JPS60193539A - Composition having fibrous clay mineral - Google Patents

Abstract

PURPOSE:To obtain a catalyst for having excellent durability, activity and mechanical strength for hydrogenation of a heavy gravity hydrocarbon oil by consisting said catalyst of fibrous clay mineral consisting essentially of Mg silicate and inorg. oxide. CONSTITUTION:1-100pts.wt. times of water is added to fibrous clay mineral (e.g., sepiolite) having a double chain structure consisting essentially of Mg silicate and is strongly agitated until an increase in viscosity of the formed pasty material with time is eliminated, thereby forming the pasty material of the clay mineral in which the fiber bundles are highly opened. Inorg. oxide such as silica or inorg. hydroxide such as boehmite is uniformly mixed therewith and the mixture is dehydrated to 40-80wt% moisture. The dehydrated mixture is molded, dried and calcined at 200-800 deg.C. As a result, the compsn. in which the pore volume of the entire compsn. is larger by at least 0.05cc/g than the arithmetic weighted mean of the pore volume possessed by the above-described fibrous clay mineral and inorg. oxide is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a composition with a novel structure consisting of a fibrous clay mineral with a double-chain structure mainly composed of magnesium silicate and an inorganic oxide, a method for producing the same, and the use of the same as a catalyst carrier. The present invention relates to a catalyst for hydrotreating heavy hydrocarbon oil.

In addition to atmospheric distillation residue oil and vacuum distillation residue oil, heavy hydrocarbon oils such as heavy oil extracted from coal, tar sands, and oil sands usually contain large amounts of asphaltenes, heavy metals,
It contains contaminants such as sulfur compounds and nitrogen compounds, which significantly hinders its effective use. Conventionally, in order to effectively utilize such heavy hydrocarbon oils as products with high added value, heavy hydrocarbon oils are brought into contact with a catalyst in the presence of hydrogen to remove the pollutants (hydrogenation). Refining) or cracking into light oil (hydrocracking) has been widely researched and is actually being carried out, but satisfactory results have not yet been obtained, and various improvements are desired. ing. When catalytically hydrotreating such heavy hydrocarbon oils, the biggest technical challenge is the development of a catalyst with excellent durability and activity. That is, the hydrogenation treatment is
This is generally carried out using a fixed bed or boiling bed reaction method, but in this case, the asphaltene contained in the heavy hydrocarbon oil is a macromolecule and difficult to diffuse into the active sites in the catalyst pores. The hydrogenolysis reaction is inhibited, and
The presence of asphaltenes promotes coke formation and reduces catalyst activity, and heavy metals in heavy hydrocarbon oils accumulate on the catalyst surface, significantly shortening catalyst life. There is a problem with putting it away. Therefore, the development of catalysts that can solve these problems has become a major issue.

- Catalysts used for hydrorefining and hydrocracking of heavy hydrocarbon oils containing large amounts of asphaltenes, heavy metals, sulfur, nitrogen, etc. are generally desired to have the following characteristics: There is. First, it must have a pore volume large enough to allow heavy metals to be deposited in significant amounts in order to maintain stable catalytic activity over a long period of time. Second, it has a large pore size that can be advantageously adapted to the diffusion of macromolecules in heavy hydrocarbon oils. A catalyst with a large pore size is also advantageous in that it prevents the surface pores of the catalyst from being blocked by deposits such as metal coke. Furthermore, thirdly, it has sufficient mechanical strength while having the large pore volume and large pore diameter as described above.

Conventionally, from the above point of view, several catalysts have been proposed as catalysts having a composition containing a mixture of clay minerals and inorganic oxides as a carrier are effective for hydrorefining heavy hydrocarbon oils. . For example, JP-A-52-71403 proposes a catalyst in which sepiolite is mixed with an inorganic oxide carrier, and this catalyst can improve the selectivity of demetalization ability with respect to desulfurization ability. Furthermore, according to Japanese Patent Publication No. 52-82690, hydrodesulfurization of heavy hydrocarbon oil consisting of alumina, clay minerals and catalytic metals,
Hydrodemetalization and catalysts effective for hydrodemetallization are disclosed. The above two types of catalysts are intended for desulfurization or demetalization.

