JPS62223013A - Solid acid substance, production thereof and decomposition of hydrocarbon using said solid acid substance - Google Patents

Abstract

PURPOSE:To provide a solid acid substance composed of a compound metal oxide expressed by a specific formula and containing ZrO2, SiO2, F and S, having strong acid concentration, containing super-strong acid point which is not easily decomposed even in contact with water and usable as a catalyst over a broad temperature range. CONSTITUTION:A solid acid substance containing strong acid point having an acid strength Ho of <=-8.2 and composed of a compound metal oxide of formula [x and y are molar numbers of ZrO2 and SiO2, respectively; the ratio x/y is ratio of numbers of Zr and Si atoms; Z and m are wt% of F atom and wt% of S atom based on the weight of (xZrO2.ySiO2); x/y is 99.9/0.1-10/90; z is 0.1-10; m is 0.01-5]. The substance has extremely strong acid strength, containing super-strong acid point which is not easily decomposed even in contact with water, usable as a catalyst over a broad temperature range and, accordingly, expected to be useful in a wide variety of applications as an industrial catalyst.

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a ZrO2-8102-based solid acid material, a method for producing the same, and a method for decomposing hydrocarbons using this solid acid material.

Attempting to obtain industrially useful fractions with 3 to 4 carbon atoms in high yield from petroleum-based hydrocarbon compounds such as naphtha. Attempts have been made for a long time, and solid acid catalysts are known to be useful in this case.

Furthermore, solid acid catalysts are known to be used in various reactions such as isomerization, alkylation, and dealkylation of hydrocarbons. One of the characteristics that characterizes such solid acids is their acid strength, and depending on the reaction, a solid super strong acid having extremely strong acidity may be required.

As such solid super strong acids, conventionally, metal fluorides such as SbF5 are deposited on SiO2-At203 metal oxides (catalyst 21 (4), 220° (H0) is 9
79)), reaction of ion exchange resin and AlCl3 (J, Catalysis 46.266 (H0)
977)), CuSO4 or CuCl2 and Al
2 units of Chinoku catalyst mixed with Cl3 (4).

233 (H0) is 979) ), ZrO2, Fe2
o3 etc. treated with sulfuric acid (catalyst 22 (4),
232° (H0) is 980)), etc. are known.

These solid super strong acids are easily decomposed by contact with ZrO2 and cannot be regenerated, and the temperature range in which they can be used as catalysts is extremely narrow, making it difficult to apply them as industrial catalysts. was there.

The present invention is intended to solve the problems associated with the prior art as described above. without disassembling,
Moreover, it is an object of the present invention to provide a novel solid acid substance that can be used as a catalyst in a wide temperature range and is therefore expected to have a wide range of uses as an industrial catalyst.

Another object of the present invention is to provide a method for producing the above-mentioned novel solid acid substance.

Yet another object of the present invention is to provide a method for decomposing hydrocarbons using the above-described novel solid acid substance as a catalyst.

Summary of the Invention The novel solid acid material according to the present invention has (xZro 2 ・
ysi02>・zF-ms [In the formula, x and y represent the number of moles of ZrO2 and Si02, and the value of x/V represents the atomic ratio of Zr/Si.

In addition, 2 and m are each (xZrO−'y'5i02 >
The weight % of F atoms and the weight % of S atoms are shown relative to the weight of . And x/y is 99.910. '1~10/90
, ZG, to, 1 to 10, and m is 0.01 to
In the range of 5. It is a composite metal oxide represented by ], and is characterized by having a strong acid point with an acid strength (HO> of -8.2 or less).

When this solid acid substance is measured by x-ray diffraction and x-ray photoelectron spectroscopy, it is found that it is a new substance that is clearly different from the composite metal oxide of ZrO2-8i02.

Further, the method for producing the above-mentioned composite metal oxide, which is a novel solid acid, according to the present invention includes a method of manufacturing a composite metal oxide represented by xZro2.ySiO2 by SF at a temperature of 300 to 800°C.
It is characterized by processing at 6.

