JPS596697B2 - Porous modified sepiolite catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a carrier made of porous modified sepiolite in which the silica/magnesia (SiO2/MgO) molar ratio is increased to 4 or more by removing the framework magnesium of natural sepiolite; The present invention relates to a porous modified sepiolite catalyst for hydrotreating comprising a supported hydrogenation active catalyst metal.

Sepiolite is a mineral commonly called sepiolite, which occurs naturally as hydrated magnesia silicate, but can also be synthesized from magnesium salt and silicate.

Since this material is a porous material, it can be used as a catalyst carrier or adsorbent by taking advantage of its porosity, but naturally produced materials have a limit to their porosity and cannot be used as they are. However, depending on the purpose of use, it is often not a sufficiently porous material. In particular, when sepiolite is used as a catalyst carrier, it is necessary to make it porous and adjust the specific surface area and pore volume. Until now, no technical means have been known that can meet such demands.

The present inventors previously discovered that when water is added to natural sepiolite and kneaded, a modified product with significantly increased pore volume and specific surface area can be obtained, and based on this knowledge, sepiolite A method for manufacturing a molded body was proposed (Japanese Patent Application No. 13018/1982).

However, since this method is based only on physical means rather than chemical means, there is a limit to how porous it can be, and the specific surface area of the product fired at 500°C exceeds 300 m"/f. and pore volume (
〉74 people) is 0.9cc/? It was extremely difficult to obtain anything above that.

According to the present invention, there is provided a catalyst for hydrotreating using a porous body made of sepiolite modified by chemical means rather than such physical means as a carrier.

That is, according to the present invention, silica/magnesia (Si02/
Porous modified sepiolite for hydrotreating, comprising a carrier made of powdered or shaped porous modified sepiolite with a molar ratio of MgO) increased to 4 or more, and a catalyst metal for hydrogenation supported on the carrier. A system catalyst is provided.

The carrier used in the present invention is natural sepiolite (a)
A step of increasing the silica/magnesia (SiO2/MgO) molar ratio in sepiolite to 4 or more by reacting an inorganic acid and/or an organic acid, or for this step, (b') kneading and finally hydrating It can be manufactured by combining the steps of adjusting the humidity to 80 to 350% by weight and/or (b) baking in any order.

In this case, the inorganic acid and/or organic acid treatment step (a) of sepiolite and the kneading adjustment treatment step (b'l) can be performed separately or simultaneously.

Furthermore, if desired, shaping steps can be combined by conventional methods in order to obtain shaped carriers.

The modified sepiolite according to the present invention is produced by allowing a reagent capable of reacting with magnesium to act on natural sepiolite as a magnesium desorbing agent.

In this case, various substances that can react with magnesium are used as the magnesium desorbing agent, and specific examples thereof include inorganic salts such as hydrochloric acid, nitric acid, and sulfuric acid;
Organic acids such as formic acid, acetic acid, oxalic acid, tartaric acid, salts whose aqueous solution is acidic such as ammonium hydrochloride, M ammonium, ammonium nitrate (referred to as acid salts in this application), and ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) , chelating agents such as acetylacetone, and the like.

The reaction between sepiolite and the magnesium desorbing agent in the present invention depends on the type of desorbing agent, but is usually carried out in an aqueous medium or an aqueous medium containing water and another suitable organic solvent. and, in some cases, in an organic solvent.

The amount of these reaction media to be used is not particularly limited, but is 100 parts by weight or more, preferably 300 parts by weight or more, based on 100 parts by weight of Sepiolite 1 dry product.

Further, the amount of the magnesium desorbing agent used is 1.2 mol or more, preferably 1.5 mol or more, per 1 mol of magnesium in the sepiolite to be desorbed.

Room temperature is sufficient for the reaction temperature, but since the rate of magnesium desorption from modified sepiolite changes depending on the reaction temperature, a heating temperature of 40 to 300°C, usually 50 to 150°C, can also be employed.