On the other hand, according to Japanese Patent Application Laid-Open No. 57-122949, a catalyst composition using a composition comprising a fibrous clay rod and a precalcined inorganic oxide as a carrier is used for hydrodemetalization and hydrogenation of hydrocarbon oil. It is said that it can be used for hydroprocessing such as desulfurization and hydrocracking. The above catalyst has a so-called bimo pore volume peak at both small and large pore diameters.
da Q type, but when the hydrocarbon oil to be treated is heavy hydrocarbon oil, the molecules involved in the reaction have a wide range of sizes, so this kind of imod
A Q-type catalyst has only moderate activity as a catalyst for hydrotreating heavy hydrocarbon oils containing large amounts of asphaltenes, heavy metals, and the like. Also, JP-A-56-
According to JP-A No. 76245 and JP-A No. 76246/1983, catalysts are proposed in which a composition containing a clay mineral and an inorganic oxide is used as a carrier. This catalyst is effective in the hydrogenation treatment of heavy hydrocarbon oils, and the surface activity of the catalyst is improved by adding inorganic oxides without damaging the pore structure developed by clay minerals alone. . Moreover, it is said to have mechanical strength that can withstand practical use. However, according to such catalyst technology, if the proportion of the inorganic oxide added in the composition for the purpose of improving the catalyst surface activity is increased, the pore structure of the clay mineral will be damaged. 1. It becomes difficult to fully exhibit the characteristics of inorganic oxides that exhibit high surface activity in the hydrogenation treatment of heavy oil.

The present inventors have conducted extensive research in order to develop a catalyst for hydrotreating heavy hydrocarbon oils that overcomes the above-mentioned drawbacks found in the prior art. As a result, hydrocracking of heavy hydrocarbon oil,
We have discovered a new composition that has pore volume and pore diameter effective for hydrorefining, exhibits high surface activity for hydrotreating reactions, and has sufficient mechanical strength to withstand practical use.

That is, according to the present invention, the fiber bundles of the fibrous clay mineral are made of an inorganic oxide and a fibrous clay mineral having a double-chain structure mainly composed of magnesium silicate, and the fiber bundles of the fibrous clay mineral are highly defibrated to reduce the total composition. A fibrous clay mineral, characterized in that the pore volume (pv) of the substance is at least 0.05 cc/g larger than the arithmetic weighted average value (PVav) of the pore volumes of the fibrous clay mineral and the inorganic oxide. A composition containing the following is provided.

In general, the pore volume of a composition obtained by mixing two or more types of particles of different sizes is calculated by calculating the pore volume of each component when small particles fit into the voids of large particles. is smaller than the weighted average value,
On the other hand, if small particles cannot fit into the voids made up of large particles, the pore volume of each component becomes approximately the arithmetic weighted average value.

-However, the composition of the present invention uses the clay mineral as a raw material not in the form of the fiber bundle that it originally constitutes, but in the form of individual fibers obtained by sufficiently defibrating the fiber bundle, Since these are combined with inorganic oxides, there are cases where clay minerals and inorganic oxides are simply mixed using conventional technology, and cases where insufficiently defibrated clay minerals and inorganic oxides are combined. It has the following properties that could not be expressed by the composition obtained by doing so.

The first characteristic of the composition of the present invention is that it has a pore volume larger than the arithmetic weighted average value of the pore volumes of the fibrous clay and the inorganic oxide. That is, the proportion by weight of the fibrous clay having a pore volume of PV 1 cc/g and the inorganic oxide having a pore volume of PV 2 cc/g in the composition of the fibrous clay. If it exists in
The pore volume PVcc/g of the composition of the present invention is PV>PVav=W-PV t + (1-W) PV
2 (1).

It has also been found that the amount of increase in the pore volume of the composition of the present invention relative to the arithmetic weighted average value of the raw material components is expressed by the following formula (2).

PV PVav-KW(1-1)=K(W-1+l"
) (2) Pv: Composition pore volume (cc/g) PVav: Arithmetic weighted average value of pore volume of fibrous clay with inorganic oxide (cc/g) w Fibrous clay in two sets of acids Weight fraction K: fibrous coefficient of fibrous clay (cc/g) from the above formula (2
), the amount of increase in pore volume of the composition of the present invention is
It is determined by the fibrous coefficient (K) described later and the weight fraction of the fibrous clay mixed. In order to significantly express the characteristics of the composition of the present invention, the pore volume increase amount must be 0.05c.
c/g or more, more preferably O,
It is desirable that it be at least Ice/g.

A second characteristic of the composition of the present invention is that once a fibrous clay with a specific fibrous clay coefficient is selected, its proportion in the composition can be arbitrarily selected in order to obtain a catalyst with a desired pore volume. This is something that can be done. That is, in the case of the composition of the present invention, over a wide range of mixing ratios of fibrous clay and inorganic oxide,
It is possible to have a pore volume with a large pore diameter. Furthermore, the third
The characteristics of this composition are that it has a large pore volume over a wide range of mixing ratios, and yet has high mechanical strength.

