JP3243494B2 - Catalyst for hydrodesulfurization of thiophene and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst for hydrodesulfurization of thiophene, a method for producing the same, and a method for using the catalyst. More specifically, the present invention relates to a thiophene hydrodesulfurization catalyst having high activity and a method for efficiently hydrodesulfurizing thiophene using the catalyst.

[0002]

2. Description of the Related Art It is said that the amount of sulfur brought to the earth's surface with petroleum is enormous, comparable to the amount of natural sulfur circulation on the earth. Without hydrodesulfurization, this enormous sulfur emitted to the atmosphere as SO _x with the oil combustion use, which has caused such as acid rain. In order to prevent pollution and improve the global environment, regulations on sulfur content in petroleum have been tightened in Japan. For example, the regulation of sulfur in light oil was increased from 0.5% to 0.2% in 1992 and further increased to 0.05% in 1997 (Muneyoshi Yamada, Catalysts, Vol. 40, No. 1, 34-35,
1998).

[0003] In order to remove sulfur from petroleum and the like, various desulfurization catalysts have been studied. For example, in recent years, Mo-
Research has been conducted on Co binary catalysts, and it is said that cobalt provides a cocatalyst effect on molybdenum. However, it is difficult to highly disperse molybdenum and cobalt on an alumina support or the like in the atomic order.
The challenge is to produce a catalyst that provides stable activity.

As a catalyst for hydrodesulfurization of thiophene, a porous smectite supporting cobalt is Mo-
It has been reported to exhibit desulfurization properties comparable to Co binary catalysts (E. Hayashi et al., Chemistry).
Letters, 1997, 433-434). However, the experiments were performed in a pulsed reaction, and it was unclear whether long-term high activity against high concentrations of thiophene persisted. In addition, the porous smectite used as the carrier has a layered octahedral sheet containing Mg.
-Octahedral smectite.

[0005]

SUMMARY OF THE INVENTION The present invention provides a catalyst comprising a Co-containing smectite-type mesoporous body containing cobalt in a layered octahedral sheet, or a platinum-supported catalyst using the same as a carrier. The purpose of the present invention is to efficiently hydrodesulfurize thiophene using the above-mentioned compound.

[0006]

Means for Solving the Problems The present inventors have conducted intensive research to develop a practical desulfurization catalyst using a smectite-based mesopore porous material as a starting material.
Based on this finding, it was found that a catalyst comprising a Co-containing smectite-based mesopore porous body or a platinum-supported catalyst using the same as a carrier was effective as a desulfurization catalyst having high activity for hydrodesulfurization of thiophene. The present invention has been completed.

That is, the present invention relates to a compound represented by the general formula [(SiO ₂ ) ₈ · (CoO _2/3 ) _a · (OH)
_{(2/3) a + b} ] ^b− · (b + c) X ⁺ (wherein X is a monovalent alkali ion, and a, b, and c are 0 <a <10, 0.b
≦ 1, 0 ≦ c ≦ 1), a specific surface area of 100 to 800 m ² / g, and an average pore diameter of 2 to 5 nm.
(Excluding 5 nm) and pore volume of 0.1 to 0.8 cm
An object of the present invention is to provide a thiophene hydrodesulfurization catalyst comprising a Co-containing smectite-type mesopore porous body having a ratio of ³ / g, or a thiophene hydrodesulfurization catalyst comprising a Co-containing smectite-type mesopore porous body supporting platinum.