The reaction between sepiolite and the magnesium desorbing agent in the present invention can be carried out using an acid or an acidic salt as the desorbing agent, but in this case, the pH of the solution
pH is 5 or less, preferably in the range of 5 to 1.

Note that the reaction can be carried out even when the pH is below 1,
In this case, the reaction time is shortened.

Furthermore, when using a relatively weakly acidic desorbing agent such as an organic acid, it is preferable to lengthen the reaction time.

After washing the modified sepiolite obtained in this way with water,
Dry and bake if necessary (e.g. 400-700℃)
and use it as a carrier.

The modified sepiolite according to the present invention has a silica/magnesia ratio of Si02/MgO compared to naturally produced sepiolite.
has been greatly increased.

That is, the Si02/MgO ratio in naturally produced sepiolite is less than 4 in molar ratio, but the modified sepiolite according to the present invention has a molar ratio of 4 or more, usually 4.5 to 50,
Generally, it has a high value of about 5 to 10.

Further, the specific surface area and pore volume of the modified sepiolite in the present invention also vary greatly depending on the SiO2/Mgo ratio.

The drawing shows the molar ratio of silica and magnesia, Si02/MgO.
Figure 2 shows the change in specific surface area of modified sepiolite.

In this case, the modified sepiolite is obtained by treating natural sepiolite with hydrochloric acid and then firing it at 500°C.

In the drawings, double circled symbols indicate the SiO2/MgO molar ratio and specific surface area of the raw material sepiolite.

Further, according to the present invention, the modified sepiolite obtained as described above has general physical properties such as a specific surface area of 160 771"/f or more and a specific pore volume of 0.6 cc/7 after firing at 500°C. It has the above.

The specific surface area of modified sepiolite after drying is usually 40
0m”/7 or more.

In the present invention, in order to obtain a support with increased porosity, the magnesium desorption step is combined with a crosstalk step using water as a medium.

That is, sufficient water is added to the modified sepiolite obtained as described above, the mixture is kneaded, and the resulting kneaded product is dried or fired to obtain a product.

Further, this cross-talk step does not necessarily need to be performed after the magnesium desorption step, and can be performed before the magnesium desorption step or simultaneously with the magnesium desorption step.

In this case, the amount of water present during cross-conducting is such that the final water content of sepiolite will be 80 to 350% by weight.

As the kneading means, a molding machine (such as an extruder) may be used in addition to a usual mixer or masticator.

The crosstalk conditions are appropriately determined depending on the desired degree of porosity of the product and its intended use.

This cross-mixing achieves the effect of further improving the specific surface area and pore volume and sharpening the pore distribution, but the more the mixture is mixed, the better the results will be.

According to the present invention, the modified sepiolite can be used as a molded body formed into various shapes such as granules, pellets, pellets, and plates in addition to powder.

There are various ways to make a molded body. For example, after crushing the raw material sepiolite, it is molded into a desired shape, and this molded body is subjected to a magnesium removal treatment. Moistening (humidity control: sepiolite water content 80 to 350% by weight) is kneaded, the resulting kneaded product is molded, and if necessary, calcined, followed by magnesium desorption treatment, pulverizing the raw material sepiolite, A method of molding using the obtained modified sepiolite as a molding material after magnesium desorption treatment. After pulverizing the raw material sepiolite and subjecting it to magnesium desorption treatment, water is added to the obtained modified sepiolite to condition the humidity. humidity: 80 to 350% by weight in terms of sepiolite water content), a method of kneading and molding the obtained mixed wire material, a method of pulverizing raw material sepiolite, kneading this pulverized material at the same time as magnesium desorption treatment, and producing a product obtained by There are ways to mold things.

When producing a molded article of modified sepiolite according to the present invention, it is not particularly necessary to add a molding aid, but the use of a molding aid is advantageous in order to obtain a molded article with high mechanical strength.

As such molding aids, conventional inorganic or organic substances can be used, such as inorganic binders such as silica sol, alumina sol, alumina silica sol, bauxite, akbargite, and montmorillonite, and higher esters, higher alcohols, and higher fatty acids. or salt thereof, starch, carboxymethylcellulose, polyvinyl alcohol, polyacrylic acid, and other organic binders.