This is thought to be because highly dispersed fibrous particles exist in the inorganic oxide, and the fibrous particles exhibit an effect similar to reinforcing bars in concrete.

The reason why the composition of the present invention has the above-mentioned unique properties is considered to be due to the following reasons. That is, the composition of the present invention has a three-dimensional structure made of highly dispersed fibrous clay, and the inorganic oxide particles have a reinforcing effect to maintain the three-dimensional structure. It has the effect of counteracting the shrinkage of pores due to the surface tension of water that acts when water is removed during the firing process, and as a result, the three-dimensional structure is maintained. It is thought that it has the above-mentioned properties that could not be exhibited at all in a composition obtained by mixing the above-mentioned substances. As mentioned above, the manifestation of such characteristics is mainly due to the properties of the fibrous clay mineral used in the present invention, and the fibrous coefficient (K) of the fibrous clay in the above formula (2) is It expresses the properties based on both the fibrous nature of the mineral and the dispersibility of its fibers. The magnitude of this coefficient represents the degree of fibrousness of the fibrous clay mineral and the degree of dispersion of individual fibers. That is, if the fibrous coefficient (K) is large, the fibers of the clay mineral are long and the fibrous property is developed, and if the fibrous coefficient (K) is small, the fibers are short and the fibrous property is not developed. Further, in the case of the same fibrous clay mineral, if the fibrous coefficient (K) is large, it indicates that the individual fibers of the fibrous clay mineral are well dispersed. To be more precise, the fibrous coefficient of the fibrous clay mineral in the present invention can be obtained from the above formula (2) by manufacturing a large number of compositions and using the pore volume values of these compositions. However,
The inventors studied this relationship and found that fibrous clay minerals are generally mechanically dispersed, and that the viscosity of the colloidal solution is closely related to the fibrous nature of the clay mineral and the degree of dispersion of individual fibers. I found it. That is, the greater the fibrous nature and the longer the fibers, the greater the viscosity, or the better the degree of dispersion, the greater the viscosity. Therefore, the fibrous coefficient (K
) was also found to be closely related to the viscosity of the colloidal solution after dispersing the clay mineral. Therefore, after the fibers in the fibrous clay mineral are well dispersed, if the relationship between the viscosity of the colloidal solution and the fibrous coefficient (K) is known, it is easy to measure the viscosity of the colloidal solution of the fibrous clay mineral. By using this method, the fibrous properties and degree of dispersion of the clay mineral can be seen comprehensively, and the fibrous coefficient can be easily estimated.

The relationship between the viscosity and fibrous coefficient of this clay mineral colloidal solution is shown in the drawing. The relationships shown in this drawing were established in the following manner.

(1) Viscosity of a colloidal solution of clay minerals Add water to the clay minerals as much as possible to make the solid content concentration 4% by weight. Gap 0.5mm
The colloidal solution was placed in a rotating blade (rotating speed: 150 m) and defibrated for 10 minutes while applying a shearing force, and the viscosity of the obtained colloidal solution at room temperature was measured using a rotational viscometer manufactured by Rion.

(2) Fibrous coefficient Using the colloidal solution of clay mineral obtained by the method described above, various compositions were manufactured, and the pore volume values of the compositions were measured. Calculate the coefficient (K).

The relationship between the fibrous coefficient (K) and the viscosity of the clay mineral colloid solution shown in the drawing represents the difference in the fibrous properties of the fibrous clay minerals. In addition, the correlation between the drawings also agrees well with the dispersibility of individual fibers of the fibrous clay mineral. Therefore, if the fibrous clay fiber bundle is insufficiently defibrated, the viscosity of the colloidal solution will not increase, and the fibrous coefficient (
It is clear that the clay mineral has a small K), that is, the fibers are not fibrillated very much. In such a case.

A composition having a pore volume 0.05 cc/g larger than the arithmetic weighted average value of the pore volumes of the fibrous clay and the inorganic oxide can no longer be obtained.

Next, a method for producing the composition of the present invention will be explained. In this case, in particular, the step of defibrating the fiber bundles constituting the clay mineral to obtain fibrous clay and the step of mixing the clay with the inorganic oxide are extremely important.

The composition of the present invention can be manufactured by the following series of steps.