[0008] According to the present invention, such a catalyst is added to an aqueous solution containing an alkali metal silicate and an alkali hydroxide,
A slurry prepared by adding an aqueous solution of a water-soluble salt of Co is subjected to a hydrothermal reaction to obtain a general formula [(SiO ₂ ) ₈ · (CoO _2/3 ) _a · (OH) _{(2/3) a + b} ] ^b- (B + c) X ⁺ ... (I) (wherein X is a monovalent alkali ion and a, b, c
Is a number in the range of 0 <a <10, 0 <b ≦ 1, 0 ≦ c ≦ 1) Co-containing smectite-based mesopore porous body is prepared, dried, and then reduced with hydrogen at a temperature of 300 to 700 ° C. Can be manufactured. Alternatively, a Co-containing smectite-based mesopore porous body obtained by the above hydrothermal synthesis method is used as a carrier, impregnated with an aqueous solution of a platinum compound, dried, and then reduced with hydrogen at a temperature of 300 to 700 ° C. The thiophene hydrodesulfurization catalyst of the invention can be produced.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the catalyst of the present invention, a Co-containing catalyst having the composition of the above general formula (I) is used as a catalyst or a carrier.
A smectite-based mesopore porous body is used. In general, Co in the general formula (I) is preferably used as a single ion, but may partially contain another divalent metal such as Mg, Ni, and Zn. X is a monovalent alkali ion derived from an alkali metal silicate or an alkali hydroxide used in the production, for example, an alkali metal ion such as a sodium ion, a potassium ion, or a lithium ion; You can choose from ions, etc. On the other hand, a, b and c are 0 <a <10 and 0 <b
≦ 1 and 0 ≦ c ≦ 1, and the value of b + c is preferably 0 <b + c ≦ 1, most preferably 0 <b + c ≦ 0.
The number is in the range of 5, and these values vary depending on the type of raw material, the usage ratio, the reaction conditions, and the like in the production of the Co-containing smectite-based mesopore porous body.

Next, in the present invention, the Co-containing smectite-based mesopore porous body has a specific surface area of 100 to 8%.
00m ² / g, average pore diameter. 2 to 5 nm (although 5nm
) And having a pore volume in the range of 0.1 to 0.8 cm ³ / g. If any of these deviates from the above range, a catalyst having desired performance cannot be obtained. From the viewpoint of the activity and selectivity of the obtained catalyst, the Co-containing smectite-based mesopore porous material has a specific surface area of 200 to 800 m ² / g, an average pore diameter of ^{2 to} 5 nm (excluding 5 nm) , Those having a pore volume in the range of 0.2 to 0.8 cm ³ / g are preferred.

In the platinum-supported catalyst of the present invention, the amount of supported platinum is preferably 0.1 to 5% by weight based on the total amount of the catalyst. If the supported amount is less than 0.1% by weight, the catalytic activity is insufficient. If it exceeds 5% by weight, the catalytic activity is not so much improved for the amount, and it is economically disadvantageous. From the viewpoint of the balance between catalyst activity and economy, the amount of supported platinum is advantageously in the range of 0.2 to 2% by weight.

To produce a catalyst according to the method of the present invention, first, an aqueous alkali solution containing an alkali metal salt of silicic acid such as sodium silicate is prepared. On this occasion,
As the alkali metal silicate, for example, commercially available water glass No. 1 to No. 4 or sodium metasilicate can be used. The sodium silicate is dissolved in water to prepare a sodium silicate-containing aqueous solution. However, if the pH of the solution is within a predetermined range, it is not necessary to add an alkali. If the pH is less than the predetermined range, the pH is adjusted to a predetermined range by adding an aqueous alkali solution such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or aqueous ammonia. This pH is determined by adjusting the pH at the time of preparing the composite precipitate described below.
It is appropriately selected according to the H value, but is usually pH 5 or more. The concentration of the alkali metal silicate is not particularly limited, but is usually selected in the range of 5 to 30% by weight.

The aqueous solution containing the aqueous cobalt salt is then added to the aqueous alkali solution containing the alkali metal silicate thus prepared. These cobalt salts
It can be selected from chloride salts, sulfates, nitrates, perchlorates, acetates and the like. The concentration of the cobalt salt is not particularly limited, but is preferably in the range of usually 10 to 50% by weight.

As described above, when the alkali aqueous solution containing the alkali metal silicate and the aqueous solution containing the aqueous salt of cobalt are mixed, a composite precipitate is formed. As a mixing method at this time, an alkali aqueous solution containing an alkali metal silicate may be added to an aqueous solution containing cobalt, or an aqueous solution containing a cobalt may be added to an aqueous alkali solution containing an alkali metal silicate. The amount ratio of sodium silicate and cobalt may be selected so as to satisfy the range of a in the general formula (I).