Roughly speaking, the method for decomposing hydrocarbons according to the present invention comprises decomposing paraffins having 5 to 10 carbon atoms or hydrocarbons containing said paraffins as a main component [these are hydrocarbons] in the presence of the novel solid acid substance as described above. (a)] to produce a lower aliphatic hydrocarbon (b) whose main component is paraffin having 3 to 4 carbon atoms.

The above formula (XZrO2・ySi02
A solid acid substance represented by >.zF-mS has extremely strong acid strength, strong acid sites do not easily decompose even when it comes into contact with moisture, and the temperature range in which it can be used as a catalyst is wide.

Hydrocarbons (a) containing paraffins having 5 to 10 carbon atoms
When reacted in the presence of the above solid acid substance, the carbon number is 3 to 4.
Lower aliphatic hydrocarbons whose main component is paraffin can be obtained in high yield.

DETAILED DESCRIPTION OF THE INVENTION The novel solid acid substance of the present invention, its manufacturing method, and the hydrocarbon decomposition reaction using this solid acid substance as a catalyst will be specifically described below.

The novel solid acid substance according to the present invention is (xZrO□・yS
iO2) -zF-ms ZrO2-8i0
A two-system composite metal oxide with an acid strength (H0) of -8,
It has a super strong acid point of 2 or less, and in some cases -12.7 or less. In the above formula, x and y represent the number of moles of ZrO2 and 5i02, and the value of x/y represents the atomic ratio of Zr/Si. Further, 2 and m represent the weight percent of F atoms and the weight percent of S atoms, respectively, with respect to the weight of (xZrO2.ySiO2).

And X/V is 99.910.1 to 10/90,
2 is in the range of 0.1 to 10, and m is in the range of 0.01 to 5. Note that in this specification, the proportions of F and S in the solid acid material according to the present invention are shown as average values for the entire solid acid material. In this composite metal oxide, the atomic ratio of Zr and Si (Zr/Si) is expressed as X/V, but in the present invention, this value is 99.910.1 to 10/V.
Within the range of 90, 90/10 to 50150
It is preferable that it is in the range of . Such (xZrO2
The solid acid substance of the present invention represented by ySiO2)-zF-mS is obtained by treating a ZrO2-8io2 complex oxide with S6 as described later, so F and S are present on the surface of the solid. It is considered that the concentration of is normally higher than the ratio within the above-mentioned range.

In the present invention, (xZrO2 ・'y'S!02
)・ZF-ms In the solid acid material, Zr/S
When the atomic ratio of i is usually larger than 99.910.1, the value of acid strength Ho increases and the acid strength usually becomes weaker.
In addition, when the atomic ratio of Zr/3i is 10/90 or less, the acid strength usually becomes weak, so in the present invention, Zr/Si
The atomic ratio (x/y) of is set within the above range.

In the present invention, Zr1si of the solid acid material according to the present invention,
The F and S contents are determined using the method shown below.

``Analysis of S: by oxygen flask combustion method.

Analysis of Zr: A sample is melted with acid to make a nitric acid solution, and then subjected to ICP plasma emission spectrometry.

Analysis of Si: Dissolve the sample in alkali@ to make an aqueous solution,
ICP plasma is based on emission spectroscopy.

Acid strength (T1o) The novel solid acid substance represented by the above formula has an acid strength H-10
) has a strong acid point of -8.2 or less, but the acid strength (H
o> is measured when the catalyst and (3) 241° (H0) is 98
The method described in 2) was used. Specifically, it is performed as follows. Sulfuryl chloride 302C
Add 5 g of granular blue silica gel to 220 cc of I and leave it for one day to dry the reagent.

Take 3 cc of this dried sulfuryl chloride in a test tube,
Immediately add the catalyst and submerge it in the liquid. A few drops of a 1% benzene solution of a Hammett indicator with a known pKa value is added to the solid acid substance, shaken lightly several times, and left to stand to observe a change in color on the catalyst surface. If the change is not clear, close the stopper and leave it for several hours. Commercially available 1°3.5-trinitrobenzene (pK
When using a-16,04), the reagent usually contains a large amount of water, so after preparing a 1% benzene solution, silica gel is added and left to dry for several days before being used as an indicator.