(a) As a fibrous clay mineral, a clay mineral with a double-chain structure mainly composed of magnesium silicate is used as it is or is crushed, and water is added in an amount of 1 to 100 times, preferably 5 to 50 times the weight of the clay mineral. In addition, the fiber bundles are defibrated by strongly stirring the clay mineral-water mixture to produce a paste-like material in which the fibers are highly dispersed. In this case, strong stirring is performed until the viscosity of the paste material substantially disappears over time.

(b) Step (a) Adding an inorganic oxide or inorganic hydroxide as it is or as a slurry to the paste-like material and mixing thoroughly.

(c) dehydrating the pasty mixture obtained in step (b) until the water content becomes 40 to 80% by weight; (d) molding the pasty mixture from step (c); A process of drying until the solid content becomes 30% by weight or more, and then firing at a temperature range of 200 to 80°C for 0.1 to 10 hours.

The step (a) is a step for obtaining a fibrous clay in which the fiber bundles, which are the first component of the composition of the present invention, are highly defibrated. In the process, it is necessary to apply sufficient shearing force to the clay mineral to highly defibrate the fiber bundles.

The fibrous clay mineral used in the present invention is specifically a porous magnesium silicate called sepiolite, attapulgite, or palygoskite. In the case of the present invention,
1 of these clay minerals alone or as a mixture, either as they are or in pulverized form, particularly preferably in the form of granules with a particle size of 40 mesh or more and 20 cm or less.
-100 times the weight, preferably 5 to 50 times the weight of water is added, and the fibers are dispersed while stirring the mixture using a colloid mill or a wet grinder capable of applying strong shearing force, such as a homogenizer.

As the fibers are dispersed, the mixture becomes gel-like and its viscosity increases significantly.

In this state, the fiber bundles of clay minerals are being defibrated into individual fibers by shearing force, and these fibers are being dispersed. In other words, the fibrous coefficient of the clay is increasing. It can be said that it is a state. If stirring is carried out sufficiently, the viscosity will hardly increase over time, and at this stage, a desired pasty fibrous clay having a sufficiently large fibrous coefficient can be obtained. In the case of the present invention, it is generally preferable to use a defibrated clay having a fibrous coefficient (K) of 0.2 or more, preferably 0.4 or more.

The pasty clay obtained by the above method is mixed with an inorganic oxide or an inorganic hydroxide in the method shown in step (b). In this case, examples of the inorganic oxide include alumina,
One selected from magnesia, boria, silica, titania, and zirconia or a mixture thereof is preferably used, but the material is not limited to these. Inorganic oxides known as catalyst supports are generally applicable. In addition, as inorganic hydroxide,
Examples include alumina hydrates such as gibbsite, viarite, nordstrandite, boehmite, pseudoboehmite, diasbore, and amorphous alumina gel, as well as magnesium hydroxide, silica sol, titanium hydroxide, and hydroxide film zirconium. 6 In the case of the present invention, the above-mentioned inorganic oxides and inorganic hydroxides can be added in powder form to the paste clay from step (a), but it is generally preferable to add them as a slurry. Wood slurry containing inorganic hydroxides is treated with hydrolyzable metal salts, e.g.
It can be obtained by hydrolyzing chlorides, sulfates, nitrates, etc.

The pore volume of the inorganic oxide or inorganic hydroxide described above is desirably large in order to increase the pore volume of the composition of the present invention, but if it is extremely large, the pore volume of the fibrous clay Even if it has a strong reinforcing effect, the strength of the composition will be insufficient, so it is generally desirable to have a content in the range of 0.2 to 2.0 cc/g.

When the inorganic oxide or inorganic hydroxide is mixed into the paste clay, the addition ratio of the inorganic oxide or inorganic hydroxide is adjusted so that the amount of increase in pore volume expressed by the above formula (2) falls within the desired range. be selected. In this case, by selecting the physical properties of both, a wide range of mixing ratios can be achieved with respect to the pore volume of the desired composition.

In the present invention, as shown from the above formula (2),
The amount of increase in the pore volume of the present composition relative to the arithmetic weighted average value of the pore volumes of the two components varies depending on the mixing ratio of both groups of acids, but the mixture can provide an increase of 0.05 cc/g or more, which is the objective of the present invention. The ratio is approximately 0.08 to 0.92 by weight of fibrous clay when the fibrous index is in the range of 0.7 to 0.9.
and can be varied over a wide range. This is a great advantage of the present invention, but the reason why such a wide range of mixing is possible is that the fibrous properties and dispersibility of the fibrous clay are comprehensively judged by the viscosity of the colloidal solution of the clay. This is done by using clay that has been sufficiently defibrated and has fibers dispersed in it.

