition Co0 4. OJi amount%MoO312,
5' SiO□ 0.5. lE amount % Al2O3 remaining amount Physical properties Specific surface area 130 doll pore volume 0.
69 cc/1 Average pore diameter 171 For the reaction, the same flow reactor as used in Comparative Example 3 was used, and 5 rgl of pretreated catalyst B was added to the upper layer of the reactor.

The lower layer was filled with 15% of catalyst F-1, and the same atmospheric residual oil used in Comparative Example 3 was passed together with hydrogen into the reactor in a downward flow to carry out a reaction under the following conditions.

Reaction temperature 400°C Raw material oil/liquid space velocity 0.3 hr-1 (relative to total catalyst amount)
Reaction pressure (hydrogen pressure) 105 to 97a! hydrogen/oil
Ratio 267ONI/1 The zero synthesis rates on the 15th day and 150th day after the start of the reaction were as follows.

15th day 0 24.0% 150th day 0 16.0% Comparative Example 4 Using the catalyst F-1 prepared in Example 1, a hydrocracking reaction of vacuum distillate oil was carried out.

The properties of the vacuum distillate oil used as the reaction raw material were as follows.

Vacuum distillate oil properties Specific gravity 15/4CO, 9223 Pour point ``C+35.0 Viscosity 50℃cst 36.53 Sulfur content % 2.45 Nitrogen content 0.084 Ni <0.0001V
<0.0001 residual carbon #
0.41 Ash content <o, ooi Vacuum fractionation properties (pressure exchange value) Initial boiling point, C351 50vo 1% point, Ic 452 97vo 1% point, "C572 The reaction was carried out using the same flow reactor as used in Comparative Example 3. The reaction was carried out under the following reaction conditions.

Catalyst amount 15- Reaction temperature 400°C Raw material oil/liquid space velocity 1. Ohr-' reaction pressure (hydrogen pressure) 80 to 9/cd hydrogen/oil ratio 267
The 0 synthesis rates on the 15th and 150th day after the start of the 0 Nl/1 reaction were 35.0% and 12.0%, respectively. Example 13 A hydrotreating reaction was carried out by passing the same vacuum distillate used in Comparative Example 4 together with hydrogen into a flow reactor filled with the same pretreatment catalyst A used in Example 11. The reaction was carried out for about 15 days under the following conditions.

Catalyst amount 500- Reaction temperature 390°C Raw material oil/liquid space velocity 2. Ohr” Reaction pressure (hydrogen pressure) 80kg/d Hydrogen/oil ratio
2670 Nl/It The sulfur and nitrogen contents in the aggregate product oil of the reaction over about 15 days and the decomposition rate caused by the reaction were as follows.

Sulfur content and nitrogen content in the pretreatment reaction product oil Sulfur content % 0.29 Nitrogen content 1 0.019 Decomposition rate in the pretreatment reaction 5% Next, this product oil was used as a raw material oil, and the catalyst prepared in Example 1 with hydrogen was used. A hydrogenolysis reaction was carried out by passing through a flow reactor filled with F-1.

The reaction was conducted under the following conditions.

Catalyst amount 15m7' Reaction temperature 400℃ Raw material oil/liquid space velocity 2. Ohr"'-' Reaction pressure (hydrogen pressure) 80 Yu/cd Water R/m ratio
267ONノ/! The total decomposition rate (in terms of vacuum distillate oil) including the zero pretreatment reaction and decomposition reaction on the 15th and 150th day after the start of the reaction was as follows.

15th day 0 33.5% 150th day 0 30.5% Example 14 Catalyst F-1 prepared in Example 1 was combined with pretreated catalyst A and the same vacuum distillation as used in the reactor of Comparative Example 4 was carried out. The hydrocracking reaction of oil was carried out again.

A flow reactor similar to that used in Comparative Example 3 filled with IQmj catalyst A and a flow reactor similar to that used in Comparative Example 3 filled with 104 catalyst F-1 were connected in series.