The amount of these molding aids to be added varies depending on the type of molding aid used and is difficult to determine unambiguously, but generally it is 0.5 parts by weight per 100 parts by weight of sepiolite on an anhydride basis. ~50 parts by weight, usually 1 to 20 parts by weight.

When producing a modified sepiolite molded body according to the present invention by first forming a raw material sepiolite into a molded body and then subjecting it to magnesium elimination treatment under acidic conditions, the sepiolite molded body tends to be easily powdered under acidic conditions. Therefore, it is necessary to take measures in advance to prevent the powder from turning into powder.

As such means, the raw material sepiolite or its molded product is heated at 200 to 1000°C, preferably 400 to 90°C.
Examples include a method of firing at 00°C, a method of using a forming aid, and a method of softening the magnesium desorption treatment conditions.

Since the modified sepiolite according to the present invention has its skeleton magnesium removed, it is extremely porous compared to natural sepiolite, and can be used as a catalyst carrier by taking advantage of its porosity. .

That is, the modified sepiolite according to the present invention has significantly increased specific surface area and pore volume, and these properties can be adjusted to desired ranges by adjusting the SiO/MgO content in the modified sepiolite. , it can be used as an optimal catalyst carrier for hydrotreating.

As a method for supporting a catalytic metal on the modified sepiolite of the present invention, a conventional method such as a dipping method can be adopted. Since it is possible, an ion exchange method can also be adopted.

In order to support metal by ion exchange method, which metal ion is desired? The modified sepiolite according to the present invention is brought into contact with an aqueous solution containing one or more types under conditions of pH 7 or less.

The hydrogenation-active catalyst metal supported on the modified sepiolite of the present invention includes conventional metals such as Ib group metals such as Cu, Nb group metals such as Zn and Cd, Sc, Y, La,
IIIa group metals such as Ce, ■a group metals such as (:'r, Mo, W, ■a group metals such as Mn1Re, and Fe
, Co, Ni, Ru, Rh, Pd, OS, Ir, and Pt.

In addition, when obtaining a modified sepiolite-based catalyst on which metals are supported according to the present invention, the required metals are supported in advance by an ion exchange method, and then other required metals are supported by a conventional method. Modified sepiolite supporting two or more metals can be obtained.

The amount of metal that can be supported by the ion exchange method is about 4% by weight at most, but when the immersion method is used, or the ion exchange method and the immersion method, it is possible to support an amount of metal as required.

The amount of metal supported when used as a catalyst is generally 40
It is not more than 25% by weight, usually not more than 25% by weight.

Further, the supported metal can take various forms such as oxides and metal salts in addition to the metal state.

The modified sepiolite-based catalyst supporting a hydrogenation-active catalyst metal according to the present invention is used as a solid catalyst in various hydrogenation catalytic reactions.

In this case, the characteristics of the modified sepiolite used as a carrier and the type of metal to be supported are selected depending on the specific type of hydrogenation reaction to be performed.

For example, a modified sepiolite according to the present invention having a SiO/MgO ratio of 2.5 to 6 is supported by replacing a part of magnesium with a metal such as Ni, Co, Fe, Cu, or Cr by an ion exchange method. , or to this periodic table Ib
, nb, ma% V, VIa, ■a, metals supported on one or more selected from Group III metals are suitable for hydrogenation reactions of hydrocarbons such as heavy oil, especially heavy Effective as a catalyst for hydrodemetallization of oil.

Next, the present invention will be explained in more detail with reference to Examples.

Reference example 1 Mg02 7.2%, Sin262.8% on dry basis
, has a composition of 1.4% AI203, 0.4% Fe20g, and 8.2% other crystal water, and has a specific surface area of 140 rrr:/gr and a pore volume of 0.57cc/g after firing at 500°C for 2 hours. gr (>75 people) sepiolite ore is crushed to 10-8 mesh and heated to 120℃.
Dry for 2 hours at room temperature, and add 40 times the weight of 3N hydrochloric acid for 10 minutes at room temperature.
It was soaked for 0 hours to produce a porous body.