In the present invention, when selecting and mixing fibrous clay and inorganic oxide or hydroxide, the mixing ratio for obtaining a composition having a desired pore volume is limited to a specific value. It is particularly noteworthy here that there are cases where it is possible to mix two different proportions in order to obtain a composition with a desired pore volume. For example, using a fibrous clay with a fibrous index of 0.8 and a pore volume of 0.88 cc/g and an inorganic oxide or hydroxide with a pore volume of 0.8 cc/g. When trying to obtain a composition having a pore volume of 1.1.0 cc/g, according to the above formula (2), the weight fraction of the fibrous clay is 0.32 or 0.32 cc/g.
It is possible to mix at two mixing ratios of 78, and in both cases the pore volume is 1° Occ/g, and the increase in pore volume relative to the arithmetic weighted average is 0.17 cc in each case.
/g and 0.14 cc/H of the composition is obtained. However, if the mixing ratio is other than this, the desired composition cannot be obtained1\.

The reason why such a characteristic binary aromatic mixture is produced in the production of the present invention is that the pore volume value Pv of the component of the present invention is larger than the arithmetic weighted average value PVav of the pore volume values of the two components. This is due to the unique characteristic 1 of the composition of the present invention.

Next, the slurry-like clay mixed as described above is
The inorganic hydroxide mixture becomes the composition of the present invention through the steps of dehydration, molding, drying, and baking.

In addition, when catalyzing the present composition, hydrogenation-active metal components present in the form of metals, oxides or sulfides, such as groups Vl-B and group I of the periodic table, may be added to the composition. At least one catalyst metal component selected from the elements is supported. Specifically, these catalytic metal components include molybdenum, chromium, copper, nickel, tungsten, novenadium, and copper. Methods for supporting such catalytic metal components are conventionally known, such as impregnation. It can be carried out by various methods such as method, spray method, etc.

The composition of the present invention has a pore volume of 0.6 to 2.0 (c/g).

It is desirable to have an average pore diameter of 200 or more.

Preferably, the pore distribution of the composition is such that at least 50% of the pore volume has a pore diameter greater than 200 pores, and more preferably at least 30% of the pore volume.
has a pore diameter of 400 Å or more. Also,
The composition of the invention is characterized by good mechanical strength (SC5) despite having a large pore volume. For example, in the case of the present invention, P%IO, 9cc
/g or more, a composition having a strength of SC5O, 5 kg/lff112 or more can be obtained.

In this case, mechanical strength (SCS) is measured as follows.

That is, the sample is fired at 450° C. for 1 hour, then pressurized with a cylinder that compresses at a constant speed using Deci air pressure, and the load at which the sample particles are destroyed is measured.

Mechanical strength is determined by performing such measurements on one sample.
The average breaking load is expressed with respect to the particle length per llIn, and when the particle diameters are different, the values are converted to a diameter of 1 mmφ.

According to a preferred embodiment of the present invention, alumina 70-80% by weight, PV O, 9-lcc/g, SC3O, 5 kg
/mm'' or more is provided, and this composition is particularly suitable as a catalyst support for the hydrotreatment of heavy hydrocarbon oils.

The composition of the present invention is generally extremely effective as a catalyst carrier for hydrorefining or hydrocracking of heavy hydrocarbon oils.

That is, since the present composition has the property of having a pore volume larger than the arithmetic weighted average value of the pore volumes of its components, it is possible to relatively easily develop a sufficiently large pore volume. However, catalyst compositions with such large pore volumes exhibit strong resistance to poisoning due to the deposition of heavy metals contained in heavy hydrocarbons or coke precipitation, and are stable over long periods of time. Can remain active. Furthermore, the present composition has the above-mentioned properties because the fibrous clay is present in the composition in the form of individual fibers and is sufficiently dispersed. The labyrinth degree of the hole is small,
It is believed that each pore can be effectively used for the reaction.

In addition, since more than 50% of the pore volume has a pore diameter larger than 200 pores, macromolecules in heavy hydrocarbon oil can quickly diffuse to the active sites, and fine particles such as heavy metals and coke can be absorbed quickly. The deposition within the pores tends to be uniform, and therefore, it can be said that the composition of the present invention has a high degree of effectiveness in terms of catalyst surface area. In addition, in the composition of the present invention, if 30% or more of the pore volume has a diameter larger than 400 pores, the macromolecules in the heavy hydrocarbon oil will more easily diffuse through the pores. It can be said that it is particularly effective as a catalyst for hydrocracking treatment carried out under high temperature conditions where diffusion resistance increases. Furthermore, according to the present invention, it is possible to improve the pore structure characteristics of the fibrous clay and to adjust the mixing ratio of inorganic oxides in the composition over a wide range, so that the composition of the present invention can be hydrogenated. Has high surface activity for reactions.