The pH value at the time of precipitation of the composite precipitate is as follows:
Generally, the pH is in the range of 5 to 13, but the preferred pH value is p
H6-10. In general, when the pH value is low, the divalent metal does not easily precipitate, and when the pH value is high, silicon tends to hardly precipitate.

The composite precipitate thus formed is taken out by a known means such as filtration, centrifugation, decantation and the like, and then sufficiently washed with water to remove by-product solutes. Next, if necessary, OH ions are added to prepare a slurry, followed by a hydrothermal reaction. The pH value at the time of this hydrothermal reaction significantly affects the characteristics of the produced Co-containing smectite-based mesopore body. For example, when the pH value is low, the average pore diameter and the pore volume generally increase, and the cation exchange capacity tends to decrease. On the other hand, as the pH value increases, the pore volume decreases, and the cation exchange capacity decreases. There is a tendency for the ion exchange capacity to increase. Preferred cation exchange capacities range from 0.1 to 1.2 meq / g. As the OH ion source, for example, hydroxide diisocyanato <br/> Liu arm, potassium water oxidation is used.

It is considered that the cation exchange ability is exhibited by the negatively charged silicate skeleton constituting the Co-containing smectite-type mesopore porous body. The amount of the skeletal negative charge corresponds to the value of b in the general formula (I), and thus corresponds to the magnitude of the cation exchange capacity.

When a Co-containing smectite-based mesopore porous body is used as a catalyst or a catalyst carrier in the hydrodesulfurization reaction of thiophene, the catalytic activity is affected by the content of the contained alkali metal. The content of the alkali metal is represented by the general formula I
Since the catalytic activity tends to decrease as the value of b + c increases, the value of b + c is preferably 0 <b + c ≦ 1, most preferably 0 <b + c ≦
0.5, the smaller the value, the higher the activity. In order to reduce this value, it is effective to replace alkali metal ions with hydrogen ions or ammonium ions by ion exchange. It is also effective to improve catalytic activity by substituting with alkali quaternary ammonium ions and removing organic substances at a high temperature of 300 to 700 ° C.
Alternatively, reducing the value of the cation exchange capacity also effectively functions to improve the catalytic activity.

The hydrothermal reaction of the slurry thus prepared is usually carried out in an autoclave or the like for 100 to 30 minutes.
It is carried out at a temperature of about 0 ° C, preferably in the range of 100 to 200 ° C. As the hydrothermal reaction temperature increases, the cation exchange capacity generally increases, and conversely, the specific surface area and pore volume tend to decrease. After completion of the hydrothermal reaction, the pH of the slurry obtained by natural cooling after the hydrothermal reaction can be measured with a pH meter. In addition, the reaction aqueous solution after the solid-liquid separation may be measured. Slurry pH after hydrothermal reaction
Is preferably a value in the range of 4 to 10, but is most preferably a value in the range of 5 to 7. P of slurry after hydrothermal
When H is out of the above range, for example, when pH is 4 or less, cobalt elutes, and when pH is 10 or more, silica elutes, and it becomes difficult to achieve a desired composition. Also, p
The higher the H, the higher the sodium content in the product,
There is a tendency for the catalytic activity to decrease. In general, the pH value of the slurry after the hydrothermal reaction slightly changes depending on the hydrothermal treatment conditions. However, if the pH value of the slurry before the hydrothermal treatment is set to a pH value that is about 1 higher than the target pH value, A pH value close to the value is obtained.

After the completion of the hydrothermal reaction, the reaction product is
Alternatively, after washing with water as necessary, a drying treatment is performed. This drying treatment may be carried out using a general dryer or vacuum dryer at a temperature of usually from about 200 ° C. to about 200 ° C., or by spray drying or freeze drying. In this case, if necessary,
After previously forming into a desired shape, for example, a honeycomb shape or a granular shape, a drying process may be performed. After drying, it may be pulverized and granulated, if necessary, and used as a carrier, or a powdery Co-containing smectite-based mesopore porous body may be formed into a honeycomb shape or a granular shape and used as a carrier. At this time, no binder is required, but a binder can be used if desired.