Table 1 shows the relationship between the Hammett indicator used to measure the acid strength (+-10>) of a solid acid substance in the present invention and its 1) Ka value. Note that the procedure for measuring 1-(o using the indicator can be carried out according to a well-known method.

That is, indicators with a large pK value and indicators with a small pKa value are added to the sample in order, and the change in color of the sample is examined to determine the highest acid strength (-10) of the sample. For example, 2,4-dinitrotoluene (pKa=-13,
75) to acidic color, but 2,4-dinitrofluorobenzene (pKa=-14,52: basic color is colorless rl
For samples that do not change color (natural color is yellow), that is, do not exhibit acidic color, the value of Ho is -14,52<Ho
It is said to be in the range <-13,75. As is well known, HOG is approximately equal to the lKa value.

Table 1 Indicators and their pKa values 2-amino-5-azotoluene +2 benzeneazodiphenylamine +1.5 dicinnamal acetone
-3 Anthraquinone -8,2p-nitrotoluene -11,352,4-dinitrotoluene -13,752,4-dinitrofluorobenzene -14,522,4,6-dolinitrotoluene -15,60 Note that the above acid strength (HO ) value indicates that the solid acid material was heated to 400 to 600°C with N2 immediately before measurement.
This is a value measured immediately after heating in a dry atmosphere and cooling to room temperature in a dry atmosphere.

By the way, according to the present invention (xZrO2-ysi02)
-zF・ms In the solid acid material, by changing the atomic ratio Zr/Si of Zr and Si in the solid acid material,
The acid strength (H0) as a solid acid changes by -10>.

The strongest acid strength (H0) is when the Zr/Si atomic ratio is 7/3
In this case, (xZrO2-y
The acid strength (HO) of si02)-zF-ms is -13,
It also reaches 75>Ho>-14,52.

K1 weight like this (xZro2-ysi02)-zF・ms
The solid acid substance shown by has a powder X-ray diffraction spectrum (X
When analyzed by RD), it has a spectrum clearly different from xZro2/ysi02.

(xZro2・yS102)・zF-mS according to the present invention
The XRD diffraction pattern of (atomic ratio of Zr and 3i 7:3) is shown in Figure 1, and XZrO2.yS! 02
The XRD diffraction pattern of (atomic ratio of Zr and 3i of 3 near) is shown in FIG.

In the solid acid material according to the present invention shown in FIG. 1, 2θ=3
Z shown in Figure 3 near 0', 50.5°, and 60°
A new peak that is not seen in the complex oxide of r 02 Si 02 appears, and (xZro 2 ・ysi
02) -zF-mS is shown to be structurally different from XZrO2.ys iQ2.

That is, according to the present invention, Z
rO2S! The atomic ratio of Zr and Si (Zr/Si) in the composite oxide before undergoing the 02 S "6 treatment is usually 99.
．． In the range of 910.1 to 10/90, X of the composite oxide
No significant peaks were observed in the RD diffraction pattern, and an XRD diffraction pattern with an amorphous crystal structure almost similar to that shown in FIG. 3 was obtained. On the other hand, this ZrO2S! According to the present invention, 1q is obtained by processing the composite oxide of 02 with 5F6rffi (xZrO2・ysi02
)-zF-ms (The atomic ratio of Zr/Si is 99.910
．． 1 to 10/90), the XRD diffraction pattern shows a clear and strong diffraction peak with 2θ=
28°, 300.31.4°, 34°, 35°, 50'
, observed at a position around 60°C. However, this
In the RD spectrum, the Zr/Si atomic ratio and SF6
Although the relative intensity ratio of the diffraction peaks may differ somewhat depending on the processing conditions, relatively strong peaks appear at approximately the same positions as described above. This SF5
New diffraction peaks that appear due to the treatment are attributed to ZrO2, and from these XRD spectra,
When ZrO2-3i02 composite oxide is treated with SF6,
It is presumed that ZrO2 in the composite oxide approaches a metastable tetragonal system. In addition, in the composite oxide according to the present invention, the XRD peak attributed to SiO2 is normally melaless, and it was considered that SiO2 was not crystallized in the S6 treatment, unlike ZrO2.

