JPS62153234A - Production of para-substituted halogenated benzene derivative - Google Patents

Abstract

PURPOSE:In the liquid-phase halogenation reaction of benzene and/or benzene derivative in the presence of a faujasite type zeolite catalyst, a sulfur compound is added to the reaction system to give the title compound in high yield. CONSTITUTION:A faujasite type zeolite, especially X-type or Y-type zeolite modified by an alkali, alkaline earth or rare-earth metal salt, is used as a catalyst to effect the liquid-phase halogenation of benzene and/or benzene deriva tive to give the title compound. At this time, a sulfur compound, preferably elementary sulfur, halogenated sulfur, thiophene, sulfide, sulfoxide or sulfone is added to the reaction system in an amount of 0.001-0.5g/g-faujastie to increase the reaction yield.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a halogenated benzene derivative by liquid-phase halogenation of benzene and/or a benzene derivative. More specifically, it relates to a method for producing para-substituted halogenated benzene derivatives by liquid-phase halogenation of benzene and/or benzene derivatives using faujasite-type zeolite as a catalyst and coexisting a sulfur-containing compound in the reaction system. It is.

[Conventional technology]

Halogenated benzene derivatives are industrially important raw material intermediates in the field of organic synthetic chemistry, including medicines and agricultural chemicals. Generally, they are produced by using benzene and/or Alternatively, it is produced by liquid phase halogenation of benzene derivatives. For example, dichlorobenzene (hereinafter abbreviated as DCB) is converted into benzene or monochlorobenzene (hereinafter referred to as MCB) in the presence of ferric chloride.
It is manufactured by blowing chlorine gas into

In the production of disubstituted benzene derivatives by liquid phase halogenation of monosubstituted benzene derivatives, 12-
Di-substituted product (ortho form), 1,3-di-substituted product (meta form)
Three types of isomers are obtained: , 1,4-disubstituted product (para-isomer), but the production ratio of each of these isomers is determined by the type of substituents already present, the type of catalyst, etc. is well known. For example, MCB in the presence of ferric chloride
During the production of DCB by O liquid phase chlorination reaction, the proportions of the three types of isomers produced are as follows.

Orthodichlorobenzene: 3o~40% Metadichlorobenzene 20~5% Paradichlorobenzene: 6o
~70% Among the three isomers, para-substituted halogenated benzene derivatives are the most important industrially and are in high demand. Therefore, a large number of methods have been proposed for selectively producing halogenated benzene derivatives.

Selectively producing halogenated benzene derivatives. As one method, without using Lewis acid catalyst,
Recently, methods have been discovered to use zeolites as catalysts. For example, Journal of Catalysis (Jo
60.1)
0 (1979), the use of zeolite as a bromination catalyst for halogenated benzene is reported. In this cited example, various ion-exchange zeolites, namely X-type and Y-type zeolites, are used as halogenation catalysts. It has been shown that para-substituted bromobenzene derivatives are selectively produced.

Also, Tetrahedron Letters (Tetrahedr)
onLetters) 21.3809 (1980)
ZSM-5, ZSM-1), mordenite,
The chlorination reaction of benzene using L-type zeolite, Y-type zeolite, etc. as a catalyst has been reported, and in particular, in the case of L-type zeolite, paradichlorobenzene (hereinafter referred to as PDCB)
It is stated that the selectivity (abbreviated as ) can be obtained.

Furthermore, for example, JP-A-59-130227;
JP-144722, JP-A No. 59-163329, etc. disclose a method for halogenating benzene or alkylbenzene using L-type zeolite or Y-type zeolite as a catalyst.

In addition to these, the present applicant has discovered that the selectivity of rose-substituted halogenated benzene derivatives can be improved by modifying Y-type zeolite, L-type zeolite, etc. with a metal salt, and has previously filed an application.