By contacting heavy hydrocarbon oil with hydrogen under normal hydrotreating conditions using the catalyst of the present invention, asphaltenes, heavy metals, sulfur, etc. in the heavy hydrocarbon oil can be removed, and Conradson residues can be removed. It is possible to reduce the carbon content, specific gravity, and viscosity, and to convert high boiling point heavy hydrocarbon oil into low boiling point hydrocarbon oil.

The composition of the present invention, its manufacturing method, effects, fields of application, etc. have been described above, but in order to further clarify the present invention, the following examples are given. These Examples specifically explain the present invention, and the present invention should not be limited by these Examples.

Preparation Example 1 of Fibrous Clay Spanish sepiolite was crushed as it was in a crusher to obtain sepiolite granules having a particle size of about 48 mesh to about 30+m. 400 g of the sepiolite granules and about 8 Q of city water were put into a Trigonal wet pulverizer manufactured by Mitsui Miike Manufacturing Co., Ltd. and vigorously stirred for 10 minutes to obtain a paste.

Next, this paste-like material was filtered and dehydrated using a vacuum filter to obtain about 1100 g of cake. This cake 1, 2
The molded product was extruded into a cylindrical shape of n++++φ, dried with hot air at about 120° C. for 3 hours, and then fired at about 500° C. for 3 hours to obtain fibrous clay fired product I.

Preparation Example 2 of Fibrous Clay Using the same Spanish sepiolite used in Preparation Example 1 of the fibrous clay, purified according to the method disclosed in JP-A-58-51939, fibrous clay was prepared. Fibrous clay fired product (2) was obtained in the same manner as in Preparation Example 1.

Preparation Example 3 of Fibrous Clay Fibrous clay fired product (2) was obtained in the same manner as in Preparation Example 1 of Fibrous Clay except that Korean sepiolite was used.

Preparation Example 4 of Fibrous Clay SoQ 5peedi D from Engelhardt, USA
Using attapulgite commercially available as ri, a fired fibrous clay product ■
I got it.

Fibrous clay fired product I shown in the above fibrous clay preparation example
Table 1 shows the properties of , ■, ■, ■, the fibrous coefficient of the fibrous clay, and the measured viscosity at room temperature of the paste obtained in the preparation process.

Note that the measured values regarding the pore structure used in this specification are the values measured for a pore portion having a pore diameter of 75 Å or more by mercury porosimetry using a porosimeter manufactured by CARLOERBA, Italy.

Table-1 Inorganic hydroxide-containing slurry preparation example 1 According to the method for producing an alumina carrier disclosed in JP-A-55-27830, aluminum sulfate and sodium aluminate were used as raw materials to prepare aluminum hydroxide-containing slurries a and b. , obtained c. These slurries were dehydrated, filtered and washed, extruded, dried at about 120°C for 3 hours, and further calcined at about 500"C for 3 hours.
Alumina A, B, and C were obtained, respectively.

Inorganic hydroxide-containing slurry preparation example 2 Sodium aluminate 1 with a concentration of 8% by weight in terms of AQ203
30 kg and 300 Q of city water were charged into a reactor having a volume of 7 ooQ, and heated to about 100°C. In this reactor, AQ
203 equivalent 20 equivalent 20 sukkai aluminum approximately 200k
The slurry d was continuously charged at a constant rate of g/hr for about 60 minutes to obtain aluminum hydroxide-containing slurry d. Alumina D was obtained from this slurry in the same manner as in inorganic hydroxide-containing slurry preparation example 1.

Inorganic hydroxide-containing slurry preparation example 3 100 g of titanium tetrachloride was dissolved in about 800 cc of city water, and 28% by weight aqueous ammonia was added to the solution until the pH was 8.
After addition, the slurry was aged at about 100'C for 20 hours to obtain titanium hydroxide-containing slurry e. Titania E was obtained from this slurry in the same manner as in inorganic hydroxide-containing slurry preparation example 1.

Table 2 shows the properties of the inorganic oxides A-H shown in the above inorganic hydroxide-containing slurry preparation examples.