In the XRD analysis performed in the present invention, a powder sample was prepared in a dry nitrogen atmosphere and measured under the conditions shown below.

Voltage: 40kvCurr
ent: 100mA Current
Full: QQQcpsTime Con5t
ant:0.5sec3 Cann1n(I S
I) eed: 4℃/min [) ivergenc
y: 1/2゜Receivinc+
5lit: 0.15mX-ray:C
uKα(H0) is 54A)
The subtraction of m3 and ZrO2-SiO2 is also shown by X-ray photoelectron spectroscopy (XPS).

z ro2-s r X before and after processing ro2 with S[6
The PS chart is shown in Figure 4 for 3d electrons of Zr.
The Is electrons of 3i are shown in FIG. 5, the 2p electrons of 3i are shown in FIG. 6, and the Is electrons of O are shown in FIG.

From these figures, it can be seen that in the solid acid material according to the present invention, the 1S electron spectrum of fluorine atoms is detected, and the main spectrum of 2p electrons of silicon atoms is shifted to the higher energy side by 1 to 2 eV. Recognize.

In addition, in the present invention, xPS analysis is performed at room temperature at 35 to 8
The experiment was carried out using a sample of 0 mesh under a vacuum of about 1×10'Pa using MgKα or AIKα as an X-ray source.

Method for preparing solid acid Next, according to the present invention (xZrO2 ・yS i 02 )
- A method for producing a solid acid substance represented by zF-ms will be explained.

The above-mentioned solid acid substance according to the present invention contains a complex metal oxide represented by Z r02 S i 02 which is prepared by a normal method in a proportion of 300 to 40%.
Obtained by treatment with SF6 at temperatures between 0 and 700°C.

zrO2S! In order to obtain the composite metal oxide represented by 02, for example, zrO(NO3)2.2■20 and Si
(Zr(OH)4 and Si(OH) obtained by hydrolysis of OC21-15>4 with aqueous ammonia, respectively)
) 4, and then washed with water, filtered and dried, and then calcined. Zr above
ZrOCl2 instead of O(N03) 2-2820
・8H20 may be used, and 5i (OC2 to 15)
Ordinary silica gel may be used instead of 4.

In the present invention, ZrO2-3!02 subjected to SF6 treatment
The method for obtaining the composite metal oxide represented by is not limited to the above method, but may be prepared using commonly known coprecipitation methods, impregnation methods, etc.

The atomic ratio of Zr and 31 is 99.91 as mentioned above.
0.1-10/90 preferably 90/10-50150
It is. This composite metal oxide represented by ZrO2-SiO2 is heated at a temperature of 300 to 800°C, preferably 400 to 700°C.
However, prior to the treatment with SF6, the ZrO2-3i02 composite metal oxide is preferably heated and evacuated at the above treatment temperature or higher.

When treating the ZrO2Si02 composite metal oxide with S'6, if the treatment temperature is less than 300'C, the obtained (
xZrO2・ySiO2)・7F・ms is unfavorable because it is difficult to form superacid sites; on the other hand, if it exceeds 800℃,
Similarly obtained (xzro2'ySI02 >-z[-
This is not preferable because super strong acid sites are difficult to form in ms.

Here, we will discuss the relationship between the treatment temperature and acid strength (H0) of -10) when xZrO-ysi02 composite metal oxide is treated with SF6, and the relationship between the treatment temperature and the F and S introduced into the oxide.
Table 2 shows the relationship between il and il.

The atomic ratio of Zr to Si in the Z r 02 S i 02 used was 7/3, and the firing temperature was 600°C.

Hydrocarbon decomposition method Next, (xZrO2・ySi02)・ZF− according to the present invention
A hydrocarbon decomposition reaction using a solid acid substance represented by ms as a catalyst will be explained.

The hydrocarbon decomposition reaction according to the present invention is as described above (x
ZrO2・VS! In the presence of a solid acid substance represented by 02>-zF-mS, a paraffin having 5 to 10 carbon atoms or a hydrocarbon containing the paraffin as a main component (these are called hydrocarbons (a)) are reacted. , carbon number 3-4
Lower aliphatic hydrocarbons containing paraffin as the main component (
These are characterized by producing hydrocarbons (referred to as hydrocarbons (b)).