On the other hand, when a Lewis acid such as ferric chloride is used as a catalyst, adding various sulfur-containing compounds as co-catalysts to the reaction system improves the selectivity of para-substituted benzene derivatives. It is known to do so. For example, in US Pat. No. 3,226,447, in the chlorination reaction of benzene, MCB, etc., an organic sulfur compound containing divalent sulfur is added to a Lewis acid such as ferric chloride as a cocatalyst to select a rutpara-substituted halogenated benzene derivative. It has been reported that the rate is improved. That is, in this cited example, when the chlorination reaction of Pe/Ze/ is carried out using iron and thioglycolic acid as catalysts, PD in the generated DCB
It has been shown that the proportion of CH reaches 77%. In addition, in the chlorination reaction of alkylbenzenes etc., as an example of producing a partially substituted halogenated benzene derivative using elemental sulfur or an inorganic sulfur compound as a catalyst together with a Lewis acid such as ferric chloride or antimony trichloride, For example, US Patent No. 1946040, British Patent No. 1) 53746
You can list the number etc.

However, it is well known to those skilled in the art that these known methods require a Lewis acid as a catalyst.

[Problem that the invention seeks to solve]

By using zeolite as a catalyst in the liquid phase halogenation reaction of benzene and/or benzene derivatives, para-substituted halogenated benzene derivatives It is clear from the prior art that scales can be selectively produced.

However, even in these prior art techniques, the selectivity of para-substituted halogenated benzene derivatives is far from sufficient, and there is a strong need for the development of a method for producing para-substituted halogenated benzene enzyme derivatives with even higher selectivity. There is.

[Means for solving problems]

In view of this current situation, the present inventors conducted a detailed study on a method for selectively producing para-substituted halogenated benzene derivatives by liquid-phase halogenation reaction of benzene and/or benzene derivatives, and in particular, a reaction using a zeolite catalyst. .

As a result, the present inventors found that, surprisingly, when faujasite-type zeolite was used as a catalyst and a sulfur-containing compound was coexisting in the reaction system, the activity hardly decreased.
It was found that the regioselectivity of halogenation changes and the selectivity of para-substituted halogenated benzene derivatives is improved.

As mentioned above, when a Lewis acid such as ferric chloride is used as a catalyst in the halogenation reaction of benzene and/or benzene derivatives, when a sulfur-containing compound is added as a cocatalyst, the selection of para-substituted halogenated benzene derivatives is improved. It is known that the rate is improved, and this is believed to be due to the sulfur-containing compound modifying the Lewis acid. That is, in a liquid phase halogenation reaction using a Lewis acid catalyst,
Lewis acids are so-called homogeneous catalysts that exhibit catalytic action when dissolved in the reaction solution. Therefore, the reason for the cocatalytic effect of sulfur-containing compounds is that, like Lewis acids, the sulfur-containing compounds dissolved in the reaction solution It is presumed that the properties of the Lewis acid are changed by coordinating with the Lewis acid.

On the other hand, in the liquid phase halogenation reaction using a zeolite catalyst, the zeolite catalyst does not dissolve at all in the reaction solution, and the zeolite acts as a solid-liquid heterogeneous catalyst, and the action mechanism of the zeolite catalyst is a Lewis acid This is completely different from the case of catalysts. Furthermore, considering that the coexistence effect of sulfur-containing compounds on zeolite catalysts is specific to faujasite zeolites among zeolites, the coexistence effect of sulfur-containing compounds is completely different from the promoter effect on Lewis acid catalysts. The present invention is constructed based on the discovery of new facts.

That is, the present invention is characterized in that when a halogenated benzene derivative is produced by a liquid phase halogenation reaction of benzene and/or a benzene derivative using a faujasite type zeolite as a catalyst, a sulfur-containing compound is allowed to coexist in the reaction system. The present invention provides a method for producing a halogenated benzene derivative.

In the method of the present invention, zeolite is used as a catalyst, and zeolite is usually called crystalline aluminosilicate. Zeolite is composed of 5i04 tetrahedrons and MO4 tetrahedra, and many types are known due to differences in the bonding modes of each tetrahedron. The zeolite used as a catalyst in the process of the invention is a faujasite type zeolite. Faujasite-type zeolite exists naturally, but it can also be synthesized by known methods, and synthetic faujasite-type zeolite is widely known as X-type zeolite and Y-type zeolite.The present invention In the method, synthetic faujasite zeolites with few impurities and high crystallinity among faujasite zeolites are preferred, and Y-type zeolites are particularly preferred.Faujasite zeolites have a characteristic crystal structure. It is possible to distinguish it from other zeolites by measuring the powder X-ray diffraction spectrum.

The chemical composition of faujasite type zeolite is expressed as 8M2/no-AJ203.bSi02 in terms of the molar ratio of oxides. Synthetic faujasite-type zeolites, ie, type-X zeolites and type-X zeolites, generally contain Na ions as cations in the as-synthesized state.

