JPH05262682A - Production of halogenated hydrocarbon compound - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain a halogenated hydrocarbon compound such as vinyl chloride important for the petrochemical industry by reacting a halogenated methane with oxygen using an alkali metallic compound, etc., as a catalyst. CONSTITUTION:A halogenated methane (preferably monochloromethane) is subjected to oxidative coupling reaction in the presence of an alkali metallic compound (e.g. lithium chloride) and a compound of a metal selected from groups Ib, IIb, Vb, VIb, VIIb, VIII, IIIa, IVa and Va of the periodic table and oxygen to afford the objective compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a halogenated hydrocarbon compound having two or more carbon atoms such as vinyl chloride, which is important in the petrochemical industry.

[0002]

2. Description of the Related Art Vinyl chloride (hereinafter abbreviated as VCM), which is a raw material for vinyl chloride resin, is currently produced in large quantities from ethylene by the so-called oxychlorination method or chlorine addition method. The oxychlorination method uses ethylene, oxygen and hydrogen chloride, and the chlorine addition method adds chlorine to ethylene to give 1,2-dichloroethane (hereinafter referred to as E
DC), and the resulting EDC is pyrolyzed to produce V
It manufactures CM.

Since this method uses ethylene obtained by naphtha or LPG decomposition as a raw material, it may be resource-constrained in the future, greatly depends on the price of naphtha, and is strongly affected by it. There is a problem that the decomposition furnace needs to be regenerated periodically because carbonaceous matter accumulates in the decomposition furnace during decomposition.

In response to such a situation, studies are being conducted to produce vinyl chloride from methane, which is a main component of natural gas, which is rich in resources. For example, R. G. Min
et al. produced VCM by reacting methane and chlorine without a catalyst at a high temperature of over 1000 ° C. to obtain a product rich in acetylene and hydrogen chloride, and further adding hydrogen chloride to acetylene in the presence of a catalyst. Has proposed a process (US Pat. No. 4,804,797). However, this method has a problem that it is a reaction at an abnormally high temperature, a large amount of energy is required, and a large amount of hydrocarbons such as benzene are by-produced.

[0005]

As described above, in the conventional technology for producing vinyl chloride, it is necessary to once produce ethylene and use it as a starting material, and it is the main component of natural gas. When methane is used as a starting material, many problems remain, such as a complicated process, high temperature required, and many by-products.

[0006]

In view of the present situation as described above, the present inventor has conducted a detailed study on the reaction of halogenated methane, and as a result, found a new fact and completed the present invention.

That is, according to the present invention, when a halogenated hydrocarbon compound having two or more carbon atoms is produced by a reaction of halogenated methane and oxygen, an alkali metal compound and a group Ib, IIb or Vb of the periodic table are used as a catalyst. , VIb group,
Group VIIb, Group VIII, Group IIIa, Group IVa, Va
It relates to a method for producing a halogenated hydrocarbon compound, characterized in that a compound of a metal selected from the group is used.

The present invention will be described in more detail below.

In the present invention, halogenated methane is subjected to an oxidative coupling reaction in the presence of a catalyst and oxygen to produce a desired halogenated hydrocarbon compound having 2 or more carbon atoms. The halogenated methane that can be used in the method of the present invention is not particularly limited as long as it contains at least one atom of halogen. Here, examples of the halogen include chlorine, bromine, iodine and fluorine. Examples of this specific compound include monochloromethane, dichloromethane, chloroform, chloromethanes such as carbon tetrachloride, bromomethanes such as monobromomethane and dibromomethane,
Examples thereof include iodomethanes such as monoiodomethane and diiodomethane, and fluoromethanes such as monofluoromethane and difluoromethane. Of course, halogenated methane containing two or more kinds of halogens can also be used.
In the present invention, it is more preferable to use monochloromethane.

In the present invention, oxygen may be molecular oxygen, and for example, pure oxygen or oxygen or air diluted with a gas inert to this reaction can be used. When using diluted oxygen, the amount of the diluent is not particularly limited as long as an industrially satisfactory reaction rate is obtained. In the present invention, the ratio of halogenated methane to oxygen is preferably such that the halogenated methane is present in excess with respect to oxygen. The ratio (molar ratio) of halogenated methane to oxygen is 20 to 1,
It is preferably 10 to 1. If this ratio exceeds 20, the conversion rate of halogenated methane may be low, while if this ratio is less than 1, the combustion reaction tends to take precedence.