The hydrocarbon (a> used as a raw material in the catalytic reaction of the present invention is a paraffin having 5 to 10 carbon atoms or a hydrocarbon containing this paraffin as a main component. As such a paraffin having 5 to 10 carbon atoms) is n-pentane, 2-methylbutane, n-hexane, 3-methylpentane, 2゜2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 3-ethyl Pentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2,3-trimethylbutane, n-octane, 3-ethylhexane, 2゜5-dimethylhexane,
Specific examples include nonane and decane, among which n-hexane, 3-methylpentane, 2,3-dimethylbutane, n-hebutane, 2-methylhexane, 3-methylhexane, 3-ethyl Pentane, 2,2-dimethylpentane, 2,3-dimethylpentane, and 2,4-dimethylpentane are preferably used.

In the present invention, it is possible not only to catalytically decompose the above-mentioned paraffins singly or in combination of two or more types, but also to decompose aromatic substances such as cyclohexane, cyclohexene, benzene, decalin, tetralin, hexene, and octene in addition to such paraffins. Hydrocarbon mixtures containing other hydrocarbons such as naphthenic components, naphthenic components, and olefinic components, and in which the content of paraffins having 5 to 10 carbon atoms is usually 30% or more, can also be used as raw materials. Examples of such hydrocarbon mixture raw materials include light naphtha, which is obtained by distillative separation or catalytic cracking of crude oil and whose boiling point range is usually in the range of 30 to 130°C.

Such a reaction is usually carried out using a known gas phase catalytic reaction apparatus under the following conditions.

The reaction is usually 100 to 600'C1, preferably 200 to
It is carried out at a temperature in the range of 600°C. reaction temperature is 100
If it is less than C1, it is not preferable because a sufficient conversion rate cannot be obtained, while if it exceeds 600C, C1. This is not preferable because the production of C2 fraction increases.

In the present invention, the raw material hydrocarbon (a) is fed into the reactor in a predetermined amount through a preheater. Liquid hourly space velocity (LH3V: Liquid 1lourlySpa
ce Velocity>, and this value is usually 0.01 to 10 hr-1, preferably 0.1 to 5 hr.
-1 range. Also, the gas hourly space velocity (G l-I
When expressed as SV), it is usually 10 to 10.0O
Ohr-1, preferably in the range 100 to 1,000h-.

Regarding the pressure of the reaction, it is usually carried out under atmospheric pressure, but it can also be carried out under appropriate pressure if necessary. In the present invention, when carrying out the reaction, an inert gas such as nitrogen may be brought into the window as appropriate.

The reaction products exiting the reactor are cooled and separated into gas and liquid products, which are each analyzed by gas chromatography.

(xZrO2-ysi02)-z"・～
Hydrocarbons having 5 to 10 carbon atoms (
When a) is reacted, butane, pentane and propane are produced with high selectivity, and the raw material hydrocarbon (a)
The conversion rate of is also extremely high.

Effects of the Invention According to the present invention, the above formula XZrO2·'i/31 is jq
The solid acid substance represented by 02 ・Z F -m, 5 has extremely strong acid strength, the super strong acid point does not decompose easily even when it comes into contact with moisture, and the temperature range in which it can be used as a catalyst is limited. wide.

Hydrocarbons (a) containing paraffins having 5 to 10 carbon atoms
When reacted in the presence of the above solid acid substance, the carbon number is 3 to 4.
Lower aliphatic hydrocarbons whose main component is paraffin can be obtained in high yield.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

亙凰■ゆうZrO(NO3)2 '2H20の112.39(0,
42 mol> was dissolved in distilled water of step 11, and NH
3 Add water and set the DI of the solution to 8 to 10 to Zr(OH)
I got 4. On the other hand, Sl (OC2H5)447)37,
5 g (0.18 mol) of CN30H50
Dissolve in 0cc and add NH3 water to 5i (Otl)
I got 4. These two gels were mixed directly and stirred roughly for 30 minutes at room temperature. These mixed gels were thoroughly washed with water, filtered, kneaded in a mixer for 1 hour, and then
It was dried at 00°C for 15 hours. The powder obtained after drying was
It was classified into ~80 meshes and calcined in air at 600'C for 3 hours to prepare a ZrO2-SiO2 composite oxide.