In the method of the present invention, Fujasai)! There are no particular restrictions on the cations contained in zeolite, and zeolites containing Na ions during synthesis may be used as catalysts, but if necessary, zeolites exchanged with other cations may also be used. No problem. In this case, ion exchange treatment may be performed by a known method using an aqueous solution containing the cations to be exchanged.

In the method of the present invention, various ion-exchanged faujasite zeolites may be used as catalysts as they are, but faujasite zeolites modified with metal salts are preferably used. For example, the modification of faujasite type zeolite with metal salts is
It can be carried out according to the method described in No. 466@Ki.

In other words, it is sufficient to bring the faujasite type zeolite and the metal salt into intimate contact with each other, and specifically, the usual impregnation method,
Examples include a mixing method and a kneading method. There are no particular restrictions on the method of modification with metal salts, but it is possible to homogeneously modify not only the outer surface of faujasite-type zeolite particles but also the inside of the pores, and it is easy to use. A conventional impregnation method in which faujasite-type zeolite is impregnated with a solution dissolved in a solvent such as water is suitable.

In this case, there are no particular restrictions on the metal salt used for modification, and halides, sulfates, carbonates, etc. of alkali metals, alkaline earth metals, rare earth metals, etc. may be used. Examples include sodium chloride, potassium chloride, strontium chloride, barium chloride, lanthanum chloride, sodium carbonate, potassium carbonate, strontium carbonate, barium carbonate, sodium sulfate, potassium sulfate, strontium sulfate, barium sulfate, and the like.

The amount of the metal salt used for modification is 0.1% by weight based on the faujasite type zeolite.
It may be 90%, preferably 10 to 80%.

In the method of the present invention, there is no particular restriction on the shape of the catalyst, and it may be used as a catalyst by being normally shaped, but there is no problem in using it as a powder. The molding method may be a conventional method, and examples thereof include extrusion molding, tablet molding, spray drying granulation, and the like. When molding,
For the purpose of increasing the mechanical strength, etc., a substance inert to this reaction may be added as a binder or molding aid. For example, silica, clays, graphite, stearic acid, starch, polyvinyl alcohol, etc.
It can be added in an amount of t%, preferably in the range of 2-30 wt%.

The catalyst obtained in this manner is dried if necessary, and then calcined for 10 minutes to 24 hours under air flow or an inert gas flow such as nitrogen or helium. Used for chemical reactions. Firing temperature is 200~
The temperature range may be 900°C, preferably 600 to 850°C.
℃ is good.

In the method of the present invention, the liquid phase halogenation reaction of benzene and/or benzene derivatives is carried out in the presence of a sulfur-containing compound in the reaction system. The sulfur-containing compound means an inorganic compound containing simple sulfur, a sulfur atom with a divalent bond, or an organic compound containing sulfur. here,
Bond valence refers to the number of bonds that one sulfur atom has with other atoms (including other sulfur atoms). In the case of an inorganic compound containing a sulfur atom whose bond valence is divalent,
Compounds consisting of a nonmetallic element, such as hydrogen, or a sulfur atom whose bond valence is divalent to an element of the carbon group, nitrogen group, or halogen group in the periodic table are preferable1. Examples of inorganic compounds include simple sulfur. In addition, -sulfur chloride, sulfur dichloride, -sulfur bromide, carbon disulfide, hydrogen sulfide,
Silicon disulfide, sulfur nitrides, and phosphorus sulfides can be mentioned, and elemental sulfur, -sulfur chloride, and sulfur dichloride are particularly preferred.

Examples of sulfur-containing organic compounds include mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan; sulfides such as dimethyl sulfite, diethyl sulfite, and diphenyl sulfide; thiophenes such as thiophene, methylthiophene, and chlorothiophene; Examples include disulfides such as dimethyl disulfide and Schiffenyl disulfide, sulfoxides such as dimethyl sulfoxide and diphenyl sulfoxide, and sulfones such as dimethyl sulfone and diphenyl sulfone.In particular, sulfides such as diphenyl sulfide, thiophenes such as thiophene, Sulfoxides such as diphenyl sulfoxide and sulfones such as diphenyl sulfone are preferred.