The dried reaction product is subjected to an activation treatment by performing a hydrogen reduction to obtain a desired thiophene hydrodesulfurization catalyst. The activation treatment by hydrogen reduction is usually performed in a desulfurization apparatus immediately before use as a catalyst. In general, heating is performed while flowing hydrogen gas to perform hydrogen reduction and activation. This hydrogen reduction temperature is 200 ° C. or higher, preferably in the range of 300 to 700 ° C., and most preferably in the range of 300 to 500 ° C.

Further, using a Co-containing smectite-type mesopore porous body represented by the general formula (I) and having the above-mentioned properties as a carrier, a platinum compound-containing aqueous solution is impregnated, and the platinum precursor is adsorbed on the carrier. Let it. The platinum compound-containing aqueous solution may be acidic, neutral or alkaline. Further, as the platinum compound, for example, chloroplatinic acid, tetraaminedichloroplatinum-water salt or the like is preferably used. The amount of platinum carried can be determined by measuring the concentration of platinum in the solution before and after adsorption by atomic absorption spectrometry.

The Co thus adsorbing the platinum precursor is
The contained smectite-based mesoporous carrier is removed by known means such as filtration, centrifugation, decantation, etc., sufficiently washed with water, dried, then activated by hydrogen reduction, and the desired thiophene hydrodesulfurization is performed. A platinum supported catalyst is obtained. This activation treatment by hydrogen reduction is usually carried out.
It is often carried out in an apparatus immediately before use as a catalyst.
In general, heating is performed while flowing hydrogen gas to perform hydrogen reduction and activation. The hydrogen reduction temperature is 200 ° C or higher,
Preferably it is in the range of 300-700C, most preferably in the range of 300-500C.

The two types of catalysts of the present invention obtained by the above-mentioned method are used for chemical analysis, X-ray diffraction, infrared absorption spectrum analysis, specific surface area measurement, pore size distribution measurement, cation exchange capacity measurement (ESR), X It can be evaluated by X-ray photoelectron spectroscopy (ESCA), thermal desorption (TPD), X-ray absorption wide area continuous fine structure spectrum measurement (EXAFS), catalyst activity measurement, and the like.

For example, the smectite structure in the catalyst of the present invention can be easily confirmed by X-ray diffraction measurement. When measured using a copper tube and a nickel filter, in the case of an amorphous material having a similar composition, 2θ = 20 ° to 25 °
°, broad diffraction lines are obtained, while Co
In the contained smectite-type mesopore porous body, 2θ = 20 °,
Broad diffraction is observed around 35 ° and 60 °.
These are similar to the diffraction pattern of natural smectite having a similar composition, but in the case of natural smectite, a vertical diffraction line (001 reflection) is clearly observed in the layer, whereas in this case, it is usually not observed. , Rarely 2θ = 2 ° ~
At 6 °, broad diffraction is weakly observed, indicating that the substance is a low-crystalline smectite-like substance. This diffraction pattern is basically maintained at a heating temperature of about 700 to 800 ° C. The function as a porous body can be confirmed by measuring the specific surface area and pore volume by nitrogen gas adsorption, or by pore diameter distribution obtained from a nitrogen adsorption / desorption curve.

Further, as a scale for examining the degree of dispersion of platinum in the catalyst of the present invention, the hydrogen adsorption atomic weight per platinum atom (H / Pt) is used. This hydrogen adsorption atomic weight is
It can be determined by a thermal desorption (TPD) method. For example, after hydrogen reduction and activation treatment at 400 ° C., hydrogen is adsorbed on the catalyst sample at room temperature under a hydrogen stream for 20 minutes,
Then, the temperature was raised at a heating rate of 30 under an argon stream of 30 ml / min.
The temperature was raised to 400 ° C. at a rate of 400 ° C./min, and the amount of desorbed hydrogen was measured by gas chromatography to obtain H /
Pt can be determined.

The value of H / Pt thus obtained is:
For example, in the case of a platinum-supported silica gel catalyst, the value is 0.19, and platinum is dispersed in a particulate state, whereas the platinum-supported Co-containing catalyst of the present invention shows a value of 1.42, and platinum is in an atomic state. It turns out that it is highly dispersed. In any case, the platinum-supported catalyst of the present invention has excellent catalytic activity because platinum is supported in a highly dispersed state.