In the present invention, an alkali metal compound as a catalyst and a group Ib, IIb, Vb or V of the periodic table.
Group Ib, Group VIIb, Group VIII, Group IIIa, IVa
A compound of a metal selected from the group and the group Va is used. As the alkali metal compound, for example, an alkali metal compound such as lithium, sodium, potassium, rubidium, or cesium can be used. These alkali metal compounds include alkali metal itself, various alkali metal inorganic salts such as chlorides, nitrates and sulfates, or formates,
Examples thereof include various alkali metal organic salts such as carboxylates such as acetate and sulfonates such as benzenesulfonate. Specific examples of such alkali metal salts include inorganic salts of alkali metals, such as lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, chlorides, lithium nitrate, sodium nitrate, potassium nitrate, nitric acid. Examples thereof include various alkali metal inorganic salts such as nitrates such as rubidium and cesium nitrate, and sulfates such as lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate and cesium sulfate. Examples of the alkali metal organic salt include lithium formate, sodium formate, potassium formate, rubidium formate, cesium formate, and other formates; lithium acetate, sodium acetate, potassium acetate, cesium acetate, and other acetate salts; and lithium benzenesulfonate. ,
Examples include various alkali metal organic salts such as sulfonates such as sodium benzenesulfonate, potassium benzenesulfonate, and cesium benzenesulfonate. In the present invention, depending on the type of the above-mentioned alkali metal salt, some compounds may be converted into other compounds during the reaction, but this is not a problem.

Next, Ib group, IIb group and Vb of the periodic table
Group, VIb group, VIIb group, VIII group, IIIa group,
As the other metal in the compound of the metal selected from the IVa group and the Va group (hereinafter abbreviated as “other metal”), examples of the Ib group of the periodic table include copper, and examples of the IIb group include , Zinc, examples of Vb groups include vanadium, V
Examples of the group Ib are chromium and molybdenum, examples of the group VIIb are manganese, and examples of the group VIII are:
Examples of iron, cobalt, nickel, and group IIIa include gallium, examples of group IVa include tin, lead, and examples of group Va include antimony and bismuth.
Of these, preferably, Group VIII iron, cobalt,
Nickel, Group Ib copper, Group VIIb manganese, IVa
It is the lead of the tribe. As the raw material for the compound of the other metal, various oxides or salts of the other metal can be used. For example, as the other metal salt, various inorganic salts such as chlorides, oxychlorides, nitrates and sulfates, and various organic salts such as acetates and acetylacetonates can be used. Two or more kinds of these other metal compounds may be used at the same time.

In the present invention, the catalyst component comprising the above-mentioned alkali metal compound and the other metal compound can be used on a carrier or without a carrier. When a carrier is used, the carrier that can be used is not particularly limited, and a known carrier can be used. Specific examples thereof include crystalline or non-crystalline oxides such as silica, alumina, silica-alumina, magnesia, titania, zirconia, and composite oxides. Among these, silica is a suitable example.
In the present invention, the method of preparing the catalyst to be used is not particularly limited and can be prepared by a known method. In the case of a supported catalyst, it can be prepared by, for example, an impregnation method or a coprecipitation method. Taking the impregnation method as an example, the alkali metal compound and the compound of the other metal are dissolved in a suitable solvent and a carrier is added thereto. Then, the solvent can be evaporated, dried and calcined to prepare the catalyst. In the impregnation method, the alkali metal compound and the compound of the other metal may be loaded simultaneously, or one of the components may be loaded first and the rest of the components may be loaded.

In the catalyst used in the present invention, the compound of the other metal used together with the alkali metal compound is preferably an oxide during the reaction. Therefore, it is preferable to convert various metal salts used as raw materials into oxides before being subjected to the reaction of the present invention. The conversion to the oxide can be easily achieved by firing in an air atmosphere. This calcination operation may be performed at any stage during catalyst preparation. The firing temperature depends on the compound of the other metal used, but is generally 1
Up to 000 ° C is enough.

In the case of the supported catalyst, the loading ratio of the alkali metal compound and the compound of the other metal is 0.1% based on the total weight of the catalyst including the carrier as the weight% of the metal.
-30% by weight, preferably 0.5-20% by weight.
When the loading rate of the alkali metal and the other metal is less than 0.1% by weight, sufficient activity cannot be obtained, and when the loading rate exceeds 30% by weight, the activity does not increase. In the case of a catalyst that does not use a carrier, the atomic ratio of the alkali metal to the other metal is 0.005 to 30, preferably 0.02 to 20.