These sulfur-containing compounds only need to coexist in the liquid phase rogogenation reaction solution, and there are no particular restrictions on the method of addition.

That is, the sulfur-containing compound may be added to the reaction system separately from the raw materials and catalyst, or the sulfur-containing compound may be adsorbed or supported on faujasite-type zeolite (K), which is the catalyst, and introduced into the reaction system together with the catalyst. . In a continuous reaction, a sulfur-containing compound may be contained in the raw material and, for example, the sulfur-containing compound may be dissolved under the pressure of a liquid raw material, and then supplied together with the raw material into the reaction system.

There are a wide variety of sulfur-containing compounds, and they are affected by the addition method, etc., so it is difficult to unambiguously limit the amount of sulfur-containing compounds. It is possible. In the method of the present invention, the amount of the sulfur-containing compound present is 1×10 I! per unit weight of the faujasite zeolite that is the catalyst. /,? - faujasite ~ t o y/g - faujasite,
Preferably 1×101)/Ii-Faujacytol 0
．． 51 calf ossia site. If the coexisting amount of the sulfur-containing compound is less than 1 x 10 1/1)-faujasite, the effect of improving the selectivity of para-substituted halogenated benzene derivatives cannot be obtained, and if the coexisting amount is more than t o ti7tt-faujasite, There is no effect of increasing the amount, and it is uneconomical.

In the method of the present invention, the benzene derivative refers to a compound in which the hydrogen of benzene is substituted with a substituent such as a halogen or an alkyl group, such as halogenated benzene, alkylbenzene, etc., such as monofluorobenzene, MCB,
Monobromobenzene, monoiodobenzene, toluene,
Examples include ethylbenzene. Further, the halogenating agent may be a single halogen, such as chlorine, bromine,
Iodine can be mentioned.

In the method of the present invention, there are no restrictions on the reaction apparatus, reaction method, and reaction conditions as long as benzene and/or benzene derivatives are brought into contact with the catalyst in a liquid state. For example, the reactor may be of a batch type, semi-batch type, or continuous type. The catalyst can be used, for example, in the form of a fixed bed or suspended bed.

The reaction may be carried out in the presence of a solvent that does not participate in the halogenation reaction, such as carbon tetrachloride.

When using a solvent, the concentration of benzene and/or benzene derivatives is preferably 5 to 99 wt%, and 20 to 99 wt%.
is preferred. If it is less than 5 wt%, there will be fewer opportunities for the raw material to come into contact with the catalyst, making it impossible to obtain a sufficient conversion rate. When continuously supplying the halogenating agent, nitrogen, helium,
An inert gas such as carbon dioxide may be included. When using an entrained gas, the concentration of the halogenating agent is 5 to 99 vol.
1. %, preferably 20 to 99 vol.

When using a batch type or semi-batch type reactor, the catalyst is mainly used in the form of a turbid solution, but the amount of catalyst per unit reaction liquid volume is preferably 0.001 to 1 Vl, and 0.005 to α1.
kV/l is preferred. o, o o i less than a sip,
The load on the catalyst is large and a sufficient conversion rate cannot be obtained. Furthermore, if the amount is more than 1 kg/j, the effect of increasing the amount of catalyst will be reduced. When the halogenating agent is continuously supplied, the amount of the halogenating agent supplied can be expressed as the amount of the halogenating agent per unit time relative to the weight of the zeolite, and is 1 to 1.
1500 mol/kiJ-cat, hr is good, 1
0 to 800 matAII-cat, hr is preferred.

jrnol/kII-cat, if it is less than hr, a sufficient halogenated benzene production rate cannot be obtained, and 1500mos
If it exceeds /5qi-cat,hr, the amount of unreacted halogenating agent increases, which is not economical.

When a continuous reactor is used, the amount of benzene and/or benzene derivatives supplied can be expressed as the amount per unit time relative to the zeolite used, and is 0.5 to 500.
1/kit-cat, hr is enough, 2-10017k
l-Cai, )lr is preferred. Other reaction conditions are:
This is the same as when a batch type or semi-batch type reactor is used.

In the method of the present invention, there are no restrictions on the reaction temperature and reaction pressure as long as benzene and/or benzene derivatives are in a liquid phase. When the reaction temperature is higher than the boiling point of benzene and/or benzene derivatives, the halogenation reaction can be carried out in the liquid phase by increasing the reaction pressure.
The reaction temperature is preferably 0 to 200°C, preferably 20 to 150'C.
is even more preferable. If it is less than 0°C, a sufficient reaction rate will not be achieved, and if it is higher than 200°C, the selectivity of the para-substituted halogenated benzene derivative will decrease.