During immersion in this hydrochloric acid, intense bubbling was initially exhibited, but it soon stopped, and the resulting aqueous solution was initially colorless and gradually turned yellow.

This is presumed to be due to the dissolution of Fe3+.

Next, the sepiolite obtained by immersion for 100 hours was washed with pure water, dried at 120°C for 2 hours, and further calcined at 500°C for 2 hours to obtain a modified sepiolite porous body.

, when this porous body is analyzed with an X-ray diffraction device, 2θ-1
It was observed that only a broad peak was shown at 8 to 28 degrees, and the characteristic peaks of sepiolite had completely disappeared.

Furthermore, when magnesium and silicon were analyzed using a fluorescent X-ray device, the Si02/MgO molar fraction (or Si/Mg atomic ratio) increased from about 2.0 in the raw material to 7.0, indicating that the It was confirmed that the main component was mostly silicic acid.

Furthermore, when the volume of pores with a diameter of 75 or more was determined using the mercury intrusion method, it was found that the porous material had a diameter of 75 mm or more. slCC/gr, and the specific surface area was determined by the chamber nitrogen adsorption method to be 228 m”/gr.
Met.

From these results, it was confirmed that the pore volume and specific surface area of the modified sepiolite porous material of the present invention were significantly increased by acid treatment.

In addition, the dry product before firing has a specific surface area of 4 1 0 7i/
g and pore volume of 0.7 cc/g.

Reference Example 2 About 40 times the weight of the same sepiolite as that used in Reference Example 1 was added to the o. i Add normal nitric acid aqueous solution and incubate at room temperature for about 10 minutes.
The skeletal magnesium of sepiolite was removed by immersion for 0 hours.

The obtained porous body was dried and fired in the same manner as in Reference Example 1, and then subjected to analysis and measurement.

When this porous body was analyzed with an X-ray diffraction device, it was found from the peak positions and relative intensity ratios that it maintained almost the same structure as the raw material sepiolite.

However, the Si02/MgO molar ratio has increased to 2.4, and the pore volume has increased to 0.6 occ/gr (>7
5 people), but the specific surface area was 2 1 3 m/g
It was observed that the amount increased compared to the raw material.

In addition, the dry product before firing has a specific surface area of 405 m/
g and pore volume o. It showed 5 sec/g.

Reference Example 3 To the same sepiolite as in Reference Example 1, about 40 times the weight of 1N hydrochloric acid was added and immersed at room temperature for about 10 hours to remove the framework magnesium of the sepiolite.

The obtained porous body was dried and fired in the same manner as in Reference Example 1, and then subjected to analysis and measurement.

As a result, the Si02/MgO molar ratio increased to 5.0, and the pore volume was 0.54 CC/gr, but the specific surface area was 322 =,/gr, which was a significant increase compared to the raw material. was recognized as doing so.

Moreover, the dry product before firing showed a specific surface area of 450 m'/7 and a pore volume of 0.60 CC,Q'.

Reference Example 4 The porous body from which the magnesium of sepiolite obtained in Reference Example 3 had been removed was kneaded with water to make it more porous by the following method.

First, a porous sepiolite material was pulverized to approximately 100 mesh or less, alumina sol was added to the anhydrous alumina content to give a content of 5%, and approximately 200% by weight of water was added and thoroughly kneaded.

After confirming that the pore volume was sufficiently large by sampling during the kneading process, the moisture content was adjusted to about 150% by weight.

This humidity control product was extruded into a cylinder with a diameter of 1.0 mm, thoroughly air-dried, then dried at 120°C for 2 hours, and further heated to 60°C.
It was baked at 0°C for 3 hours.

The specific surface area of the porous body thus obtained is 3 6 6 r
tp:/gr1 pore volume is 0. 9 1 CC/g
It was r.

From this, it was found that by removing the framework magnesium of sepiolite and then adding water and kneading it, a porous material with significantly increased specific surface area and pore volume could be obtained.