These two catalysts of the present invention can be used for hydrodesulfurization of thiophene. Also used for hydrodesulfurization of other thiophenes, for example, alkylbenzothiophenes such as benzothiophene and methylbenzothiophene, alkyldibenzothiophenes such as 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. Is possible. The thiophene hydrodesulfurization catalyst of the present invention is used for the hydrodesulfurization reaction of these thiophenes. In the present invention, thiophene means these thiophenes.

Thiophene, benzothiophene, methylbenzothiophene, 4-methyldibenzothiophene, 4,
Thiophenes such as 6-dimethyldibenzothiophene are
It is contained in crude oil, heavy oil, light oil, kerosene, gasoline, LPG, butane gas, natural gas, etc. By using the catalyst of the present invention, it is possible to remove sulfur components from thiophene and benzothiophenes contained in these liquid and gaseous substances by a hydrodesulfurization reaction,
As a result, the sulfur content can be reduced.

When the hydrodesulfurization reaction is carried out using thiophene, normal butane, 1-butene, trans 2-butene, cis 2-butene and the like are generally produced. When the catalyst of the present invention is used, the amount of normal butane produced is small,
The sequence is trans 2-butene> cis 2-butene>1-butene> normal butane.

Using the hydrodesulfurization reaction of thiophene at 350 ° C. as a catalyst, two types of catalysts of the present invention (a catalyst comprising a Co-containing smectite-type mesoporous material and a catalyst comprising the same, which were activated in a hydrogen stream at 400 ° C. for 3 hours) When the catalyst is carried out using a platinum-supported silica catalyst, a platinum-supported silica catalyst, and a platinum-supported silica catalyst, the respective catalytic performances are as follows. The concentration of thiophene in the hydrogen used was 2.9 Vol. %Met.

As shown in the examples described later,
Hydrothermal synthesis at 200 ° C from pH 6.1 slurry of medium
The resulting catalyst (SM (Co) a) and a pH 6.1 slurry
Co-containing smectite mesopores obtained from Lee
1 wt. % Platinum supported catalyst (1 wt.% P
In the case of t / SM (Co) a), the conversion of the reaction is 41%.
And 60%. On the other hand, 10 wt.
% Cobalt supported silica catalyst (10 wt.% Co / Si
O_Two) And 1 wt. % Platinum supported silica catalyst, the reaction
Conversions were 19% and 36%, respectively. Accordingly
Thus, the strength of the catalytic activity is 1 wt.% Pt / SM (Co) a> SM (Co) a> 1 wt.% Pt / SiO_Two> 10w
t.% Co / SiO_Two  It becomes the order of. Thus, the catalyst of the present invention
Has a strong activity against hydrodesulfurization reaction.

[0033]

Next, the present invention will be described in more detail by way of examples.
As will be explained, the present invention is in no way limited by these examples.
It is not something to be done. Example 1 In this example, a Co-containing smectite-based mesopore porous body was used.
A catalyst consisting of 20 water in a 1 liter beaker
0 ml, and the No. 3 glass (SiO_Two : 28w
t. %, Na_Two O: 9 wt. %, SiO_Two / Na_Two Omo
After dissolving 86 g, a further 2 M hydroxylation was carried out.
Add 150 ml of aqueous sodium solution and mix at pH 13.8.
A combined solution (solution A) was prepared. On the other hand, chloride in 200 ml of water
Add 71.4 g of cobalt hexahydrate (primary reagent) and add pH
A 2.0 solution (solution B) was prepared. Next, the magnetic
Stir solution A with custala, and add solution B into it.
The mixture was added dropwise over a period of 1 minute, and the mixture was further stirred for 1 hour. Then generate
The combined precipitate was collected by filtration, washed sufficiently with water, and then washed with 20 ml of water.
Into a slurry by adding
At a pressure of 1.66 MPa and a temperature of 200 ° C.
The hydrothermal reaction was performed under the conditions for 2 hours. The pH before and after the reaction is 6.
It changed from 9 to 6.1. In addition, Co-containing smectite
The chemical composition of the porous mesopore material is (SiO_Two)₈(CoO)_5.98(OH)_4.13(Na_TwoO)_0.11  And corresponds to a = 5.98 and b + c = 0.22
You. The specific surface area of this carrier is 380m^Two / G, pore volume is
0.34cm^Three / G and an average pore diameter of 3.6 nm.
Was.