Next, the vacuum distillate oil was passed through the two connected reactors together with hydrogen so as to flow downward into each reactor to carry out a reaction.

The entire product of the first step was passed to the second step.

The reaction was carried out under the following conditions.

Pretreatment reaction catalyst amount using pretreatment catalyst A: 10 milk! Reaction 1 degree 390℃ Raw material oil liquid space velocity 2. Ohr Reaction pressure (hydrogen pressure) 80 kliF/cd Hydrogen/oil ratio 2670 Nl/1 Hydrogenolysis reaction catalyst amount using catalyst F-1 IQmj Reaction temperature 400°C Feedstock oil/liquid space velocity 2. Ohr' reaction pressure (hydrogen pressure) 130 to 9/cd hydrogen/oil
The total decomposition rates on the 15th day and 150th day after the start of the ratio 2670 Nil/II reaction were as follows.

15th day 0 32°5% Before 150th day 0 29.5% Comparative Example 5 Hydrogenation of the same vacuum distillate as used in the reaction of Comparative Example 4 using the catalyst F-5fJl prepared in Example 3. The decomposition reaction was carried out under the following conditions.

Catalyst amount 15 mJ' Reaction temperature 400°C Raw material oil/liquid space velocity 1. Ohr Reaction pressure (hydrogen pressure) 80 YU/d Water-hydrogen extraction ratio 267 ONl/1 15 after the start of the reaction
The pre-zero solution rates on day 150 and day 150 were as follows.

15th day 0 36.0% Before 150th day 0 12.0% Example 15 Catalyst F-5 prepared in Example 3 was combined with pretreated catalyst C and the same vacuum distillate was used in the reaction of Comparative Example 4. A hydrogenolysis reaction was carried out.

The properties of pretreatment catalyst C are as follows.

Chemical composition Co 0 3.8% by weight MoO323,
4' people! 20. Residue physical properties Specific surface area 210 m/I Pore volume 0.380 cc/1 Average pore diameter 80 A Same as the flow reactor used in Comparative Example 3 filled with 51 mj of catalyst C (15 mj of catalyst F-5 Charge the temperature
The same flow reactors as used in Comparative Example 3 were connected in series.

Next, one reaction was carried out by passing the above-mentioned vacuum distillate oil into the two connected reactors together with hydrogen in a downward flow to each reactor.

The entire product of the first stage feed was passed to the second stage.

The reaction was carried out under the following conditions.

Pretreatment reaction with pretreatment catalyst C Catalyst amount: 5m Reaction temperature: 390°C Raw material oil/liquid space velocity 4. Ohr-” Reaction pressure (hydrogen pressure) 80 to 9/d hydrogen/oil ratio
26'1 ONl/1 Hydrogenolysis reaction catalyst amount with catalyst F-5 15 rrtl Reaction temperature 400°C Raw material oil liquid space velocity 1.3hr'' Reaction pressure (hydrogen pressure) 80 to 9/d hydrogen/Tsukuda ratio 2670 Nl/ 1 The total decomposition rate, desulfurization S, and denitrification cable on the 15th day and 15050th day after the start of the reaction were as follows.

(Decomposition rate) (Desulfurization rate) (Denitrification &) 15th day 34.5% 99% 85% 150th day 3 Clogging 8% 95% 85% Example 16 In Example 14, instead of catalyst F-1 K.

Exactly the same reaction as in Example 14 was carried out using catalyst F-6 prepared in Example 4. 15 days after the start of the reaction and 1
The resolution rate on day 5050 was as follows.

15th day 31.3% 15050th day 28.8% Example 17 In Example 14, using catalyst F-7 prepared in Example 5 instead of catalyst F-1,! i! Exactly the same reaction as in Example 14 was carried out. 15 days after the start of the reaction and 1505
The resolution rate on day 0 was as follows.