〔Effect of the invention〕

According to the method of the present invention, industrially valuable para-substituted halogenated benzene derivatives can be obtained in higher yields than known methods in the liquid phase halogenation reaction of benzene and/or benzene derivatives. Therefore, the present invention is extremely significant from an industrial perspective.

〔Example〕

Below, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited only to these examples. Note that the conversion rate and selectivity shown in the examples represent numerical values calculated using the following formula.

×100 Examples 1 to 6 4.29.9 ml of sodium chloride was placed in the magnetic beaker of 1), and this was dissolved in 150 d of distilled water.

This solution was kept at 95°C using a hot bath, and stirred thoroughly with a glass stirring blade.
10 g of Na-Y type zeolite (Toyo Soda Kogyo ■l!8) with a kl 203 ratio of 5.5 was added. Evaporated to dryness on a hot bath until the water disappeared, and then heated in a dryer kept at 130°C.
After drying for 15 hours, it was calcined at 540°C for 3 hours under air circulation to reduce NaCl to 30! -It% supported Na-Y
A type zeolite catalyst was obtained, and a liquid phase chlorination reaction of MCB was carried out using this catalyst and sulfur monochloride as a sulfur-containing compound. The reaction was carried out in a Rex reactor (inner diameter 40 m, height 10 m).
0++a+) with an MCB of 40.9 and 0.016.9
．． 0.035g, 0.0691). 0.140g, 0.
245.9.0.574'#, - filled with sulfur chloride,
Furthermore, the above 1,4I zeolite catalyst was added to form a suspension.

While thoroughly stirring the reaction mixture with a magnetic stirrer, chlorine gas (along with constant nitrogen gas) was blown in at a feed rate of 30 min. The reaction temperature was controlled at 100° C. by using an oil bath around the reactor. Three hours after the start of blowing chlorine gas, the product was analyzed by gas chromatography. The results are shown in Table 1. 'Comparative Example 1 NaCl! prepared in the same manner as in Example 1. Example 1 except that Na-Y type zeolite modified by was used as a catalyst and no sulfur-containing compound was allowed to coexist in the old yarn.
A liquid phase chlorination reaction of MCB was carried out in exactly the same manner as described above. Table 1 shows the reaction results 3 hours after the start of chlorine gas blowing.

Example 7 Elemental sulfur 0.07,f was dissolved in 15jlj of carbon disulfide, 3g of Na-Y type zeolite modified with NaCl prepared in Example 1 was added to the solution, and carbon disulfide was dissolved using an evaporator. Distilled and sulfur-supported Na
A C1 modified Na-Y type zeolite catalyst was prepared. In this case, the weight of sulfur per unit weight of faujasite is o, 0331/9-faujasite.

Using this catalyst 1.52.9, a liquid phase chlorination reaction of MCB was carried out in exactly the same manner as in Example 1, except that -sulfur chloride was not allowed to coexist. Six hours after the start of blowing chlorine gas, the MCB conversion rate was 65.0% and the PDCB selectivity was 88.8%.

Example 8 NaCl-modified Na-Y prepared in the same manner as Example 1
type zeolite as a catalyst, and 0.0% thiophene instead of sulfur chloride. 3 g of OB was allowed to coexist, and the reaction temperature was 8.
A liquid phase chlorination reaction of MCB was carried out at 0°C.

In this case, the weight of sulfur per unit weight of faujasite was 0.0321)79-faujasite.

Note that the reaction conditions other than those described above are completely the same as in Example 1.

Table 2 shows the reaction results 3 hours after the start of chlorine gas blowing.

Examples 9-1) NaC# modified Na-Y prepared in the same manner as Example 1
type zeolite as catalyst, - 0.108 # diphenyl sulfide instead of sulfur chloride, or 0.12
1# diphenyl sulfoxide aluminum is 0.131#
A liquid phase chlorination reaction of MCB was carried out in exactly the same manner as in Example 1, except that diphenyl sulfone was allowed to coexist. Table 2 shows the reaction results 6 hours after the start of chlorine gas blowing.