After drying at 80 ° C. for 16 hours, 40 ml /
For 3 hours at 400 ° C. for 3 minutes under a hydrogen stream to obtain a catalyst of the present invention.

Example 2 Using a normal pressure flow reactor, using 0.1 g of the catalyst obtained in Example 1, a mixed gas of hydrogen and thiophene (thiophene concentration: 2.9 vol.%) Was 20 ml / Per minute and reacted at a constant temperature of 350 ° C. The analysis of the produced gas was performed using a gas chromatograph measurement device.

The conversion of the reaction was determined at a reaction temperature of 35 hours after 6 hours.
It was 41% at 0 ° C. The selectivity of the product is normal butane 8%, 1-butene 18%, trans 2-butene 42
% And cis-type 2-butene were found to be 30%, indicating that the desulfurization reaction in which trans-butene and cis-type 2-butene were generated from thiophene easily proceeded.

Example 3 In this example, a platinum-supported catalyst was produced using the Co-containing smectite-based mesopore porous body obtained in Example 1 as a carrier. Dissolve 0.013 mol of tetraaminedichloroplatinum-water salt in 1 liter of water and adjust the pH to 1 using aqueous ammonia.
Adjusted to 2 to obtain a solution with a concentration of 2.5 mg Pt / ml. 5 g of the carrier was immersed in 20 ml of this aqueous solution of tetraaminedichloroplatinum for 3 days to adsorb the platinum precursor. The amount of platinum carried was 1 wt. %Met. After filtration and washing, vacuum drying was performed at 110 ° C. for 3 hours, and reduction was performed at 400 ° C. for 3 hours under a hydrogen stream of 40 ml / min to obtain a platinum-supported catalyst of the present invention.

Example 4 1 wt. When a thiophene hydrodesulfurization reaction was carried out in the same manner as in Example 2 using a% platinum-supported catalyst, the conversion of the reaction at a reaction temperature of 350 ° C. after 6 hours was 60%. The gas composition of the product was 15% normal butane, 17% 1-butene, 39% trans 2-butene and 28% cis 2-butene on a molar basis. By supporting platinum on the Co-containing smectite-based mesoporous material, it was found that the conversion of the reaction increased by about 50%, the proportion of 2-butenes slightly decreased, and the proportion of normal butane tended to increase. did.

Comparative Example 1 (1) Preparation of Co-Supported Silica Gel Catalyst Commercially available silica gel [Aldrich
Co., Ltd., trade name “Davisil 646] is sized to 32-60 mesh and used as a carrier.
(CH ₃ COO) ₂ .4H ₂ O aqueous solution, and 10 wt. % Supported 10 wt.
% Co supported silica gel was prepared. Using a 1 liter beaker, 2.1 g of cobalt acetate tetrahydrate reagent (special grade reagent, purity 99%) was dissolved in 500 ml of water, and 0.001
A 7 molar aqueous solution of cobalt acetate was prepared. 0.52 g of silica gel is added to 52 ml of this aqueous cobalt acetate solution.
Soak in the sun for 10 wt. % Cobalt supported silica gel was prepared. After drying, a reduction treatment was performed at 400 ° C. for 3 hours under a hydrogen stream to obtain 10 wt. % Co supported silica gel catalyst was obtained. (2) Hydrodesulfurization Reaction When a thiophene hydrodesulfurization reaction was performed at 350 ° C. using this catalyst, the conversion of the reaction was 19%. The gas composition of the product is normal butane 2%, 1-butene 23
%, Trans 2-butene 43% and cis 2-butene 31%. Compared with Example 1, it was found that the ratio of normal butane decreased and the ratio of 1-butene increased. Compared to Example 1, the conversion of the reaction was about half the value.