15th day 30.4% 15050th day 26.5% Example 18 In Example 14, instead of catalyst F-1.

Using the catalyst F-8ft prepared in Example 6, Example 14
I had exactly the same reaction. The dissolution rates on the 15th day and 15050th day after the start of the reaction were as follows.

15th day 34.0% 15050th day 26.7% Example 19 In Example 14 instead of catalyst F-°1.

Exactly the same reaction as in Example 14 was carried out using catalyst F-9 prepared in Example 7. 15 days after the start of the reaction and 1
5050th day decomposition rate, desulfurization rate.

The denitrification rate was as follows.

(Decomposition 'a) (Denitrification rate) (Denitrification rate) 15th day 32.7% 98% 89% 150th day Clogging, 6% 98% 88% Comparative example 6 In Comparative example 4, catalyst F-1 Exactly the same reaction as in Comparative Example 4 was carried out using a known catalyst instead. The properties of the known catalyst are as follows.

Chemical composition NiO6, 51% by weight WOs 19.4 t Si02 23.6' Aj203 Residue physical properties Specific surface area 259 m'/jl Pore volume 0.462 cc/j Average pore diameter 54A 15th day and 15050th day after the start of the reaction The estimated accuracy rate was as follows.

15th day 30.0% 15050th day 10.0% Comparative Example 7 In Example 14, the reaction was carried out under exactly the same conditions as in Example 14, using the known catalyst In used in Comparative Example 6 instead of catalyst F-1. Ta.

The dissolution rates on the 15th day and 15050th day after the start of the reaction were as follows.

15th day: 28.0% 150th day: Clogging: 15.0% Table 1 summarizes the results of the decomposition rates of Examples 11 to 19 and Comparative Examples 3 to 7.

As seen in Examples 11-19 and Comparative Examples 3 to 7 in the N11 table, when the crystalline catalyst composition used in the present invention is used alone in the reaction of either atmospheric residual oil or vacuum distillate oil. In contrast, when a reaction is carried out by combining the crystalline catalyst composition with a pretreated catalyst, the crystalline catalyst composition of the feedstock (liquid space relative to Although the decomposition rate is somewhat low due to the high speed, a high decomposition rate is obtained for long-term ashstones of 150 days or more at °C.

This is true regardless of the filling ratio of the pretreatment catalyst and decomposition catalyst, and whether or not gases such as ammonia and hydrogen sulfide generated when passing through the pretreatment catalyst are extracted.
Regardless, the same thing can be said.

As described above, when various hydrocarbons are hydrocracked using the crystalline catalyst composition used in the present invention, a more efficient level of activity can be expected if it is used in combination with a pretreatment catalyst. On the other hand, when a normal hydrocracking catalyst instead of a crystalline catalyst is used as a catalyst, as shown in Comparative Examples 6 and 7, the hydrocracking activity is sharply reduced even when used in combination with a 5 Km treated catalyst. Furthermore, it can be seen that in the process of the present invention, not only the hydrogenolysis activity is high, but also the desulfurization and denitrification rates are at a high level, and the high activity is sustained for a long period of time.

Claims (1)

[Claims] Hydrocarbons are hydrogenated using a pretreatment catalyst consisting of an inorganic oxide, a metal component of group 6 of the periodic table, and a metal component of group 8 of the periodic table, and then crystalline aluminosilicate zeolite is 95% by weight, 5-95% by weight of inorganic oxides,
1 to 20% by weight of Group 6 metal components of the periodic table in terms of oxides
, 0 to 7% by weight of Group 8 metal components of the periodic table in terms of oxides
, and the weight ratio of the Group 6 metal component calculated as phosphorus element and/or boron element to oxide is 0.01 to 0.08, and the phosphorus element and boron element are Each is 0.045
1. A method for hydrocracking hydrocarbons, the method comprising hydrocracking using a crystalline catalyst composition containing a crystalline catalyst composition in a ratio of less than or equal to 1.