Example 12 As a catalyst, 1. A liquid phase chlorination reaction of MCB was carried out in exactly the same manner as in Example 1, except that OI Na-Y type zeolite (manufactured by Toyo Soda Kogyo ■) was used and 0.540 I of sulfur chloride was allowed to coexist. Table 3 shows the reaction results 3 hours after the start of chlorine gas blowing.

Comparative Example 2 A liquid phase chlorination reaction of MCB was carried out in exactly the same manner as in Example 12 except that sulfur monochloride was not present. Table 3 shows the reaction results 3 hours after the start of chlorine gas blowing.

Table 3 t) ODCB-ortho dichlorobenzene 2) Metadichlorobenzene, trichlorobenzenes, etc. Example 16 As a catalyst, Na- with a Siov'Ahos ratio of 2.5
A liquid phase chlorination reaction of MCB was carried out in exactly the same manner as in Example 12, except that X-type zeolite (manufactured by Toyo Soda Kogyo ■) was used. 5 hours after starting to blow chlorine gas, MC
The B conversion rate was 38.1%, and the PDCB selectivity was 73.8%.

Comparative Example 3 An MCBO liquid phase chlorination reaction was carried out in exactly the same manner as in Example 13, except that sulfur monochloride was not present. Five hours after starting to blow chlorine gas, the MCB conversion rate was 3.
7.2%, and the PDCB selectivity was 72.0%.

Comparative Example 4.5 M in the same manner as in Example 12 in the presence or absence of yellow.
A liquid phase chlorination reaction of CB was performed. Table 4 shows the reaction results 3 hours after the start of chlorine gas blowing.

Comparative Example 6.7 ZSM-5 zeolite was synthesized according to the method described in US Pat. No. 3,790,471. It was confirmed that the obtained zeolite was ZSM-5 by powder X-ray diffraction using a copper alpha doublet. After firing this ZSM-5 at 540°C under air circulation, ion exchange treatment was performed using an aqueous sodium chloride solution to form Na-ZSM-5.
Obtained zeolite. This Na-ZSM-5 had the following composition expressed in molar ratio of oxides.

180°5 Na2O・AJ203・23.35i02
A liquid phase chlorination reaction of MCB was carried out in the same manner as in Example 12 in the presence or absence of -sulfur chloride using the above NaZSM-5 as a catalyst. The reaction results after 3 hours from the start of blowing chlorine gas are shown in the fourth column.
Shown in the table.

Example 14 A liquid phase chlorination reaction of toluene was carried out in the same manner as in Example 1 except that MCB was replaced with toluene. Three hours after starting to blow chlorine gas, the toluene conversion rate was 54.2% and the parachlorotoluene selectivity was 66.8%.

Comparative Example 8 A liquid phase chlorination reaction of toluene was carried out in exactly the same manner as in Example 14, except that sulfur monochloride was not added. Three hours after starting to blow chlorine gas, the toluene conversion rate was 54.6% and the parachlorotoluene selectivity was 62.4%.
Met.

Comparative Example 9 As a catalyst, 0.4 ferric chloride was used instead of a zeolite catalyst.
MCB
A liquid phase chlorination reaction was carried out. Three hours after starting to blow chlorine gas, the MCB conversion rate was 64.7%, P
The percentage who chose DCB was 68.5%.

Claims (6)

[Claims] (1) In producing a halogenated benzene derivative by a liquid phase halogenation reaction of benzene and/or a benzene derivative using a faujasite-type zeolite as a catalyst,
A method for producing a halogenated benzene derivative, which comprises coexisting a sulfur-containing compound in a reaction system. (2) Claim No. 1, wherein the faujasite-type zeolite is an X-type zeolite or a Y-type zeolite.
The method described in section. (3) Faujasite-type zeolite is an alkali metal,
The method according to claim 1, wherein the zeolite is X-type zeolite or Y-type zeolite modified with an alkaline earth metal or rare earth metal salt. (4) The method according to claim (1), wherein the sulfur-containing compound is an inorganic compound containing elemental sulfur or a sulfur atom with a divalent bond valence. (5) The method according to claim (1), wherein the sulfur-containing compound is an organic compound containing a sulfur atom. (6) The method according to claim (1), wherein the sulfur-containing compound is elemental sulfur, halogenated sulfurs, thiophenes, sulfides, sulfoxides, or sulfones.