This ZrO□-8i02 composite oxide 2 was filled into a quartz reaction tube, and the tube was vacuum-exhausted at 600°C for 1 hour. After cooling to room temperature, S 6 gas was introduced until the pressure reached normal pressure. The reaction tube was heated to 600°C and held for 1 hour.Then, the inside of the reaction tube was replaced with N2, and then heated to 600'C.
Vacuum evacuation was performed for 1 hour.

Obtained (ZrO2 “5i02 >”F”F in S
The table below shows the results of measuring S and S as well as the specific surface area.
Shown in 3. Also, ZrO2-SiO before treatment with SF6
The specific surface area of 2 is also shown in Table 3.

Table 3 also shows the specific surface area of 2rO□-8io2 before treatment with SF6. Roughly, the acid strength (H0) of this substance (-10) was measured by the indicator method according to the method explained in the specification, and it was found to be -13,75>1-to>-1.
4,52, indicating that this material is a solid superacid. The atomic ratio of Zr and 3i in the obtained substance was 7=3 as seen from the raw material blending ratio.

The same procedure as in Example 1 was carried out except that the atomic ratio of Zr:3i: was changed from 7=3 to 9:1. F and S in the obtained substance and specific surface area were measured and shown in Table 3.

Further, the acid strength (Ho) of this material was measured in the same manner as in Example 1.

The same procedure as in Example 1 was carried out except that the atomic ratio of Zr:Si: was changed from 7:3 to 1=1. F in the obtained substance
Table 3 shows the results of measuring S and specific surface area. Further, the acid strength (t-10>) of this material was measured in the same manner as in Example 1.

Example 1 except that the atomic ratio of X dust I Zr:Si was changed to 3 near
I did the same thing. Table 3 shows the results of measuring the S and specific surface area of the 1q substance. Also, the acid strength (+-10>) of this substance was measured in the same manner as in Example 1.

From this Table 3, it can be seen that when the Zr/Si atomic ratio is around 7/3, there is an extremely strong super acid site with an acid strength of -13.75 or less (
It can be seen that this occurs during xZrO2 ``y's!02 >-zF・ms.

Example 5 The atomic ratio of Zr:3i, which was 19 in Example 1, was 7/3
A decomposition reaction of n-hexane was carried out as follows using a solid super strong acid as a catalyst.

A pulse reactor directly connected to a gas chromatography system was used as a reactor, and the pulse reactor was filled with 100 mg of catalyst, the reaction pressure was set to 1'j/ciG, and the reaction temperature was set to 200
Table 4 shows the results of the reaction performed by supplying 0.5 μg of n-hexane.

Analysis of the reaction products and conversion rate of n-hexane were performed by gas chromatography directly connected to the pulse reactor.

Example 6 Prior to carrying out a decomposition reaction of n-hexane using the solid super strong acid with an atomic ratio of Zr:3i of 7/3 obtained in Example 1 as a catalyst, a pulse reactor was filled with
Table 4 shows the results of injecting 0.5 μg of water into the catalyst at 600'C for 10 pulses, bringing the catalyst into contact with steam, flowing N2 gas at the same temperature for 30 minutes, and then carrying out the reaction at 200'C. It was shown to. It can be seen that the catalytic activity of the solid acid material of the present invention hardly changes even when it comes into contact with water.

In Example 5, the decomposition reaction of n-hexane was carried out in the same manner as in Example 5 except that the reaction temperature was 250'C.

The results are shown in Table 4.

In Example 5, n-hexane was decomposed in the same manner as in Example 5 except that the reaction temperature was 300'C.

The results are shown in Table 4.

In the catalysts used in Examples 5 to 8, ZrO2-3i 0 was not subjected to SF6 treatment to obtain the catalysts.
2 (Zr/S i =7/3), the reaction was carried out in the same manner as in the example, but no reaction occurred in this case.