Table 2 Example 1 Seviolite paste similar to that described in Preparation Example 1 of fibrous clay and aluminum hydroxide-containing slurry a were
The mixture was mixed at the mixing ratio shown in Table 3 so that the total solid weight was about 40 g, and about 1.8 Q of water was added, followed by stirring for about 1 minute using a paddle mixer.

The mixture was dehydrated using a vacuum filter to obtain about 130 g of cake. Thereafter, it was molded, dried, and fired in the same manner as in Preparation Example 1 of Fibrous Clay to obtain Composition (1).

Example 2 As described in Preparation Example 2 of fibrous clay at the mixing ratio shown in Table 3,
Example 1 was prepared by using the same Seviolite paste and aluminum hydroxide-containing slurry b as described in Preparation Example 3, and using the same Seviolite paste and aluminum hydroxide-containing slurry 〇 as described in Preparation Example 3. Compositions (2) and (3) were obtained in the same manner as above. In addition, the same attapulgite paste and aluminum hydroxide-containing slurry d as described in Preparation Example 4 were used, and
Compositions (4) and (5) were obtained in the same manner as in Example 1 using the same sepiolite-like material and titanium hydroxide-containing slurry ○ as described in Preparation Example 1.

Comparative Example 1 The Spanish sepiolite used in Fibrous Clay Preparation Example 2 was ground into fine particles of 40 mesh or less, and the cake obtained by dehydrating aluminum hydroxide-containing slurry C was added to the sepiolite powder. and alumina so that the weight ratio is 3:1, and further water is added so that the water content is about 63% by weight, and this mixture is mixed with a mixer to
The mixture was kneaded for hours to obtain a kneaded product. Below, this kneaded material is molded,
It was dried and fired to obtain a composition (6). Further, a fired clay mineral product (2) was obtained in the same manner as above without adding the cake obtained from the aluminum hydroxide-containing slurry to the sepiolite powder.

Compositions (1) to (6) shown in the above Examples and Comparative Examples
), the amount of increase in pore volume with respect to the arithmetic weighted average value, and the pore volume value calculated from the above formula (2) (PV=K
(W−W”)+PVav) are summarized in Table 3.

As shown in Table 3 above, compositions (1) to 1 of the present invention
The pore volumes of (5) all approximately match the pore volume values obtained by equation (2). Moreover, composition (1) -
(5) has a pore volume that is 0.05 cc/g or more larger than the pore volume weighted average value (PVav) of the fibrous clay and the inorganic oxide. In particular, compositions (2) and (3) using fibrous clays (1) and (2) having a large fibrous coefficient have pore volumes that are 0.2 cc/g or more larger than the arithmetic weighted average value. On the other hand, the pore volume of Comparative Example Composition (6) is smaller than the arithmetic weighted average value.

Furthermore, even when the mixing ratio of fibrous clay is small as in composition (1), or when the inorganic oxide is of relatively small pore type as in compositions (2) and (5), Even if there is, all the compositions of the present invention have a larger pore volume on the outer diameter side. Furthermore, compositions (1) to (5) of the present invention
) has a large pore volume, and its mechanical strength is increased due to the inclusion of fibrous clay. for example,
Composition (1) is a mixture of only 20% by weight of fibrous clay in inorganic oxide A, but compared to inorganic oxide A, although the pore volume is increased, the strength is has improved significantly.

Example 3 60 cc of warm water was added to 12.0 g of ammonium molybdate, and an aqueous solution obtained by dissolving 12.6 g of cobalt nitrate in 30 cc of distilled water was added, mixed, and 45 cc of aqueous ammonia with a concentration of 28% by weight was added. . Distilled water was further added to the liquid to adjust the mixed liquid volume to 150 cc.

30 cc of this liquid was collected and the resulting composition (1)
After 30 g of the catalyst was uniformly impregnated and left sealed for one day and night, it was dried with hot air at about 120°C for 3 hours and further calcined at about 500°C for 3 hours to obtain catalyst (a).

Comparative Example 2 Catalytic metals were supported on the fired fibrous clay material (1) containing no inorganic oxide and the composition (6) of Comparative Example 1 in the same manner as in Example 3, and catalysts (2) and (2) were supported, respectively. c) was obtained.

Table 4 shows the properties of catalysts (a), (b), and (c) shown in Example 1 and Comparative Example above.

Table 4 Example 4 Using catalysts (a), (b), and (c), heavy hydrocarbon oil having the properties shown in table 5 was treated under the reaction conditions shown in table 6 with a catalyst loading of 30 cc. Hydrogenation was carried out using a fixed bed flow reactor equipped with a reactor. About 300 hours after the start of oil passage, the reaction product was sampled and subjected to analysis. The results of the hydrogenation treatment are shown in Table-7.