Reference Example 5 The same sepiolite as in Reference Example 1 was molded in the same manner as in Reference Example 4.

However, silica sol was added as a binder instead of alumina sol, and the mixture was fired at 500°C for 2 hours.

The specific surface area of this material is 17 s m'/gr, and the pore volume is 0. 72 CC/gr.

This molded body was immersed in anhydrous acetylacetone 20 times its weight and kept at 60 to 80°C for about 20 hours to remove the skeleton magnesium in sepiolite.

After thoroughly washing the obtained porous body with ethanol,
It was baked at 00°C for 1 hour.

The specific surface area of this material is 2 2 7 rrr”/gr,
Also, the pore volume (>75 people) is 0. 7 9 CC/g
It was x-.

Furthermore, the Si02/MgO molar ratio was approximately 2.2 before the acetylacetone treatment, but increased to 2.6 after the treatment.

Examples 1, 2, 3 Cu, Ni, and Cr were supported on the porous body obtained in Reference Example 3 by an ion exchange method.

That is, metal support was carried out by adding 10 times the amount of 0.1 N metal nitrate aqueous solution to the porous material dried at 120°C, keeping it at room temperature for 5 hours, washing thoroughly with pure water, and then drying at 500°C. Bake for 2 hours.

The amount of metal supported in the fired product was as follows. Metal supported amount Example I Cu0 1.6% tt2 NiO O. 7% 〃 3 Cr203 1.1% Example 4 Molybdenum was supported on the copper-supported porous body obtained in Example 1 by a normal dipping method so that Mo0 was 32.6% by weight.

Using this metal-supported porous material, vanadium 130
ppm, 42 ppm nickel and 2.62% sulfur.

The reaction uses a normal high-pressure flow reactor, and hydrogen pressure i 4
The reaction was conducted at a reaction temperature of 0 kg/crA, a liquid hourly space velocity of 1.01/hr, and a reaction temperature of 400°C.

The properties of the produced oil approximately 100 hours after the start of the reaction were as follows.

Vanadium 4 7 ppm1 Nickel 2 4 ppm1
Sulfur 1.91%.

Example 5 5 1 ppm of vanadium, A solvent deasphalted oil containing 19 ppm nickel and 2.42% sulfur was hydrodemetallized.

Demetallization was carried out using the same equipment as in Example 4, at a hydrogen pressure of 100
kg/cA, liquid space velocity 1. Ot/hr, reaction temperature 4
The test was carried out at 00°C.

The properties of the produced oil approximately 100 hours after the start of the reaction were as follows.

Vanadium 0. 1 ppm1-:Tsuke/L/0.
7 ppm, sulfur 1.22%.

[Brief explanation of drawings]

The drawing is a graph showing the relationship between specific surface area and Si02/MgO molar ratio in modified sepiolyte 1. according to the present invention.

Claims (1)

[Claims] 1. By removing the framework magnesium of natural sepiolite, the silica/magnesia (Sio2/MgO) molar ratio is reduced to 4.
A porous modified sepiolite-based catalyst for hydrogenation treatment, comprising a carrier made of powdered or molded porous modified sepiolite increased in size as described above, and a hydrogenation-active catalyst metal supported on the carrier. 2 The modified porous sepiolite carrier is prepared by reacting natural sepiolite with (a) an inorganic acid and/or an organic acid to form silica/magnesia (SiO2/MgO) in the sepiolite.
2. The catalyst according to claim 1, which is formed by a combination of the following steps in any order: increasing the molar ratio to 4 or more; and (b) calcination. 3 The modified porous sepiolite carrier is made by reacting natural sepiolite with (a) an inorganic acid and/or an organic acid to form silica/magnesia (Sin2/MgO) in the sepiolite.
A treatment step combining in any order the following steps: increasing the molar ratio to 4 or more, (b) kneading to finally adjust the moisture content to 80 to 350% by weight, and (e) baking. The catalyst of claim 1 which is formed by processing.