In the method of the present invention, the catalyst prepared as described above can produce a halogenated hydrocarbon compound having 2 or more carbon atoms from halogenated methane as a raw material. For example, VCM and / or EDC or the like can be produced by using monochloromethane as a raw material. Similarly, monobromomethane,
If monoiodomethane or monofluoromethane is used as a raw material, a halogenated hydrocarbon compound having two or more carbon atoms in which chlorine atom is replaced with bromine, iodine or fluorine atom can be produced as a product in the case of monochloromethane.

In the present invention, the reaction is carried out in the gas phase. The reaction format is a known method, for example, fixed bed, fluidized bed,
Alternatively, use a moving bed. As the catalyst, a material having a required shape may be used depending on the reaction mode, and may be a powder, a pellet, or a spherically shaped material.

It is difficult to unconditionally set the reaction conditions because optimum reaction conditions differ depending on the catalyst, but the reaction temperature is 450 ° C to 800 ° C, preferably 500 ° C to 7 ° C.
50 ° C is good. The reaction pressure is from atmospheric pressure to 30 atm, preferably from atmospheric pressure to 10 atm. The reaction time can be represented by the catalyst weight (W / F; g · min / ml) with respect to the flow rate of the raw material gas, and W / F is 0.001 to 10, preferably 0.005 to 5.

[0019]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the loading rates are shown as metal weight%.

Example 1 2.685 g of potassium nitrate, manganese nitrate hexahydrate
Dissolve 194 g in 20 ml of water and add 50
10 g of silica (manufactured by Fuji Devison Co., Ltd .; trade name Carract-15) calcined at 0 ° C. was added. After drying under reduced pressure at 60 ℃, calcination at 775 ℃ under air flow gives 8.5% K.
Was obtained -5.0% Mn / SiO ₂ catalyst (catalyst A). 1.0 g of this catalyst was packed in a fixed-pressure fixed-bed flow reactor, and monochloromethane, oxygen, and helium were respectively added therein at 10 ml, 3.5 ml, and 16.5 ml per minute, for a total of 30 m per minute.
It was supplied at a flow rate of 1 l. When the product was analyzed by gas chromatography, the product shown in Table 1 was obtained. The product was identified by GC-MS (QP-1000 manufactured by Shimadzu Corporation).
S) was used.

Examples 2 to 11 In the same manner as in Example 1, alkali metal nitrate,
Catalysts B to K having the following compositions were prepared using iron, cobalt, nickel, lead, copper, and manganese nitrates as the other metal compound, and the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.

Catalyst B 8.5% K-5.1% Fe / SiO ₂ Catalyst C 8.5% K-5.4% Co / SiO ₂ Catalyst D 8.5% K-5.3% Ni / SiO ₂ Catalyst E 8.5% K-18.9% Pb / MgO Catalyst F 8.5% K-5.8% Cu / SiO ₂ Catalyst G 8.5% K-5.0% Mn / Al ₂ O ₃ Catalyst H 1.5% Li-5.0% Mn / SiO ₂ catalyst I 5.0% Na-5.0% Mn / SiO ₂ catalyst J 4.0% K-5.0% Mn / SiO ₂ catalyst K 28.7% Cs-5.0% Mn / SiO _{2 In} addition, the magnesia carrier was made by Kanto Kagaku Co., Ltd. reagent grade magnesium oxide, and the alumina carrier was made by Sumitomo Chemical Co., Ltd., trade name. KHA-24 was used.

Comparative Example 1 The reaction and the analysis of the product were performed in exactly the same manner as in Example 1 except that no catalyst was used. The results are shown in Table 1.

[0024]

[Table 1]

[0025]

Industrial Applicability According to the present invention, a halogenated hydrocarbon compound having two or more carbon atoms can be produced from halogenated methane in a single step, which is extremely significant from an industrial viewpoint.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B01J 23/74 311 X 8017-4G 321 X 8017-4G C07C 17/26 19/045 9280-4H / / C07B 61/00 300

Claims (2)

[Claims] 1. An alkali metal compound as a catalyst and a periodic table I when producing a halogenated hydrocarbon compound having two or more carbon atoms by reacting a halogenated methane with oxygen.
Group b, Group IIb, Group Vb, Group VIb, Group VIIb, VI
A method for producing a halogenated hydrocarbon compound, which comprises using a compound of a metal selected from Group II, Group IIIa, Group IVa, and Group Va. 2. The process according to claim 1, wherein the halogenated methane is monochloromethane and the halogenated hydrocarbon compound is vinyl chloride and / or 1,2-dichloroethane.