Table 5 Table 6 Table 7 As shown in Tables 3 and 4, the catalyst composition (a) of the present invention has a high content of inorganic oxides, but it is effective against heavy hydrocarbon oils. It has a pore structure suitable for hydrogenation treatment. In addition, as shown in Table 7, the present catalyst composition (a) was more effective in asphaltene decomposition reaction and demetalization reaction than the catalyst containing no inorganic oxide (b) and the catalyst (c) of Comparative Example 2. It shows high reaction activity in all types of desulfurization and desulfurization reactions.

In addition, after 600 hours had passed after the start of oil passage, the catalysts (a) and (c) used in the hydrogenation treatment were taken out, and the state of vanadium deposited within the spent catalyst particles was analyzed using an X-ray microanalyzer. A catalyst effectiveness coefficient was calculated based on the value, and the effectiveness of the catalyst pores was determined. According to this,
The effectiveness coefficient of the catalyst (c) whose pore volume was smaller than the arithmetic weighted average value was 0.66, whereas the catalyst (a) of the present invention had an average pore diameter smaller than that of the catalyst (c). Although it was small, it showed a large effective coefficient of 0.78. This indicates that the composition of the present invention has a pore volume larger than the arithmetic weighted average value, so that the pores are used extremely effectively.

[Brief explanation of the drawing]

The drawing shows the relationship between the viscosity of a colloidal solution of clay minerals and the fibrous coefficient of the clay. Patent applicant Toshiaki Ikeura, patent attorney representing Chiyoda Corporation

Claims (8)

[Claims] (1) Consisting of a fibrous clay mineral with a double-chain structure mainly composed of magnesium silicate and an inorganic oxide, the fiber bundles of the fibrous clay mineral are highly fibrillated to reduce the pore volume of the entire composition. A composition containing a fibrous clay mineral, wherein (PV) is at least 0.05 cc/g larger than the arithmetic weighted average value (PVav) of pore volumes of the fibrous clay mineral and the inorganic oxide. . (2) The composition of claim 1 having a pore volume (PV) of 0.6 to 2.0 cc/g, and at least 50% of the pore volume having a pore diameter greater than 200 cc/g. thing. (3) Pore volume f* (PV) (7) At least 30%
The composition of claim 2, wherein the composition has a pore diameter of greater than 400 pores. (4) Consisting of a fibrous clay mineral with a double-chain structure mainly composed of magnesium silicate, an inorganic oxide, and a hydrogenation-active metal component, the fiber bundles of the fibrous clay mineral are highly defibrated and completely The pore volume (PV) of the composition is at least 0.05 cc/g greater than the arithmetic weighted average value (PVav) of the pore volumes of the fibrous clay mineral and the inorganic oxide.
A catalyst for hydrotreating heavy hydrocarbon oil characterized by its large size. (5) The composition of claim 4 having a pore volume (PV) of 0.6 to 2.0 cc/g, with at least 50% of the pore volume having a pore diameter greater than 200 cc/g. thing. (6) The composition of claim 5, wherein at least 30% of the pore volume (PV) has a pore diameter greater than 400 pores. (7) In a method for producing a composition comprising a fibrous clay mineral having a double-chain structure containing magnesium silicate as a main component and an inorganic oxide, (a) 1 to 100 magnifications relative to the fibrous clay mineral; of water and stirring vigorously until the viscosity of the produced paste substantially disappears over time to produce a clay mineral paste in which the fiber bundles are highly defibrated; (b) For the paste obtained in step (a),
a step of uniformly mixing an inorganic oxide or an inorganic hydroxide; (c) the mixture obtained in step (b) has a moisture content of 40
(d) After molding the mixture obtained in step (c), the solid content is 30% by weight.
Dry until it reaches % by weight or more, and then heat at 200 to 800℃.
The pore volume of the entire composition (
a fibrous clay mineral, characterized in that a composition is obtained in which the pv) is at least 0.05 cc/g greater than the arithmetic weighted average value (pvav) of the pore volumes of the fibrous clay mineral and the inorganic oxide. Method for producing the composition. (8) The mixing ratio of clay minerals and inorganic oxides in the composition is determined by the formula % (where K: fibrous coefficient of fibrous clay W: weight fraction of fibrous clay in the composition). 8. The method of claim 7, wherein the ratio is satisfactory.