Comparative Example 2 A 35 wt. % Co supported silica gel catalyst was prepared. However, in this case, 0.001
0.74 in 259 ml of 7 molar aqueous cobalt acetate solution
g of silica gel. Using this catalyst, 350
When the hydrodesulfurization reaction of thiophene was carried out at ℃, the conversion of the reaction was 23%. The amount of cobalt supported was 10 wt. % To 35 wt. %, The conversion of the reaction increased only slightly from 19% to 23%. That is, it was found that the hydrodesulfurization activity of thiophene when cobalt was supported on silica gel was not significantly improved even if the amount of supported cobalt was increased.

Comparative Example 3 The same silica gel (trade name: Davisil 646) sized to 32 to 60 mesh as in Comparative Example 1 was used as a carrier, and 1 wt. % Platinum supported catalyst was prepared. The conversion of the hydrodesulfurization reaction of thiophene at 350 ° C. was 36%. The gas composition of the product was as follows: normal butane 80%, 1-butene 4%, trans type 2-
It was found that the content was 8% for butene and 6% for cis-type 2-butene, and most of it was normal butane.

Comparative Example 4 In Example 1, 86 g of No. 3 water glass and 2
M sodium hydroxide aqueous solution 150ml and magnesium chloride
Um hexahydrate (primary reagent) except for 60.99 g
As in Example 1, Mg-containing smectite mesopores
A catalyst composed of a porous body was prepared. The pH before and after the hydrothermal reaction is
It changed from 10.1 to 9.2. Also, the obtained product
The chemical composition of (SiO_Two)₈(MgO)_6.13(OH)_4.34(Na_TwoO)_0.19  Met. This Mg-containing smectite-based mesoporous body
Has a specific surface area of 485m^Two / G, pore volume 0.40 cm^Three
 / G and the average pore diameter were 3.3 nm.

The thiophene had almost no activity in the hydrodesulfurization reaction at 350 ° C., and the conversion was 1% or less.

Comparative Example 5 Using the Mg-containing smectite-based mesopore porous body of Comparative Example 4 as a carrier, 35w was obtained in the same manner as in Comparative Example 3.
t. % Cobalt supported catalyst was prepared. In the hydrodesulfurization reaction of thiophene at 350 ° C., the conversion of the reaction was 24%. The gas composition of the product is normal butane 7%, 1-butene 22%, trans 2-butene 41%
And cis-type 2-butene was 30%.

Comparative Example 6 In Example 1, 86 g of No. 3 water glass and 2
A catalyst was prepared in the same manner as in Example 1, except that 190 ml of M sodium hydroxide aqueous solution and 71.4 g of cobalt chloride hexahydrate (primary reagent) were used. The pH before and after the hydrothermal reaction changed from 9.4 to 8.9. The chemical composition of the obtained product is (SiO ₂ ) ₈ (CoO) _6.25 (OH) _4.85 (Na ₂ O) _0.82 , which corresponds to a = 6.25 and b + c = 1.64. The specific surface area of this carrier was 210 m ² / g, the pore volume was 0.17 cm ³ / g, and the average pore diameter was 3.2 nm. The hydrodesulfurization reaction of thiophene at 350 ° C. showed almost weak catalytic activity, and the conversion was 3% or less.

Example 5 Using the catalysts of Examples 1 and 3 (products of the present invention), a one-week continuous test was carried out on the hydrodesulfurization reaction of thiophene at a reaction temperature of 350 ° C. to confirm the long-term stability of the catalyst. Examined. Table 1 shows the results. From Table 1, the catalytic activity for hydrodesulfurization of thiophene of the products of the present invention of Examples 1 and 3 is slightly weak in the initial stage, but the activity is improved in 6 hours and shows a substantially constant conversion. The activity was hardly changed, and it was found that it had excellent long-term stability. Thus, thiophene 2.9 Vol. % Of the sample of the present invention has a function of maintaining high activity for a long time with respect to a sample containing a high concentration of 0.1%.

[0047]

[Table 1]

Example 6 The hydrodesulfurization reaction of thiophene using the catalysts of Examples 1 and 3 (products of the present invention) was carried out at a reaction temperature of 300 to
The temperature was changed to 450 ° C., and the conversion after 6 hours was measured. Table 2 shows the measurement results. From the results in Table 2, it was found that the higher the reaction temperature, the higher the catalytic activity.