In Example 1, ZrO (NO3>2-2H20 and S
i (QC2tl 5 ) 4 and ZrO obtained from
Z
rO2-3i02-F-3 catalyst was prepared, and the reaction temperature was adjusted to 200°C and 300'C1350'C using this solid super acid.
The decomposition reaction of n-hexane was carried out in the same manner as in Example 5 except for the following.

The results are shown in Table 5.

In Example 1, Z r O (NO3>2 ・2H20
And 3! (ZrO2S obtained from OC2115>4!
After baking the 02 composite oxide at 600°C for 2 hours, SF
ZrO2 was treated with 6 gases at a temperature of 500'C for 1 hour.
A decomposition reaction of n-hexane was carried out in the same manner as in Example 5, except that a "S!02'F'S catalyst was prepared and the solid superacid was used at 250°C and 300'C1350°C.

The results are shown in Table 6.

[Brief explanation of drawings]

Figures 1 and 2 are (X Z r02 ・ys ! 0
2)-zF-ms (x/y=7/3.3/7), and Figure 3 shows the powder X-ray diffraction spectrum of
y'S! 02 (x/y=7/3). Also, in Fig. 4, xZrO2・ysr
Fig. 5 shows the spectra of Zr3d electrons before and after SF6 treatment of
ys! The spectra of F1S electrons before and after the 02S6 treatment are shown by X-ray photoelectron spectroscopy.
The spectra of 5i2p electrons obtained by X-ray photoelectron spectroscopy before and after the SF6 treatment of rO2.ySiO2 are shown, and FIG. 7 shows the spectra of OIS electrons obtained by X-ray photoelectron spectroscopy before and after the SF6 treatment of XZrO2.ySiO2.

Claims (1)

[Claims] 1. Formula (xZrO_2・ySiO_2)・zF・mS・
...[I] [In the formula, x and y are ZrO_2 and Si
It shows the number of moles of O_2, and the value of x/y shows the atomic ratio of Zr/Si. Also, z and m are each (xZrO_2・ySiO_2)
The weight % of F atoms and the weight % of S atoms are shown relative to the weight of . And x/y is in the range of 99.9/0.1 to 10/90, z is in the range of 0.1 to 10, and m is in the range of 0.01 to 5. ] A ZrO_2-SiO_2-based solid acid material, which is a composite metal oxide represented by the following formula and has a strong acid point with an acid strength (H_0) of -8.2 or less. 2. ZrO_2-SiO_2 composite metal oxide from 300 to
Characterized by treatment with SF_6 at a temperature of 800°C, the acid strength (H_0) is -
Method for producing ZrO_2-SiO_2-based solid acid material having a strong acid point of 8.2 or less: Formula (xZrO_2・ySiO_2)・zF・mS...
... [I] [In the formula, x and y are ZrO_2 and SiO_
The value of x/y indicates the atomic ratio of Zr/Si. Also, z and m are each (xZrO_2・ySiO_2)
The weight % of F atoms and the weight % of S atoms are shown relative to the weight of . And x/y is in the range of 99.9/0.1 to 10/90, z is in the range of 0.1 to 10, and m is in the range of 0.01 to 5. ] 3. Paraffin having 5 to 10 carbon atoms or a hydrocarbon containing the paraffin as a main component (these are referred to as hydrocarbons (a)) is ZrO_2-SiO_ shown by the following formula [I].
A method for decomposing hydrocarbons (a), which comprises producing lower aliphatic hydrocarbons (b) whose main component is paraffin having 3 to 4 carbon atoms by reacting with the presence of a 2-based solid acid substance. : Formula (xZrO_2・ySiO_2)・zF・mS...
... [I] [In the formula, x and y are ZrO_2 and SiO_
The value of x/y indicates the atomic ratio of Zr/Si. Also, z and m are each (xZrO_2・ySiO_2)
The weight % of F atoms and the weight % of S atoms are shown relative to the weight of . And x/y is in the range of 99.9/0.1 to 10/90, z is in the range of 0.1 to 10, and m is in the range of 0.01 to 5. ]