[0049]

[Table 2]

[0050]

The present invention provides a catalyst comprising a Co-containing smectite-based mesopore porous body having a specific chemical composition containing cobalt and a specific property of a mesopore structure, or a carrier comprising the Co-containing smectite-based mesopore porous body. Pertains to a platinum-carrying catalyst carrying platinum,
According to the present invention, 1) a novel catalyst for hydrodesulfurization of thiophene can be provided. 2) The catalyst of the present invention has high activity for the hydrodesulfurization reaction of thiophene, and changes the production method. Thus, the catalyst activity can be controlled by the method, 3) the high activity can be maintained for a long time with respect to a high concentration of thiophene, 4) the sulfur content can be efficiently removed from petroleum, etc., 5) the petroleum, etc. A special effect such as being useful for reducing sulfur is obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yui Minato 2-1-1 Katahira, Aoba-ku, Aoba-ku, Sendai City, Miyagi Prefecture Inside the Institute for Reactive Chemistry, Tohoku University (72) Kuriko Aoki 2-1-1 Katahira, Aoba-ku, Sendai-shi, Miyagi Prefecture No. 1 Tohoku University Research Institute for Reaction Chemistry (56) References JP-A-9-225304 (JP, A) JP-A-10-202100 (JP, A) JP-B-7-115856 (JP, B2) 10-505277 (JP, A) (58) Fields studied (Int. Cl. ⁷ , DB name) B01J 21/00-38/74 C01B 33/20-33/46 C10G 45/02-45/30 JICST file (JOIS)

Claims (8)

(57) [Claims] 1. A compound of the general formula [(SiO ₂ ) _8. (CoO _2/3 ) _a. (OH)
_{(2/3) a + b} ] ^b− · (b + c) X ⁺ (wherein X is a monovalent alkali ion, and a, b, and c are 0 <a <10, 0.b
≦ 1, 0 ≦ c ≦ 2), a specific surface area of 100 to 800 m ² / g, and an average pore diameter of 2 to 5 nm.
(Excluding 5 nm) and pore volume of 0.1 to 0.8 cm
^A thiophene hydrodesulfurization catalyst comprising a Co-containing smectite-based mesopore having a content of ³ / g. 2. The thiophene hydrodesulfurization catalyst according to claim 1, wherein the value of (b + c) is a number in the range of 0 <b + c ≦ 0.5. 3. A thiophene hydrodesulfurization catalyst comprising platinum supported on a Co-containing smectite-based mesopore porous body represented by the general formula of claim 1. 4. An aqueous solution of an aqueous solution of Co is added to an aqueous solution containing an alkali metal silicate and an alkali hydroxide to precipitate the solution.
And the resulting composite precipitate is washed with water to remove by-product solutes.
After that, the slurry prepared by adding water and, if necessary, OH ions is subjected to a hydrothermal reaction to obtain the general formula [(SiO ₂ ) ₈ · (CoO _2/3 ) _a · (OH)
_{(2/3) a + b} ] ^b− · (b + c) X ⁺ (where X is a monovalent alkali ion, and a, b, and c are 0 <a <10, 0 <b
≦ 1, 0 ≦ c ≦ 2).
The method for producing a catalyst for hydrodesulfurization of thiophene according to claim 1, wherein a smectite-based mesopore-containing porous material is prepared, dried, and then reduced with hydrogen at a temperature of 300 to 700 ° C. 4. 5. The method for producing a thiophene hydrodesulfurization catalyst according to claim 4, wherein the pH of the slurry after the hydrothermal treatment is 5 to 7. 6. A Co-containing smectite-based mesopore porous body produced by the production method according to claim 4 or 5, which is used as a carrier, then impregnated with an aqueous solution of a platinum compound, dried, and then heated to 300 to 700 ° C. The method for producing a catalyst for hydrodesulfurization of thiophene according to claim 3, wherein the catalyst is subjected to hydrogen reduction at a temperature of: 7. A method for hydrodesulfurizing thiophene, comprising bringing thiophene into contact with hydrogen at 250 to 500 ° C. in the presence of the catalyst according to claim 1 or 2. 8. A method for hydrodesulfurizing thiophene, comprising contacting thiophene with hydrogen at 250 to 500 ° C. in the presence of the catalyst according to claim 3.